JP2018145536A - Spun-bonded non-woven fabric - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a spun-bonded polypropylene non-woven fabric without impairment to flexibility and with fuzzing reduced.SOLUTION: A spun-bonded non-woven fabric comprises 50 mass% or more and 100 mass% or less of a propylene resin fiber having a fiber diameter of 0.5 denier or more and 1.5 denier or less, the fabric having an emboss area occupancy of 5% or more and 25% or less.SELECTED DRAWING: None

Description

  The present invention relates to a polypropylene-based spunbonded nonwoven fabric.

  In recent years, polyolefin fibers and non-woven fabrics have been used in various applications such as disposable diapers, sanitary products, sanitary products, clothing materials, bandages, and packaging materials. The fibers and non-woven fabrics are often used in applications that come into direct contact with the body, and the required performance regarding a good wearing feeling and a feeling of touch on the body has been further increased in recent years. For this reason, regarding non-woven fabrics, there has been a demand for technological development related to improvement of texture for a good wearing feeling and thinning for product weight reduction.

  For example, Patent Document 1 discloses a technique for thinning fibers constituting a nonwoven fabric while maintaining spinning stability. Patent Document 2 discloses a non-woven fabric made of crimped fibers that are highly stretchable and have strong crimpability.

  However, a polypropylene-based spunbonded nonwoven fabric formed using thinned fibers or crimped fibers is excellent in flexibility but has a problem of fluffing.

International Publication No. 2014/119687 International Publication No. 2015/141750

  The problem to be solved by the present invention is to provide a polypropylene-based spunbonded nonwoven fabric which does not impair flexibility and has less fuzz.

The present disclosure relates to the following.
<1> A spunbonded nonwoven fabric comprising 50% by mass to 100% by mass of propylene resin fibers having a fineness of 0.5 denier or more and 1.5 denier or less, and an embossed area occupancy of 5% or more and 25% or less.
<2> The propylene resin component contained in the propylene resin fiber is a propylene resin (A) having an initial elastic modulus of 500 MPa or more and 2,000 MPa or less, and a propylene resin (B) having an initial elastic modulus of 1 MPa or more and less than 500 MPa. The spunbonded nonwoven fabric according to the above <1>.
<3> The content of the propylene resin (B) is 1% by mass or more and 30% by mass or less with respect to 100% by mass of the total amount of the propylene resin (A) and the propylene resin (B). The spunbonded nonwoven fabric as described in <2> above.
<4> According to ISO 1133: 1997, the MFR of the propylene-based resin (A) measured under conditions of a temperature of 230 ° C. and a load of 21.18 N is 5 g / 10 min or more and 100 g / 10 min or less, The spunbonded nonwoven fabric according to 2> or <3>.
<5> The spunbonded nonwoven fabric according to any one of the above <2> to <4>, wherein the melting endotherm (ΔH-D) of the propylene-based resin (B) is 0 J / g or more and 80 J / g or less. .
<6> The spunbonded nonwoven fabric according to any one of <2> to <5>, wherein the propylene-based resin (B) is a propylene homopolymer.
<7> The spunbonded nonwoven fabric according to any one of <2> to <6>, wherein the propylene-based resin (B) has a mesopentad fraction [mmmm] of 20 mol% to 60 mol%.
<8> The above <2>, wherein the propylene-based resin (B) contains at least one structural unit selected from the group consisting of ethylene and an α-olefin having 4 to 30 carbon atoms, exceeding 0 mol% and not more than 20 mol%. The spunbonded nonwoven fabric according to any one of to <5>.
<9> The spunbond nonwoven fabric according to any one of <1> to <8>, wherein the number of crimps of the spunbond nonwoven fabric is 6 pieces / 25 mm or less.
<10> The spunbonded nonwoven fabric according to any one of <1> to <9>, which is a single layer.
<11> The spunbonded nonwoven fabric according to any one of <1> to <9>, which is a multilayer.
<12> A fiber product comprising the spunbonded nonwoven fabric according to any one of <1> to <9> in the outermost layer.

  The polypropylene-based spunbonded nonwoven fabric of the present invention does not impair flexibility and has less fuzz.

  Hereinafter, the present invention will be described in detail. In this specification, the term “A to B” relating to the description of numerical values means “A or more and B or less” (when A <B) or “A or less and B or more” (when A> B). . Moreover, in this invention, the combination of a preferable aspect is a more preferable aspect.

  The spunbonded nonwoven fabric of the present invention contains 50% by mass to 100% by mass of propylene resin fibers having a fiber diameter of 0.5 denier or more and 1.5 denier or less, and has an embossed area occupation ratio of 5% or more and 25% or less. is there.

  The propylene resin fiber contained in the spunbond nonwoven fabric of the present invention contains a propylene resin component. The content of the propylene resin component in the propylene resin fiber is preferably 80% by mass or more, more preferably 90% by mass or more, and still more preferably 95% by mass or more with respect to 100% by mass of the total composition of the propylene resin fiber. It is.

  The propylene-based resin fiber can contain any additive in addition to the propylene-based resin component as long as the effects of the present invention are not impaired. Specific examples of additives include foaming agents, crystal nucleating agents, anti-glare stabilizers, UV absorbers, light stabilizers, heat stabilizers, antistatic agents, mold release agents, flame retardants, synthetic oils, waxes, electrical properties Improver, anti-slip agent, anti-blocking agent, viscosity modifier, anti-coloring agent, anti-fogging agent, lubricant, pigment, dye, plasticizer, softener, anti-aging agent, hydrochloric acid absorbent, chlorine scavenger, antioxidant And anti-adhesive agents.

  The propylene resin component includes a propylene resin (A) having an initial elastic modulus of 500 MPa to 2,000 MPa and a propylene resin (B) having an initial elastic modulus of 1 MPa to less than 500 MPa from the viewpoint of fiber spinning stability and thinning. ) Is preferably included.

(Propylene resin (A))
The propylene resin (A) may be a propylene homopolymer or a copolymer. In the case of a copolymer, the copolymerization ratio of propylene units exceeds 50 mol%, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol%. That's it. The copolymerizable monomer is at least one selected from the group consisting of ethylene and an α-olefin having 4 to 30 carbon atoms. Specific examples include ethylene, 1-butene, 1-pentene, 1-hexene, Examples include 1-octene and 1-decene.
When the propylene resin (A) is a copolymer, the propylene resin (A) contains 0 mol% of at least one structural unit selected from the group consisting of ethylene and an α-olefin having 4 to 30 carbon atoms. It is preferable to contain more than 20 mol%.

  From the viewpoint of spinning stability, the initial elastic modulus of the propylene-based resin (A) is preferably 500 MPa or more, more preferably 600 MPa or more, still more preferably 700 MPa or more, and preferably 2,000 MPa or less, more preferably It is 1,800 MPa or less.

In addition, the initial elastic modulus in this specification is measured with the following measuring methods.
<Measurement method of initial elastic modulus>
A press sheet having a thickness of 1 mm was prepared. From the obtained press sheet, a test piece according to JIS K7113 (2002) -2 No. 1/2 was sampled. Using a tensile tester (manufactured by Shimadzu Corp., “Autograph AG-I”), set the initial length L0 to 40 mm, stretch at a pulling speed of 100 mm / min, and measure strain and load during the stretching process. The initial elastic modulus was calculated from the following formula.
Initial elastic modulus (N) = 5% strain load (N) /0.05

  The melt flow rate (MFR) of the propylene-based resin (A) is preferably 5 g / 10 min or more, more preferably 7 g / 10 min or more, further preferably 10 g / 10 min or more, from the viewpoint of fiber spinning stability. Yes, and preferably 100 g / 10 min or less, more preferably 80 g / 10 min or less, and even more preferably 50 g / 10 min or less. In the present invention, the MFR of the propylene-based resin (A) is measured under conditions of a temperature of 230 ° C. and a load of 21.18 N in accordance with ISO 1133: 1997.

Commercially available products of the propylene resin (A) include “NOVATEC ^™ PP” series (eg “NOVATEC SA03”) (manufactured by Nippon Polypro Co., Ltd.), “ExxonMobil ^™ polypropylene” series (eg “PP3155”) (ExxonMobil Chemical Company) Product), “Prime Polypro ^™ ” series (for example, “Y2000GP”) (manufactured by Prime Polymer Co., Ltd.) and the like can be used.

  The content of the propylene-based resin (A) in the propylene-based resin component is 100% by mass of the total amount of the propylene-based resin (A) and the propylene-based resin (B) from the viewpoint of fiber spinning stability and thinning. On the other hand, it is preferably 70% by mass or more, more preferably 75% by mass or more, further preferably 80% by mass or more, and preferably 99% by mass or less, more preferably 95% by mass or less, still more preferably 90% by mass. % Or less.

(Propylene resin (B))
The propylene-based resin (B) may be a propylene homopolymer or a copolymer. In the case of a copolymer, the copolymerization ratio of propylene units exceeds 50 mol%, preferably 60 mol% or more, more preferably 70 mol% or more, still more preferably 90 mol% or more, still more preferably 95 mol%. That's it. The copolymerizable monomer is at least one selected from the group consisting of ethylene and an α-olefin having 4 to 30 carbon atoms. Specific examples include ethylene, 1-butene, 1-pentene, 1-hexene, Examples include 1-octene and 1-decene.
When the propylene-based resin (B) is a copolymer, the propylene-based resin (B) contains 0 mol% of at least one structural unit selected from the group consisting of ethylene and an α-olefin having 4 to 30 carbon atoms. It is preferable to contain more than 20 mol%.

  The initial elastic modulus of the propylene-based resin (B) is preferably 5 MPa or more, more preferably 10 MPa or more, still more preferably 20 MPa or more, and preferably less than 500 MPa, more preferably 400 MPa, from the viewpoint of the flexibility of the nonwoven fabric. Hereinafter, it is more preferably 300 MPa or less.

The propylene-based resin (B) preferably satisfies at least one of the following (1) and (2), and more preferably satisfies at least one of the following (3) to (6). In addition, these can be adjusted with selection of the catalyst at the time of manufacturing propylene-type resin (B), and reaction conditions.
(1) The melting endotherm (ΔHD) is 0 J / g or more and 80 J / g or less.
(2) Mesopentad fraction [mmmm] is 20 mol% or more and 60 mol% or less.
(3) Mesotriad fraction [mm] is 20 mol% or more and 95 mol% or less.
(4) The weight average molecular weight (Mw) is 30,000 or more and 200,000 or less.
(5) The molecular weight distribution (Mw / Mn) is less than 3.0.
(6) The melting point (Tm-D) measured by a differential scanning calorimeter (DSC) is 0 ° C. or higher and 120 ° C. or lower.

(1) Melting endotherm (ΔH-D)
The melting endotherm (ΔHD) of the propylene-based resin (B) is preferably 0 J / g or more, more preferably 5 J / g or more, from the viewpoint of fiber spinning stability and nonwoven fabric flexibility and smoothness. It is preferably 10 J / g or more, and preferably 80 J / g or less, more preferably 60 J / g or less, and still more preferably 50 J / g or less.
In the present invention, the melting endotherm (ΔH-D) is determined by using a differential scanning calorimeter (DSC), holding the sample at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then increasing the temperature at 10 ° C./min. Obtain the area surrounded by the line containing the peak of the melting endotherm curve obtained by this, the line on the low temperature side without any change in calorie, and the line on the high temperature side without any change in calorie (referred to as the base line) Is calculated by

(2) Mesopentad fraction [mmmm]
The mesopentad fraction [mmmm] of the propylene-based resin (B) is preferably 20 mol% or more, more preferably 25 mol% or more, still more preferably 30 mol% or more, from the viewpoint of fiber spinning stability. , Preferably 60 mol% or less, more preferably 58 mol% or less, and still more preferably 55 mol% or less.

(3) Mesotriad fraction [mm]
The mesotriad fraction [mm] of the propylene-based resin (B) is preferably 20 mol% or more, more preferably 30 mol% or more, still more preferably 40 mol% or more, from the viewpoint of fiber spinning stability. Preferably, it is 95 mol% or less, More preferably, it is 80 mol% or less, More preferably, it is 65 mol% or less.

In the present invention, mesopentad fraction [mmmm], TA Zanberi (A.Zambelli) or the like by "Macromolecules, 6, 925 (1973)" complies with the method proposed in, the ¹³ C-NMR spectrum of methyl It is the meso fraction in pentad unit in the polypropylene molecular chain measured by the signal. As the mesopentad fraction [mmmm] increases, the stereoregularity increases. The mesotriad fraction [mm] is also calculated by the above method.

In the present invention, the ¹³ C-NMR spectrum was measured using the following apparatus and conditions. 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

<Calculation 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

(4) Weight average molecular weight (Mw)
The weight average molecular weight (Mw) of the propylene-based resin (B) is preferably 30,000 or more, more preferably 50,000 or more, further preferably 70,000 or more, from the viewpoint of fiber spinning stability. , Preferably 200,000 or less, more preferably 180,000 or less, and still more preferably 150,000 or less.

(5) Molecular weight distribution (Mw / Mn)
The molecular weight distribution (Mw / Mn) of the propylene-based resin (B) is preferably less than 3.0, more preferably 2.5 or less, and still more preferably 2.3 or less. When the molecular weight distribution of the propylene-based resin (B) is within the above range, the occurrence of stickiness in the fiber obtained by spinning is suppressed.

Said weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) are calculated | required by a gel permeation chromatography (GPC) measurement. The weight average molecular weight is a polystyrene equivalent weight average molecular weight measured with the following apparatus and conditions, and the molecular weight distribution is a value calculated from the number average molecular weight (Mn) measured in the same manner and the above weight average molecular weight.
<GPC measurement device>
Column: “TOSO GMHHR-H (S) HT” manufactured by Tosoh Corporation
Detector: RI detection for liquid chromatogram "WATERS 150C" manufactured by Waters Corporation
<Measurement conditions>
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)

(6) Melting point (Tm-D)
The melting point (Tm-D) of the propylene resin (B) is preferably 0 ° C. or higher, more preferably 30 ° C. or higher, still more preferably 60 ° C. or higher, from the viewpoint of fiber spinning stability, and preferably It is 120 degrees C or less, More preferably, it is 100 degrees C or less.
The melting point (Tm-D) of the propylene-based resin (B) in the present invention is increased at 10 ° C./min after being held at −10 ° C. for 5 minutes in a nitrogen atmosphere using a differential scanning calorimeter (DSC). It is defined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by heating.

(Producing method of propylene resin (B))
The propylene-based resin (B) can be produced using, for example, a metallocene-based catalyst as described in International Publication No. 2003/087172. In particular, those using a transition metal compound in which a ligand forms a cross-linked structure via a cross-linking group are preferred, and in particular, a transition metal compound that forms a cross-linked structure via two cross-linking groups and Metallocene catalysts obtained by combining promoters are preferred.

For example,
(I) 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 a substituted heterocyclopentadienyl group, an amide group, a phosphide group, a hydrocarbon group, and a silicon-containing group, which forms a cross-linked structure through A ¹ and A ² They may be the same or different from each other, X represents a sigma-binding ligand, and when there are a plurality of X, the plurality of X may be the same or different, and other X, E ¹ , It may be cross-linked with 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, and 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 as or different from each other. q represents an integer of 1 to 5 and represents [(M valence) -2], and r represents an integer of 0 to 3. ]
And (ii) (ii-1) a compound capable of reacting with the transition metal compound of component (i) or a derivative thereof to form an ionic complex, and (ii-2) aluminoxane And a polymerization catalyst containing at least one component selected from the group consisting of:

  As the transition metal compound (i), a ligand is preferably a (1,2 ′) (2,1 ′) double-bridged transition metal compound, such as (1,2′-dimethylsilylene) ( 2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride.

  Specific examples of the compound of component (ii-1) include triethylammonium tetraphenylborate, tri-n-butylammonium tetraphenylborate, trimethylammonium tetraphenylborate, tetraethylammonium tetraphenylborate, methyl tetraphenylborate (tri- n-butyl) ammonium, benzyl tetraphenylborate (tri-n-butyl) ammonium, dimethyldiphenylammonium tetraphenylborate, triphenyl (methyl) ammonium tetraphenylborate, trimethylanilinium tetraphenylborate, methylpyridinium tetraphenylborate, tetra Benzylpyridinium phenylborate, methyl tetraphenylborate (2-cyanopyridinium), trikis (tetrafluorophenyl) borate triethyla Monium, tetrakis (pentafluorophenyl) tri-n-butylammonium borate, tetrakis (pentafluorophenyl) triphenylammonium borate, tetrakis (pentafluorophenyl) tetra-n-butylammonium borate, tetraethylammonium tetrakis (pentafluorophenyl) borate Benzyl tetrakis (pentafluorophenyl) ammonium borate (tri-n-butyl), methyldiphenylammonium tetrakis (pentafluorophenyl) borate, triphenyl (methyl) ammonium tetrakis (pentafluorophenyl) borate, tetrakis (pentafluorophenyl) boric acid Methylanilinium, tetrakis (pentafluorophenyl) borate dimethylanilinium, tetrakis (pentafluoropheny L) Trimethylanilinium borate, methyl pyridinium tetrakis (pentafluorophenyl) borate, benzyl pyridinium tetrakis (pentafluorophenyl) borate, methyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), benzyl tetrakis (pentafluorophenyl) borate (2-cyanopyridinium), methyl tetrakis (pentafluorophenyl) borate (4-cyanopyridinium), triphenylphosphonium tetrakis (pentafluorophenyl) borate, tetrakis [bis (3,5-ditrifluoromethyl) phenyl] dimethylaniline borate Ferrocenium tetraphenylborate, silver tetraphenylborate, trityl tetraphenylborate, tetraphenylporphyrin manganese tetraphenylborate, Trakis (pentafluorophenyl) borate ferrocenium, tetrakis (pentafluorophenyl) borate (1,1′-dimethylferrocenium), tetrakis (pentafluorophenyl) decamethylferrocenium borate, tetrakis (pentafluorophenyl) silver borate, Tetrakis (pentafluorophenyl) triborate borate, tetrakis (pentafluorophenyl) lithium borate, tetrakis (pentafluorophenyl) sodium borate, tetrakis (pentafluorophenyl) borate tetraphenylporphyrin manganese, silver tetrafluoroborate, silver hexafluorophosphate, hexa Examples thereof include silver fluoroarsenate, silver perchlorate, silver trifluoroacetate, and silver trifluoromethanesulfonate.

  Examples of the aluminoxane as the component (ii-2) include known chain aluminoxanes and cyclic aluminoxanes.

  Also, trimethylaluminum, triethylaluminum, triisopropylaluminum, triisobutylaluminum, dimethylaluminum chloride, diethylaluminum chloride, methylaluminum dichloride, ethylaluminum dichloride, dimethylaluminum fluoride, diisobutylaluminum hydride, diethylaluminum hydride, ethylaluminum sesquichloride, etc. The organoaluminum compound may be used in combination to produce the propylene-based resin (B).

  The content of the propylene-based resin (B) in the propylene-based resin component is preferably 100% by mass of the total amount of the propylene-based resin (A) and the propylene-based resin (B) from the viewpoint of fiber flexibility. It is 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, and preferably 30% by mass or less, more preferably 25% by mass or less, and further preferably 20% by mass or less.

  The fineness of the propylene-based resin fiber is preferably 0.5 denier or more, more preferably 0.6 denier or more, and preferably 1.5 denier or less, from the viewpoint of the balance of the texture, flexibility and strength of the nonwoven fabric. More preferably, it is 1.4 denier or less. The fineness of the propylene-based resin fiber is calculated by the measurement method shown below. As described above, the spunbonded nonwoven fabric of the present invention is small in fineness and excellent in spinning stability even under molding conditions where yarn breakage tends to occur.

[Fineness measurement]
Observe the fibers in the nonwoven fabric using a polarizing microscope, measure the average value (d) of 100 randomly selected fiber diameters, and use the resin density (ρ = 900,000 g / m ³ ) to fabricate the nonwoven fabric. Calculate the fineness of the sample from the following formula.
Fineness (denier) = ρ × π × (d / 2) ² × 9000

  The content of the propylene-based resin fiber in the spunbonded nonwoven fabric of the present invention is 50% by mass or more, preferably 60% by mass with respect to 100% by mass of the spunbonded nonwoven fabric, from the viewpoint of improving the flexibility of the nonwoven fabric and suppressing fuzz. As mentioned above, More preferably, it is 75 mass% or more, and an upper limit is 100 mass%.

The spunbonded nonwoven fabric of the present invention is preferably not crimped from the viewpoint of suppressing fuzz. The number of crimps (unit: piece / 25 mm) of the spunbonded nonwoven fabric of the present invention is preferably 10 or less, more preferably 6 or less, still more preferably 5 or less, and even more preferably 3 or less.
The number of crimps of the nonwoven fabric is measured using a crimp elastic modulus measuring device in accordance with JIS L1015: 2010. One fiber was extracted from the line sample before embossing so that the fiber was not elastic, and the length was measured when an initial load of 0.18 mN / tex was applied to a 25 mm sample. The number was counted, and the number of crimps per 25 mm was obtained. It shows that it is a nonwoven fabric with high crimpability, so that there are many crimp numbers.

  The embossed area occupation ratio of the spunbonded nonwoven fabric of the present invention is 5% or more, preferably 7% or more from the viewpoint of suppressing fuzzing, and 25% or less, preferably 20% from the viewpoint of fiber flexibility. It is as follows. Here, the “embossed area occupation ratio” indicates an occupation ratio of the embossed pattern area per unit area. In the present invention, the embossed area occupancy is measured by observing the nonwoven fabric surface with an electron microscope.

[Multilayer nonwoven fabric]
The spunbond nonwoven fabric of the present invention may be a multilayer nonwoven fabric formed by laminating two or more layers. In that case, from the viewpoint of the smoothness of the surface, it is preferable that at least one layer of the nonwoven fabric constituting the outer layer of the multilayer nonwoven fabric is a spunbond nonwoven fabric comprising the core-sheath composite fiber of the present invention.

[Fiber products]
Although it does not specifically limit as a fiber product using the spun bond 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 skin materials, soundproof materials, cushion materials, speaker dustproof materials, air cleaner materials, insulator skins, backing materials, adhesive nonwoven fabric sheets, door trims and other automotive parts, copying machine cleaning Various cleaning materials such as wood, carpet surface and backing materials, agricultural distribution, wood drain Shoes for members, bag for members such as sports shoes skin, industrial sealing material, such as wiping material and sheets can be mentioned.

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

[DSC measurement]
Using a differential scanning calorimeter (Perkin Elmer, “DSC-7”), 10 mg of the sample was held at −10 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. It calculated | required as a melting endotherm ((DELTA) HD) from a melting endothermic curve. Moreover, melting | fusing point (Tm-D) was calculated | required from the peak top of the peak observed on the highest temperature side of the obtained melting endothermic curve.
The melting endotherm (ΔH-D) is a differential scanning calorimeter (manufactured by Perkin Elmer Co., Ltd.) with a line connecting a point on the low temperature side where there is no change in heat quantity and a point on the high temperature side where there is no change in heat quantity as the baseline. , “DSC-7”), and calculating the area surrounded by the line portion including the peak of the melting endothermic curve obtained by DSC measurement and the base line.

[Weight average molecular weight (Mw), molecular weight distribution (Mw / Mn) measurement]
The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured by gel permeation chromatography (GPC) method to determine the molecular weight distribution (Mw / Mn). For the measurement, the following equipment and conditions were used, and polystyrene-reduced weight average molecular weight and number average molecular weight were obtained. The molecular weight distribution (Mw / Mn) is a value calculated from these weight average molecular weight (Mw) and number average molecular weight (Mn).
<GPC measurement device>
Column: “TOSO GMHHR-H (S) HT” manufactured by Tosoh Corporation
Detector: RI detection for liquid chromatogram "WATERS 150C" manufactured by Waters Corporation
<Measurement conditions>
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 following apparatus and conditions. 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

<Calculation 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

The mesopentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic mesoracemi mesopentad fraction [rmrm] are described in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al. The meso fraction, the racemic fraction, and the racemic meso-racemic meso in the pentad unit in the polypropylene molecular chain measured by the methyl group signal in the ¹³ C-NMR spectrum were obtained according to the proposed method. It is a fraction. The triad fractions [mm], [rr] and [mr] were also calculated by the above method.

[Measurement method of initial elastic modulus]
A press sheet having a thickness of 1 mm was prepared. From the obtained press sheet, a test piece according to JIS K7113 (2002) -2 No. 1/2 was sampled. Using a tensile tester (manufactured by Shimadzu Corp., “Autograph AG-I”), set the initial length L0 to 40 mm, stretch at a pulling speed of 100 mm / min, and measure strain and load during the stretching process. The initial elastic modulus was calculated from the following formula.
Initial elastic modulus (N) = 5% strain load (N) /0.05

Production Example 1
(Production of propylene polymer (B1))
In a stainless steel reactor with an internal volume of 20 L equipped with a stirrer, 20 L / hr of n-heptane, 15 mmol / hr of triisobutylaluminum, dimethylanilinium tetrakispentafluorophenylborate, (1,2'-dimethylsilylene) The catalyst component obtained by contacting (2,1′-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride and triisobutylaluminum with propylene in a mass ratio of 1: 2: 20 in advance is converted into zirconium. At 6 μmol / hr.
Propylene and hydrogen were continuously supplied at a polymerization temperature of 65 ° C. so that the gas phase hydrogen concentration was 8 mol% and the total pressure in the reactor was maintained at 1.0 MPa · G. The propylene polymer (B1) was obtained by adding antioxidant to the obtained polymerization solution so that the content rate might become 1000 mass ppm, and then removing n-heptane which is a solvent.
The above-mentioned measurement was performed about the obtained propylene polymer (B1). The results are shown in Table 1.
Further, the MFR was measured for the propylene-based polymer (B1) in accordance with ISO 1133: 1997 under conditions of a temperature of 230 ° C. and a load of 21.18N. The MFR of the propylene polymer (B1) was 50 g / 10 minutes.

  In the following examples, the following raw materials were used.

Propylene homopolymer (A1):
"NOVATEC SA03" (manufactured by Nippon Polypro Co., Ltd.)
The propylene homopolymer (A1) measured by the above method had a melting point (Tm-D) of 160 ° C. and an initial elastic modulus of 1,650 MPa. The propylene homopolymer (A1) was measured for MFR under the conditions of a temperature of 230 ° C. and a load of 21.18 N in accordance with ISO 1133: 1997. The MFR of the propylene homopolymer (A1) was 30 g / 10 minutes.

Propylene homopolymer (A2):
“PP3155” (manufactured by ExxonMobil Chemical)
The propylene homopolymer (A2) measured by the above method had a melting point (Tm-D) of 161 ° C. and an initial elastic modulus of 1,550 MPa. The propylene homopolymer (A2) was measured for MFR under the conditions of a temperature of 230 ° C. and a load of 21.18 N in accordance with ISO 1133: 1997. The MFR of the propylene homopolymer (A1) was 36 g / 10 minutes.

Lubricant:
Slip agent masterbatch (lubricant masterbatch): a composition comprising 90% by mass of highly crystalline polypropylene “Y6005GM” (manufactured by Prime Polymer Co., Ltd.) and 10% by mass of erucamide.

Example 1
To a resin mixture consisting of 90% by mass of the propylene homopolymer (A1) and 10% by mass of the propylene polymer (B1), an amount of slip agent masterbatch that is 2000 ppm of erucamide on the basis of the resin mixture is added, A resin composition was prepared.
The resin composition was melt-extruded at a resin temperature of 240 ° C. using a single-screw extruder having a gear pump, and a single-hole discharge rate of 0.4 g / min from a nozzle having a nozzle diameter of 0.5 mm (hole number: 2675 holes). The molten resin was discharged and spun. While cooling the fiber obtained by spinning with a cooling air of 12.5 ° C., it is sucked under a nozzle with a pressure of 4.0 kg / cm ² by an ejector and is moved to a net surface moving at a line speed of 119 m / min. The fibers were laminated. The fiber bundle laminated on the net surface was embossed at a nip pressure of 40 N / mm with a calender roll heated to 135 ° C. and wound around a take-up roll.

Example 2
A resin composition comprising 85% by mass of a propylene homopolymer (A2) and 15% by mass of a propylene-based polymer (B1) was prepared.
The resin composition was melt-extruded at a resin temperature of 250 ° C. using a single-screw extruder having a gear pump, and a single-hole discharge rate of 0.57 g / min from a nozzle having a nozzle diameter of 0.6 mm (hole number: 5800 holes / m). The molten resin was discharged at a speed and spun. While cooling the fiber obtained by spinning with air, the fiber was laminated on the net surface moving at a line speed of 222 m / min by sucking under a nozzle at a cabin pressure of 6500 Pa under a nozzle. The fiber bundle laminated on the net surface was embossed at a nip pressure of 100 N / mm with a calender roll heated to 147 ° C. and wound around a take-up roll.

Comparative Example 1
In Example 1, a resin composition prepared by adding a slip agent master batch in an amount of 2000 ppm of erucamide to the propylene homopolymer (A1) on the basis of the polymer was used, and the ejector pressure was A spunbonded nonwoven fabric was produced in the same manner as in Example 1 except that the amount was changed to 1.0 kg / cm ² .

Comparative Example 2
In Example 1, a spunbonded nonwoven fabric was produced in the same manner as in Example 1 except that the ejector pressure was changed to 1.0 kg / cm ² .

Comparative Example 3
In Example 2, a spunbonded nonwoven fabric was produced in the same manner as in Example 2 except that the cabin pressure was changed to 4500 Pa.

  The nonwoven fabric obtained in each example was subjected to the following measurements and evaluations. The results are shown in Table 2.

[Embossed area occupancy]
The surface of the nonwoven fabric was observed with an electron microscope, and the embossed area occupancy was measured.

[Measurement of basis weight]
A mass of 20 cm × 20 cm of the obtained nonwoven fabric was measured, and a basis weight (gsm) was measured.

[Measurement of fineness]
Observe the fibers in the nonwoven fabric using a polarizing microscope, measure the average value (d) of 100 randomly selected fiber diameters, and use the resin density (ρ = 900,000 g / m ³ ) to fabricate the nonwoven fabric. The fineness of the sample was calculated from the following equation.
Fineness (denier) = ρ × π × (d / 2) ² × 9000

(Measurement of breaking strength and breaking strain)
From the obtained nonwoven fabric, a test piece having a length of 200 mm and a width of 50 mm was sampled in the machine direction (MD) and the direction perpendicular to the machine direction (CD). Using a tensile tester (manufactured by Shimadzu Corp., “Autograph AG-I”), set the initial length L0 to 100 mm, stretch at a pulling speed of 300 mm / min, and measure strain and load during the stretching process. The values of load and strain at the moment when the nonwoven fabric broke were taken as the breaking strength and breaking strain, respectively.

[Measurement of static friction coefficient]
From the obtained nonwoven fabric, test pieces having a length of 220 mm × width of 100 mm and length of 220 mm × width of 70 mm were sampled in the machine direction (MD) and the direction perpendicular to the machine direction (TD). Static friction coefficient measurement tester (Toyo Seiki Seisakusho Co., Ltd., "Friction measuring machine AN type") Put two non-woven fabrics on the base and place a 1,000g weight on it to set the inclination of the base. The angle was changed at a speed of 2.7 degrees / minute, and the angle when the nonwoven fabric slipped 10 mm was measured. The static friction coefficient was calculated from the weight (1,000 g) of the weight and the angle when the nonwoven fabric slipped 10 mm.
In addition, it shows that textures, such as a touch feeling of a nonwoven fabric, are so favorable that the value of a static friction coefficient is small.

[Cantilever test]
A test piece having a length of 100 mm and a width of 100 mm was prepared from the obtained non-woven fabric, and the test was performed using a cantilever testing machine having an inclined surface having an inclination angle of 45 ° C. at one end of the base. The test piece was slid on the pedestal in the slope direction at a constant speed, and the moving distance at the moment when the test piece was bent and one end touched the slope was measured. The measurement was made in the machine direction (MD) and the direction perpendicular to the machine direction (CD).

[Handometer test]
A 200 mm × 200 mm test piece is set on a 1/4 inch wide slit so as to be perpendicular to the slit, and the position of 67 mm (1/3 of the test piece width) from the side of the test piece is set with a penetrator blade. Pushed in 8 mm. The resistance value at this time was measured to evaluate the flexibility of the test piece. The feature of this measuring method is that the test piece slips slightly on the test table, and the combined force of the friction force generated thereby and the resistance force (flexibility) at the time of pushing is measured. It shows that the softness | flexibility of a nonwoven fabric is so favorable that the value of the resistance value obtained by the measurement is small.

[Fuzz resistance]
About the obtained nonwoven fabric, fluff was evaluated by the Martindale method described in JIS L1096: 2010 8.19.5E method.
Specifically, a Martindale type wear machine “NU-MARTINDALE 864230 / 110V HEA90” (manufactured by James H. Heal & Co. Ltd) is used as the apparatus, the load of the friction element is 9 kPa, and the measurement surface is for JIS dyeing fastness test. Cotton (based on JIS L0803) was used and installed so that the measurement surface of the cloth and the test piece could be rubbed.
After attaching the test piece, the measurement surface of the test piece and the cotton were moved and rubbed along the Lissajous curve for 120 seconds. The measurement surface of the test piece subjected to friction was observed, and the fluff resistance was evaluated by ranking according to the following criteria.
A: There is no fuzz.
B: Fluffy so that a small hairball starts to form in one place.
C: A clear hairball starts to be formed, and a plurality of small hairballs are seen.
D: The fibers are frayed as the specimen becomes thinner.
E: The fiber is peeled off as the specimen is broken.

  As can be seen from Table 2, the spunbonded nonwoven fabrics of Comparative Examples 1 to 3 whose fineness was outside the range of the present invention were all fluffed. On the other hand, the spunbond nonwoven fabric of the present invention does not impair flexibility and has less fuzz.

Claims (12)

  A spunbonded nonwoven fabric comprising 50% by mass to 100% by mass of propylene-based resin fibers having a fineness of 0.5 to 1.5 denier and an embossed area occupancy of 5% to 25%.   The propylene-based resin component contained in the propylene-based resin fiber includes a propylene-based resin (A) having an initial elastic modulus of 500 MPa to 2,000 MPa and a propylene-based resin (B) having an initial elastic modulus of 1 MPa to less than 500 MPa. Item 11. The spunbonded nonwoven fabric according to item 1.   The content of the propylene resin (B) is 1% by mass or more and 30% by mass or less with respect to 100% by mass of the total amount of the propylene resin (A) and the propylene resin (B). The spunbond nonwoven fabric described in 1.   The MFR of the propylene-based resin (A) measured under the conditions of a temperature of 230 ° C. and a load of 21.18 N in accordance with ISO 1133: 1997 is 5 g / 10 min or more and 100 g / 10 min or less. The spunbond nonwoven fabric described in 1.   The spunbonded nonwoven fabric according to any one of claims 2 to 4, wherein a melting endotherm (ΔH-D) of the propylene-based resin (B) is 0 J / g or more and 80 J / g or less.   The spunbonded nonwoven fabric according to any one of claims 2 to 5, wherein the propylene-based resin (B) is a propylene homopolymer.   The spunbonded nonwoven fabric according to any one of claims 2 to 6, wherein a mesopentad fraction [mmmm] of the propylene-based resin (B) is 20 mol% or more and 60 mol% or less.   Any of Claims 2-5 in which the said propylene-type resin (B) contains at least 1 structural unit chosen from the group which consists of ethylene and a C4-C30 alpha olefin more than 0 mol% and 20 mol% or less. 2. The spunbond nonwoven fabric according to item 1.   The spunbonded nonwoven fabric according to any one of claims 1 to 8, wherein the number of crimps of the spunbonded nonwoven fabric is 6 pieces / 25 mm or less.   The spunbonded nonwoven fabric according to any one of claims 1 to 9, which is a single layer.   The spunbonded nonwoven fabric according to any one of claims 1 to 9, which is a multilayer.   A textile product comprising the spunbonded nonwoven fabric according to any one of claims 1 to 9 as an outermost layer.