The present disclosure relates to non-woven fabric laminates, stretchable non-woven fabric laminates, textile products, absorbent articles and sanitary masks.
Background technology
[0002]
　In recent years, non-woven fabrics have been widely used in various applications because of their excellent breathability and flexibility. Therefore, the non-woven fabric is required to have various properties according to its use, and is also required to improve the properties.
[0003]
　For example, non-woven fabrics used for sanitary materials such as disposable diapers and sanitary napkins, and base cloths for poultices are required to have water resistance and excellent moisture permeability. It is also required to have elasticity and bulkiness depending on the place where it is used.
[0004]
　As one of the methods for imparting elasticity to the non-woven fabric, a method using a thermoplastic elastomer as a raw material for the spunbonded non-woven fabric (see, for example, JP-A-7-503502) and a method using low crystalline polypropylene (for example, special feature). Kai 2009-62667 (see Japanese Patent Application Laid-Open No. 2009-79341) and the like have been proposed.
[0005]
　Japanese Unexamined Patent Publication No. 2009-62667 and Japanese Unexamined Patent Publication No. 2009-79341 propose to add a highly crystalline polypropylene or a mold release agent to low crystalline polypropylene in order to improve the stickiness of the spunbonded non-woven fabric. ing. International Publication No. 2016/143833 discloses a laminate of a non-woven fabric containing low crystalline polypropylene and a mixed fiber spunbonded non-woven fabric of thermoplastic elastomer long fibers and thermoplastic resin long fibers.
Outline of the invention
Problems to be solved by the invention
[0006]
　In the methods described in JP-A-2009-62667 and JP-A-2009-79341, each rotating device in the apparatus, including an embossing step, occurs when a spunbonded non-woven fabric is produced using low crystalline polypropylene. In order to prevent adhesion to other parts that come into contact with the non-woven fabric, it is necessary to increase the amount of high-crystalline polypropylene or mold release agent added to the low-crystalline polypropylene, and as a result, the residual strain of the obtained spunbonded non-woven fabric is large. Therefore, the elasticity tends to be inferior. In the method described in International Publication No. 2016/143833, elasticity is maintained by laminating low crystalline polypropylene and stretchable spunbonded non-woven fabric, but further improvement in elasticity is strongly required. ..
[0007]
　In addition, for sanitary materials such as disposable diapers and sanitary napkins, and base cloths for compresses, it is required that the stress during elongation is small so that it can be worn with a weak force, and the stress during recovery is high so that it does not shift when worn. It is required to be large. That is, in the above application, not only the value of expansion / contraction characteristics (ratio of stress during elongation / stress during recovery) is reduced, but also the absolute value of stress during elongation is reduced and the absolute value of stress during recovery is increased. Is required.
[0008]
　Furthermore, in applications such as disposable diapers, sanitary materials such as sanitary napkins, and base cloths for poultices, the stress during recovery does not decrease in the range of room temperature (23 ° C) to body temperature (for example, the range of 23 ° C to 40 ° C). That is, it is required to have excellent stress maintenance. As a result, even if sanitary materials such as disposable diapers and sanitary napkins rise to body temperature when worn, they will not easily shift.
[0009]
　In view of the above problems, it is an object of the present disclosure to provide a non-woven fabric laminate having excellent stretchability and stress maintenance, and a stretchable non-woven fabric laminate using the same, a textile product, an absorbent article, and a sanitary mask. do.
Means to solve problems
[0010]
　Means for solving the above problems include the following embodiments.
<1> An elastic non-woven fabric containing an α-olefin copolymer having a ratio (E40 / E23) of a storage elastic modulus E40 at 40 ° C. and a storage elastic modulus E23 at 23 ° C. of 37% or more, and at least one side of the elastic non-woven fabric. The long fibers of the thermoplastic elastomer (A) and the long fibers of the thermoplastic resin (B) other than the thermoplastic elastomer (A), which are arranged on the side, are 10% by mass to 90% by mass: 90% by mass to 10%. A non-woven laminate having a mixed fiber spunbonded non-woven fabric contained in a proportion of% by mass (((A): (B), where (A) + (B) = 100% by mass))
<2> . The non-woven fabric laminate according to <1>, wherein the α-olefin copolymer has a storage elastic modulus E23 at 23 ° C. of 45 MPa or less.
<3> The α-olefin copolymer is a copolymer of ethylene and propylene. <1> or <2> according to <1> or <2>,
wherein the tensile elastic modulus of the α-olefin copolymer is 30 MPa or less, according to any one of <1> to <3>. The non-woven laminate according
to any one of <1> to <4>, wherein the α-olefin copolymer has a melting point of 145 ° C. or lower and a melting point of 145 ° C. or lower.
<6> The item according to any one of <1> to <5>, wherein the heat of fusion determined from the largest heat absorption peak of the differential scanning calorimeter (DSC) of the α-olefin copolymer is 29 mJ / mg or less. Non-woven laminate.
<7> The non-woven laminate according to any one of <1> to <6>, wherein the glass transition temperature of the α-olefin copolymer is −10 ° C. or lower.
<8> The non-woven fabric laminate according to any one of <1> to <7>, wherein the long fibers of the thermoplastic resin (B) have a maximum point elongation of 50% or more when made into a spunbonded non-woven fabric.
<9> The nonwoven fabric laminate according to any one of <1> to <8>, wherein the thermoplastic elastomer (A) is a thermoplastic polyurethane elastomer.
<10> The thermoplastic polyurethane elastomer has a solidification start temperature of 65 ° C. or higher measured by DSC, and is dimethylacetamide measured by a particle size distribution measuring device equipped with an aperture of 100 μm based on the pore electric resistance method. The non-woven laminate according to <9>, wherein the number of particles of the solvent-insoluble matter is 3 million / g or less.
<11> The nonwoven fabric laminate according to <9> or <10>, wherein the thermoplastic polyurethane elastomer is a thermoplastic polyurethane elastomer satisfying the following relational expression (I).
　　a / (a ​​+ b) ≤ 0.8 (I)
(In the formula, a represents the total amount of heat of fusion obtained from the endothermic peaks in the range of 90 ° C. to 140 ° C. measured by DSC, and b is DSC. Represents the total heat of fusion calculated from the endothermic peaks in the range of more than 140 ° C and 220 ° C or less measured by.)
<12> The thermoplastic resin (B) is a polyolefin <1> to <11. > The non-woven laminate according to any one of the items.
<13> The nonwoven fabric laminate according to any one of <1> to <11>, wherein the thermoplastic resin (B) is a propylene-based polymer.
<14> The nonwoven fabric laminate according to any one of <1> to <13>, wherein the thermoplastic resin (B) is composed of 99 to 80% by mass of a propylene-based polymer and 1 to 20% by mass of high-density polyethylene. ..
<15> A stretchable nonwoven fabric laminate obtained by stretching the nonwoven fabric laminate according to any one of <1> to <14>.
<16> A textile product containing the nonwoven fabric laminate according to any one of <1> to <14> or the stretchable nonwoven fabric laminate according to <15>.
<17> An absorbent article containing the nonwoven fabric laminate according to any one of <1> to <14> or the stretchable nonwoven fabric laminate according to <15>.
<18> A sanitary mask containing the nonwoven fabric laminate according to any one of <1> to <14> or the stretchable nonwoven fabric laminate according to <15>.
The invention's effect
[0011]
　According to the present disclosure, a non-woven fabric laminate having excellent stretchability and stress maintenance, and a stretchable non-woven fabric laminate using the same, a textile product, an absorbent article, and a sanitary mask are provided.
A brief description of the drawing
[0012]
FIG. 1 is a schematic view of a gear stretching device.
Mode for carrying out the invention
[0013]
　Hereinafter, embodiments for carrying out the present invention will be described in detail. However, the present invention is not limited to the following embodiments. In the following embodiments, the components (including element steps and the like) are not essential unless otherwise specified and clearly considered to be essential in principle. The same applies to the numerical values ​​and their ranges, and does not limit the present invention.
[0014]
　In the present specification, the term "process" is included in this term not only as an independent process but also as long as the purpose of the process is achieved even if it cannot be clearly distinguished from other processes. Further, the numerical range indicated by using "-" in the present specification indicates a range including the numerical values ​​before and after "-" as the minimum value and the maximum value, respectively. Further, in the present specification, the content of each component in the composition is the same when a plurality of substances corresponding to each component are present in the composition, unless otherwise specified. Means the total amount of.
[0015]

　The non-woven fabric laminate of the present disclosure contains an α-olefin copolymer in which the ratio (E40 / E23) of the storage elasticity E40 at 40 ° C. to the storage elasticity E23 at 23 ° C. is 37% or more. The elastic non-woven fabric, the long fibers of the thermoplastic elastomer (A) arranged on at least one side of the elastic non-woven fabric, and the long fibers of the thermoplastic resin (B) other than the thermoplastic elastomer (A) are 10% by mass. Mixed fiber spunbonded non-woven fabric contained in a ratio of ~ 90% by mass: 90% by mass to 10% by mass ((A): (B), where (A) + (B) = 100% by mass) , Simply referred to as "mixed fiber spunbonded non-woven fabric"). The non-woven fabric laminate may be composed of other layers.
[0016]
　The nonwoven fabric laminate according to the present disclosure contains an α-olefin copolymer as an elastic nonwoven fabric. Therefore, it is considered that a non-woven fabric laminate having excellent expansion and contraction characteristics and excellent stress maintenance can be obtained as compared with the case of using an elastic non-woven fabric containing no α-olefin copolymer, for example, an elastic non-woven fabric made of a polypropylene homopolymer. Be done.
　Further, the α-olefin copolymer has a storage elastic modulus E40 at 40 ° C. and a storage elastic modulus E23 at 23 ° C. (E40 / E23) of 37% or more. That is, even in a temperature change environment (for example, 40 ° C. to 23 ° C.), the decrease in elasticity of the elastic nonwoven fabric is likely to be suppressed. Therefore, it is considered that a non-woven fabric laminate having excellent stress maintenance can be obtained.
[0017]
　In the non-woven fabric laminate of the present disclosure, since the mixed-fiber spunbonded non-woven fabric is arranged on at least one side of the elastic non-woven fabric, the non-woven fabric laminate adheres to members of various rotating devices and the like in the apparatus used in the embossing process and the like. Can be prevented and the moldability is excellent. Further, since the spunbonded nonwoven fabric arranged on at least one side of the elastic nonwoven fabric is made of a specific mixed fiber, it is less sticky and has excellent elasticity, so that the elasticity of the elastic nonwoven fabric due to its excellent elasticity can be easily maintained.
[0018]
　The non-woven fabric laminate of the present disclosure preferably has a structure in which at least a mixed fiber spunbonded non-woven fabric is arranged on a surface on the side of contact with a rotating device attached to the non-woven fabric manufacturing apparatus. This makes it possible to avoid production troubles due to winding around rotating equipment and the like. More preferably, it has a structure in which the mixed fiber spunbonded non-woven fabric is arranged on both sides of the elastic non-woven fabric. As a result, it becomes possible to stably obtain a non-woven fabric laminate having excellent expansion and contraction characteristics and excellent stress maintenance.
[0019]
　The nonwoven fabric laminate of the present disclosure usually has a basis weight of 360 g / m 2 or less, preferably 240 g / m 2 or less, more preferably 150 g / m 2 or less, and further preferably 120 g / m 2 to 15 g. It is within the range of / m 2 . The basis weight can be measured by the method used in the examples described later.
[0020]
　The composition ratio (weighting ratio) of the elastic non-woven fabric and the mixed fiber spunbonded non-woven fabric can be appropriately determined according to various uses. Usually, the basis weight ratio (elastic non-woven fabric: mixed fiber spunbonded non-woven fabric) is in the range of 10:90 to 90:10, preferably in the range of 20:80 to 80:20, and more preferably 20: It is in the range of 80 to 50:50. When there are two or more elastic non-woven fabrics (or mixed fiber spunbonded non-woven fabrics), the basis weight of the elastic non-woven fabrics (or mixed fiber spunbonded non-woven fabrics) is a total of two or more.
[0021]
　The nonwoven fabric laminate of the present disclosure usually has a residual strain of 19.5% or less in at least one direction, preferably 19% or less. When the residual strain in at least one direction is 19% or less, the elasticity is good. The residual strain can be measured by the method used in the examples described later.
[0022]
　The non-woven fabric laminate of the present disclosure usually has a maximum load elongation of 50% or more in at least one direction, preferably 100% or more. The maximum load elongation can be measured by the method used in the examples described later.
[0023]
　The nonwoven fabric laminate of the present disclosure preferably has a stress at 50% elongation of 1.10 N / 50 mm or less, more preferably 1.05 N / 50 mm or less, and 1.00 N / 50 mm, when the basis weight is 65 g. It is more preferably 50 mm or less. Further, the stress at 50% recovery is preferably 0.30 N / 50 mm or more, more preferably 0.32 N / 50 mm or more, and further preferably 0.35 N / 50 mm or more. The 50% elongation stress and the 50% recovery stress are different from the stretch characteristics (50% elongation stress / 50% recovery stress) and change depending on the basis weight of the non-woven fabric laminate, and the larger the basis weight, the larger the stress. It tends to be.
[0024]
　The nonwoven fabric laminate of the present disclosure preferably has stretch characteristics (stress at 50% elongation / stress at 50% recovery) of 3.0 or less, more preferably 2.7 or less, and 2.6 or less. It is more preferable to have. The smaller the value, the better the elasticity property. The expansion and contraction characteristics can be measured by the method used in the examples described later.
[0025]

　The elastic nonwoven fabric constituting the non-woven fabric laminate of the present disclosure has an α- that has a storage elastic modulus E40 at 40 ° C. and a storage elastic modulus E23 at 23 ° C. (E40 / E23) of 37% or more, which will be described later. Contains olefin copolymer. From the viewpoint of effectively achieving the object of the present invention, the ratio (E40 / E23) of the storage elastic modulus E40 at 40 ° C. to the storage elastic modulus E23 at 23 ° C. in the elastic non-woven fabric is 37% or more. The proportion of the copolymer is preferably 60% by mass or more, more preferably 70% by mass or more, and further preferably 80% by mass or more. It is particularly preferably 100% by mass. As an α-olefin copolymer having a storage elastic modulus E40 at 40 ° C. and a storage elastic modulus E23 at 23 ° C. (E40 / E23) of 37% or more, Vistamaxx (trade name, manufactured by ExxonMobil Chemical Co., Ltd.) is used. Can be mentioned.
[0026]
　In the present disclosure, the elastic non-woven fabric refers to a non-woven fabric having a property of recovering by elasticity when stress is released after stretching.
[0027]
　The elastic nonwoven fabric can be produced by various known methods. Specific examples thereof include a spunbond method, a melt blow method, and a flash spinning method. Among the elastic non-woven fabrics, the spunbonded non-woven fabric obtained by the spunbond method or the melt-blow non-woven fabric obtained by the melt-blow method is preferable.
[0028]
　The elastic nonwoven fabric usually has a basis weight of 120 g / m 2 or less, preferably 80 g / m 2 or less, more preferably 50 g / m 2 or less, and further preferably 40 g / m 2 to 2 g / m 2 . It is in the range.
[0029]
　The fibers constituting the elastic nonwoven fabric usually have a fiber diameter of 50 μm or less, preferably 40 μm or less, and more preferably 35 μm or less.
[0030]
[Α-olefin copolymer in which the ratio (E40 / E23) of the storage elastic modulus E40 at 40 ° C. to the storage elastic modulus E23 at 23 ° C. is 37% or more] The
　elastic non-woven fabric has the storage elastic modulus E40 and 23 at 40 ° C. It contains an α-olefin copolymer (hereinafter, also referred to as an α-olefin copolymer) having a storage elastic modulus (E40 / E23) of 37% or more at ° C.
　The α-olefin copolymer represents a copolymer in which copolymerization components having two or more kinds of α-olefin skeletons are copolymerized.
　Examples of the copolymerizing component having an α-olefin skeleton include ethylene, propylene, 1-butene, 1-pentene, 3-methyl-1-butene, 4-methyl-1-pentene, 1-hexene, 1-octene, and the like. Examples thereof include α-olefins such as 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene.
　Among the above, the α-olefin copolymers are ethylene (hereinafter, also referred to as “C2”) and propylene (hereinafter, also referred to as “C2”) and propylene (hereinafter, also referred to as “C2”) and propylene (hereinafter, also referred to as “C2”) and propylene (hereinafter, also referred to as “C2”) from the viewpoint of making the non-woven fabric laminate more stress-free and more excellent in elasticity. It is preferable to contain a copolymer (also referred to as "C3").
[0031]
　The content of the structural unit derived from ethylene in the copolymer of ethylene and propylene (hereinafter, also simply referred to as “ethylene content”) is preferably 1% by mass to 50% by mass, and 5% by mass to 25%. It is more preferably 10% by mass to 20% by mass, more preferably 10% by mass to 20% by mass.
[0032]
　The α-olefin copolymer may be any of an alternating copolymer, a graft copolymer, a block copolymer and a random copolymer.
[0033]
　The ratio (E40 / E23) of the storage elastic modulus E40 at 40 ° C. and the storage elastic modulus E23 at 23 ° C. of the α-olefin copolymer is 37% or more from the viewpoint of obtaining a non-woven fabric laminate excellent in stress maintenance. be. The larger the value, the more preferably the ratio (E40 / E23) is, more preferably 40% or more, further preferably 45% or more, and particularly preferably 50% or more.
[0034]
　Examples of the method for setting the storage elastic modulus ratio E40 / E23 of the α-olefin copolymer in the above-mentioned specific range include a method in which the α-olefin copolymer is a copolymer of ethylene and propylene. Be done.
[0035]
　The storage elastic modulus E23 of the α-olefin copolymer at 23 ° C. is preferably 45 MPa or less, more preferably 35 MPa or less, and more preferably 25 MPa, from the viewpoint of making the nonwoven fabric laminate more excellent in elasticity. The following is more preferable.
　E40 / E23 is preferably 37% or more, more preferably 40% or more, further preferably 45% or more, and particularly preferably 50% or more.
[0036]
　Each storage elastic modulus of the α-olefin copolymer shall be a value measured by the following equipment and conditions.
　Temperature: 23 ° C or 40 ° C
　Equipment: RSA-III (manufactured by TI Instruments)
　Deformation mode: Tensile mode
　Temperature range: -20 ° C to 120 ° C
　Temperature rise rate: 2 ° C / min
　Deformation frequency: 10Hz
　initial Distortion: 0.1%
　Measured temperature sensation: 0.3 ° C
　Environment: Under N 2
[0037]
　The melting point of the α-olefin copolymer used in the elastic non-woven fabric of the present disclosure shall be raised at 10 ° C./min after being held at −100 ° C. for 5 minutes under a differential scanning calorimeter (DSC) using a differential scanning calorimeter (DSC). It is defined as the peak top of the peak observed on the hottest side of the melting endothermic curve obtained by. Specifically, using a differential scanning calorimeter (DSC-7, manufactured by PerkinElmer), 5 mg of the sample was held at -100 ° C for 5 minutes in a nitrogen atmosphere, and then the temperature was raised at 10 ° C / min. It can be obtained as the peak top of the peak observed on the highest temperature side of the obtained melt endothermic curve.
　The melting point of the α-olefin copolymer used in the elastic nonwoven fabric of the present disclosure is preferably 145 ° C. or lower, more preferably 130 ° C. or lower, still more preferably 115 ° C. or lower.
[0038]
　The heat of fusion of the α-olefin copolymer used in the elastic non-woven fabric of the present disclosure is kept at −100 ° C. for 5 minutes under a differential scanning calorimeter (DSC) and then heated at 10 ° C./min. It is defined as the amount of heat of fusion at the largest endothermic peak of the melted endothermic curve obtained. Specifically, using a differential scanning calorimeter (DSC-7, manufactured by PerkinElmer), 5 mg of the sample was held at -100 ° C for 5 minutes in a nitrogen atmosphere, and then the temperature was raised at 10 ° C / min. It can be obtained from the largest endothermic peak among the obtained melt endothermic curves.
　The heat of fusion of the α-olefin copolymer used in the elastic nonwoven fabric of the present disclosure is preferably 29 mJ / mg or less, more preferably 25 mJ / mg or less, still more preferably 20 mJ / mg or less.
[0039]
　The glass transition temperature of the α-olefin copolymer used in the elastic non-woven fabric of the present disclosure is raised at 10 ° C./min after being held at -100 ° C. for 5 minutes under a differential scanning calorimeter (DSC) using a differential scanning calorimeter (DSC). The baseline of the melting endothermic curve obtained by allowing is defined as the shifted temperature. Specifically, using a differential scanning calorimeter (DSC-7, manufactured by PerkinElmer), 5 mg of the sample was held at -100 ° C for 5 minutes in a nitrogen atmosphere, and then the temperature was raised at 10 ° C / min. The intersection of the baseline of the obtained melt heat absorption curve and the tangent at the inflection point can be obtained as the glass transition temperature.
[0040]
　The glass transition temperature of the α-olefin copolymer used in the elastic nonwoven fabric of the present disclosure is preferably −10 ° C. or lower, more preferably −20 ° C. or lower, still more preferably −25 ° C. or lower.
[0041]
　Density of the present disclosure is used in the elastic nonwoven α- olefin copolymer (ASTM D 1505) is, 0.850 g / cm 3 ~ 0.950 g / cm 3 preferably in the range of, 0.855 g / cm 3 ~ 0.900 g / cm 3 , more preferably in the range of, 0.860 g / cm 3 ~ 0.895 g / cm 3 and still more preferably in the range of.
　The density of the α-olefin copolymer is a value obtained by measuring according to the density gradient method of JIS K7112 (1999).
[0042]
　The tensile elastic modulus of the α-olefin copolymer used in the elastic nonwoven fabric of the present disclosure is preferably 30 MPa or less, more preferably 20 MPa or less, from the viewpoint of making the nonwoven fabric laminate more excellent in elasticity. It is preferably 15 MPa or less, and more preferably 15 MPa or less.
The tensile elastic modulus is a value obtained by measuring by a method conforming to JIS K7161 (2011 version).
[0043]
　The molecular weight distribution (Mw / Mn) of the α-olefin copolymer used in the elastic nonwoven fabric of the present disclosure is preferably in the range of 1.5 to 5.0. Mw / Mn is more preferably in the range of 1.5 to 4.5 in that fibers having good spinnability and particularly excellent fiber strength can be obtained.
[0044]
　The mass average molecular weight (Mw) and number average molecular weight (Mn) of the α-olefin copolymer used in the elastic non-woven fabric of the present disclosure are values ​​obtained by GPC (gel permeation chromatography) and are measured under the following conditions. It is the value that was calculated. The mass average molecular weight (Mw) is the mass average molecular weight in terms of polystyrene, and the molecular weight distribution (Mw / Mn) is a value calculated from the number average molecular weight (Mn) and the mass average molecular weight (Mw) measured in the same manner. ..

　Column: TOSO GMHHR-H (S) HT
　detector: RI detector for liquid chromatogram WATERS 150C
　Solvent: 1,2,4-trichlorobenzene
　Measurement temperature: 145 ° C.
　Flow velocity: 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)
[0045]
　The melt flow rate (MFR) of the α-olefin copolymer used in the elastic nonwoven fabric of the present disclosure is not particularly limited, but is preferably 1 g / 10 minutes to 100 g / 10 minutes, for example, 10 g / 10 minutes to 80 g. It is more preferably / 10 minutes, and even more preferably 15 g / 10 minutes to 70 g / 10 minutes.
[0046]
　The melt flow rate of the α-olefin copolymer used in the elastic nonwoven fabric of the present disclosure is measured under the conditions of ASTMD-1238, 230 ° C., and a load of 2160 g.
[0047]
　The α-olefin copolymer used in the elastic nonwoven fabric of the present disclosure may be a synthetic product or a commercially available product.
　When the α-olefin copolymer is a synthetic product, the α-olefin copolymer can be prepared by using a vapor phase method, a bulk method, or the like in the presence of a conventionally known catalyst such as a Cheegler-Natta catalyst or a metallocene catalyst. It can be prepared by polymerizing or copolymerizing by a conventionally known polymerization method such as a slurry method or a solution method.
　Examples of commercially available α-olefin copolymers include Vistamaxx series (manufactured by ExxonMobil Chemical Co., Ltd.) and the like.
[0048]
　The composition of the α-olefin copolymer can be adjusted by using a conventionally known method (for example, IR analysis, NMR analysis, trace analysis, etc.).
[0049]
　The ratio of the α-olefin copolymer to the total amount of the elastic nonwoven fabric is preferably 90% by mass or more and 100% by mass or less, and more preferably 98% by mass or more and 100% by mass or less.
[0050]
　The α-olefin copolymer used in the elastic non-woven fabric of the present disclosure has an antioxidant, a heat-resistant stabilizer, a weather-resistant stabilizer, an antioxidant, a slip agent, and an antifogging agent as optional components, as long as the object of the present invention is not impaired. It may contain various known additives such as agents, lubricants, dyes, pigments, natural oils, synthetic oils and waxes.
[0051]
　
　The mixed fiber spunbonded non-woven fabric constituting the non-woven fabric laminate of the present disclosure contains long fibers of a thermoplastic elastomer (A) and long fibers of a thermoplastic resin (B) other than (A). It is a mixed fiber spunbonded non-woven fabric contained in a ratio of 10 to 90% by mass: 90 to 10% by mass (((A): (B), where (A) + (B) = 100% by mass)). ..
[0052]
　From the viewpoint of elasticity and flexibility, the proportion of the long fibers of the thermoplastic elastomer (A) in the mixed fiber spunbonded non-woven fabric is preferably 20% by mass or more, and more preferably 30% by mass or more. From the viewpoint of workability (stickiness resistance), the proportion of the long fibers of the thermoplastic elastomer (A) in the mixed fiber spunbonded non-woven fabric is preferably 70% by mass or less, and more preferably 60% by mass or less. preferable.
[0053]
　The fiber diameters (average values) of the long fibers of the thermoplastic elastomer (A) and the long fibers of the thermoplastic resin (B) forming the mixed fiber spunbonded non-woven fabric are usually 50 μm or less, preferably 40 μm or less, respectively. , More preferably 35 μm or less. The fiber diameters of the long fibers of the thermoplastic elastomer (A) and the long fibers of the thermoplastic resin (B) may be the same or different.
[0054]
　The mixed fiber spunbonded non-woven fabric has a total texture of 120 g / m 2 or less, preferably 80 g / m 2 or less, and more preferably 80 g / m 2 or less in total from the viewpoint of flexibility and breathability in sanitary material applications such as diapers. It is preferably 50 g / m 2 or less, and more preferably 40 g / m 2 to 15 g / m 2 .
[0055]
[Thermoplastic Elastomer (A)] As the
　thermoplastic elastomer (A), various known thermoplastic elastomers can be used, and one type may be used alone or two or more types of thermoplastic elastomers may be used in combination. good.
　Examples of the thermoplastic elastomer (A) include styrene-based elastomers, polyester-based elastomers, polyamide-based elastomers, thermoplastic polyurethane-based elastomers, polyolefin-based elastomers, vinyl chloride-based elastomers, and fluorine-based elastomers.
[0056]
　Styrene-based elastomers include polystyrene-polybutadiene-polystyrene block copolymers (SBS), polystyrene-polyisoprene-polystyrene block copolymers (SIS), their hydrogenating products, polystyrene-polyethylene-butylene-polystyrene block copolymers (SEBS), and polystyrene. -A polymer block represented by polyethylene-propylene-polystyrene block copolymer (SEPS), which is composed of at least one aromatic vinyl compound such as styrene, and at least one conjugated diene such as butadiene and isoprene. It is a block copolymer composed of a polymer block composed of a compound, a block copolymer composed of the compound, or a hydrogenated product thereof. Styrene-based elastomers include, for example, KRATON polymer (trade name, manufactured by Shell Chemical Co., Ltd.), SEPTON (trade name, manufactured by Kuraray Co., Ltd.), TUFTEC (trade name, manufactured by Asahi Kasei Kogyo Co., Ltd.), and Leostomer (trade name). , Made by Riken Technos Co., Ltd.).
[0057]
　The polyester-based elastomer is an elastomer typified by a block copolymer composed of a highly crystalline aromatic polyester and an amorphous aliphatic polyether. Polyester-based elastomers are sold under trade names such as HYTREL (trade name, manufactured by EI DuPont Co., Ltd.) and Perprene (trade name, manufactured by Toyobo Co., Ltd.).
[0058]
　Polyamide-based elastomers are elastomers typified by block copolymers composed of crystalline and high melting point polyamides and non-crystalline and low glass transition temperature (Tg) polyethers or polyesters. Polyamide-based elastomers are sold under trade names such as PEBAX (trade name, Atofina Japan Co., Ltd.).
[0059]
　The thermoplastic polyurethane-based elastomer is an elastomer typified by a block copolymer in which a hard segment is composed of polyurethane and a soft segment is composed of a polycarbonate-based polyol, an ether-based polyol, a caprolactone-based polyester, an adipate-based polyester, or the like.
[0060]
　The polyolefin-based elastomer is an elastomer composed of a single polymer such as an amorphous or low-crystalline ethylene / α-olefin random copolymer, a propylene / α-olefin random copolymer, and a propylene / ethylene / α-olefin random copolymer. Or, the amorphous or low crystalline random copolymer and the propylene homopolymer, the copolymer of propylene and a small amount of α-olefin, and the crystalline polyolefin such as high density polyethylene and medium density polyethylene. It is an elastomer that is a mixture. Examples of the polyolefin-based elastomer include TAFMER (trade name, manufactured by Mitsui Kagaku Co., Ltd.), Energy (trade name, manufactured by DuPont Dow Elastomers), which is an ethylene-octene copolymer, and CATALLOY (trade name, manufactured by DuPont Dow Elastomers). It is sold under product names such as Montel Co., Ltd. and Vistamaxx (product name, Exxon Mobile Chemical Co., Ltd.).
[0061]
　Vinyl chloride elastomers are sold under trade names such as Leonil (trade name, manufactured by Riken Technos Co., Ltd.) and Posmeal (trade name, manufactured by Shin-Etsu Polymer Co., Ltd.).
[0062]
　Among these thermoplastic elastomers, thermoplastic polyurethane elastomers and polyolefin elastomers are preferable, and thermoplastic polyurethane elastomers are more preferable from the viewpoint of elasticity and processability.
[0063]
(Thermoplastic Polyurethane Elastomer)
　Among the thermoplastic polyurethane elastomers, the thermoplastic polyurethane elastomer having a solidification start temperature of 65 ° C. or higher, preferably 75 ° C. or higher, and most preferably 85 ° C. or higher is preferable. The solidification start temperature is preferably 195 ° C. or lower. Here, the solidification start temperature is a value measured using a differential scanning calorimeter (DSC), and the thermoplastic polyurethane elastomer was heated to 230 ° C. at 10 ° C./min and held at 230 ° C. for 5 minutes. After that, it is the start temperature of the exothermic peak derived from the solidification of the thermoplastic polyurethane elastomer generated when the temperature is lowered at 10 ° C./min. When the solidification start temperature is 65 ° C. or higher, molding defects such as fusion of fibers, thread breakage, and resin lumps can be suppressed when a mixed fiber spunbonded non-woven fabric is obtained, and molding is performed during heat embossing. It is possible to prevent the mixed fiber spunbonded non-woven fabric from being wrapped around the embossing roller. In addition, the obtained mixed fiber spunbonded non-woven fabric is less sticky and is suitably used as a material that comes into contact with the skin, such as clothing, sanitary materials, and sports materials. On the other hand, by setting the solidification start temperature to 195 ° C. or lower, the molding processability can be improved. The solidification start temperature of the molded fiber tends to be higher than the solidification start temperature of the thermoplastic polyurethane elastomer used for this.
[0064]
　In order to adjust the solidification start temperature of the thermoplastic polyurethane elastomer to 65 ° C or higher, the polyol, isocyanate compound and chain extender used as raw materials for the thermoplastic polyurethane elastomer are selected to have the optimum chemical structure. At the same time, it is necessary to adjust the amount of hard segments. Here, the amount of hard segment is the mass obtained by dividing the total mass of the isocyanate compound and the chain extender used in the production of the thermoplastic polyurethane elastomer by the total amount of the polyol, the isocyanate compound and the chain extender and multiplying by 100. It is a percentage (mass%) value. The amount of the hard segment is preferably 20% by mass to 60% by mass, more preferably 22% by mass to 50% by mass, and further preferably 25% by mass to 48% by mass.
[0065]
　The thermoplastic polyurethane-based elastomer preferably has 3 million particles (3 million particles / g) or less, more preferably 2.5 million particles / g or less, based on 1 g of the thermoplastic polyurethane-based elastomer. Yes, more preferably 2 million pieces / g or less. Here, the polar solvent insoluble component in the thermoplastic polyurethane-based elastomer is mainly a lump such as fish eye or gel generated during the production of the thermoplastic polyurethane-based elastomer. Causes of generation of polar solvent insoluble components include components derived from hard segment aggregates of thermoplastic polyurethane elastomers, components in which hard segments and / or soft segments are crosslinked by allophanate bonds, bullet bonds, etc., thermoplastic polyurethanes. Examples thereof include raw materials constituting the elastomer and components generated by a chemical reaction between the raw materials.
[0066]
　The number of particles insoluble in the polar solvent was measured by attaching a 100 μm aperture to a particle size distribution measuring device using the pore electric resistance method to measure the insoluble content when the thermoplastic polyurethane elastomer was dissolved in the dimethylacetamide solvent. The value. When a 100 μm aperture is attached, the number of particles of 2 μm to 60 μm in terms of uncrosslinked polystyrene can be measured.
[0067]
　By reducing the number of particles insoluble in the polar solvent to 3 million / g or less, problems such as an increase in the distribution of fiber diameters and yarn breakage during spinning can occur within the solidification start temperature range of the thermoplastic polyurethane elastomer. It can be suppressed more. A thermoplastic polyurethane-based elastomer having a low content of insoluble in a polar solvent can be obtained by carrying out a polymerization reaction of a polyol, an isocyanate compound and a chain extender and then filtering.
[0068]
　From the viewpoint of suppressing the mixing of air bubbles into the strands and the occurrence of thread breakage in the molding of the non-woven fabric with a large spunbond molding machine, the moisture value of the thermoplastic polyurethane elastomer is preferably 350 ppm or less, preferably 300 ppm or less. More preferably, it is more preferably 150 ppm or less.
[0069]
　From the viewpoint of elasticity, the total amount of heat of fusion obtained from the endothermic peaks of the thermoplastic polyurethane-based elastomer in the range of 90 ° C. to 140 ° C. measured by a differential scanning calorimeter (DSC) (a). And the total amount of heat of fusion (b) obtained from the endothermic peak in the range of the peak temperature exceeding 140 ° C. and 220 ° C. or lower preferably satisfies the relationship of the following formula (I), and the following formula (II). It is more preferable to satisfy the relationship of the following formula (III), and it is further preferable to satisfy the relationship of the following formula (III).
[0070]
　a / (a ​​+ b) ≤0.8 (I)
　a / (a ​​+ b) ≤0.7 (II)
　a / (a ​​+ b) ≤0.55 (III)
　Here, "a / (a ​​+ b)" is a thermoplastic polyurethane. It means the heat-melting ratio (unit:%) of the hard domain of the system elastomer. When the heat-melting ratio of the hard domain of the thermoplastic polyurethane-based elastomer is 80% or less, the strength and elasticity of the fibers, particularly the fibers and the non-woven fabric in the mixed fiber spunbonded non-woven fabric are improved. In the present disclosure, the lower limit of the heat-melting ratio of the hard domain of the thermoplastic polyurethane elastomer is preferably about 0.1%.
[0071]
　The thermoplastic polyurethane elastomer preferably has a melt viscosity of 100 Pa · s to 3000 Pa · s, more preferably 200 Pa · s to 2000 Pa · s, and 1000 Pa · s under the conditions of a temperature of 200 ° C. and a shear rate of 100 sec -1. -It is more preferably s to 1500 Pa · s. Here, the melt viscosity is a value measured by a capillograph (manufactured by Toyo Seiki Co., Ltd., a nozzle length of 30 mm and a diameter of 1 mm is used).
[0072]
　A thermoplastic polyurethane-based elastomer having such properties can be obtained, for example, by the production method described in JP-A-2004-244791.
[0073]
　Since the mixed fiber spunbonded non-woven fabric molded using the thermoplastic polyurethane-based elastomer has an excellent tactile sensation, it can be suitably used for applications such as sanitary materials that come into contact with the skin. In addition, the filter installed inside the extruder for filtering impurities and the like is less likely to be clogged, and the frequency of equipment adjustment and maintenance is reduced, which is industrially preferable.
[0074]
(Polyolefin-based elastomer) Among the
　polyolefin-based elastomers, amorphous or low-crystalline polyolefin-based elastomers are preferable, and amorphous or low-crystalline ethylene and propylene, 1-butene, 1-pentene, 1-hexene, 4 Ethylene / α-olefin copolymer, which is a copolymer with one or more α-olefins having 3 to 20 carbon atoms such as -methyl-1-pentene, 1-hexene, 1-octene, 1-decene, etc. And amorphous or low crystalline propylene and ethylene, 1-butene, 1-pentene, 1-hexene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-decene, etc. have 2 carbon atoms. A propylene / α-olefin copolymer which is a copolymer with one or more kinds of α-olefins of to 20 (excluding 3 carbon atoms) is more preferable. The amorphous or low-crystalline polyolefin-based elastomer is, for example, a polyolefin-based elastomer having a crystallinity of 20% or less (including 0%) measured by X-ray diffraction.
[0075]
　Specific examples of the amorphous or low-crystalline ethylene / α-olefin copolymer include an ethylene / propylene random copolymer and an ethylene / 1-butene random copolymer. The melt flow rate (MFR) of the ethylene / α-olefin copolymer is not particularly limited as long as it has spinnability, but usually MFR (ASTM D1238 190 ° C., 2160 g load) is usually MFR (ASTM D1238 230 ° C., (2160 g load) is in the range of 1 g / 10 minutes to 1000 g / 10 minutes, preferably 5 g / 10 minutes to 500 g / 10 minutes, and more preferably 10 g / 10 minutes to 100 g / 10 minutes.
[0076]
　Specific examples of the amorphous or low-crystalline propylene / α-olefin copolymer include a propylene / ethylene random copolymer, a propylene / ethylene / 1-butene random copolymer, and a propylene / 1-butene random copolymer. Coalescence can be exemplified. The MFR of the propylene / α-olefin copolymer is not particularly limited as long as it has spinnability, but the MFR (ASTM D1238 230 ° C., 2160 g load) is usually 1 g / 10 min to 1000 g / 10 min, preferably 5 g / min. It is in the range of 10 minutes to 500 g / 10 minutes, more preferably 10 g / 10 minutes to 100 g / 10 minutes.
[0077]
　The polyolefin-based elastomer may be a single polymer of amorphous or low crystallinity, and is a propylene homopolymer or a copolymer of propylene and a small amount of α-olefin with respect to the amorphous or low crystalline polymer. , High-density polyethylene, medium-density polyethylene and other crystalline polyolefins may be mixed in an amount of about 1% by mass to 40% by mass.
[0078]
　Particularly preferable compositions as the polyolefin-based elastomer are isotactic polypropylene (i): 1% by mass to 40% by mass and propylene / ethylene / α-olefin copolymer (ii) (propylene in 45 mol% to 89 mol%). , A copolymer of 10 mol% to 25 mol% of ethylene and α-olefin having 4 to 20 carbon atoms, however, the copolymerization amount of α-olefin having 4 to 20 carbon atoms does not exceed 30 mol%. ): An elastomer composition comprising a polypropylene resin composition containing 60% by mass to 99% by mass.
[0079]
[Thermoplastic resin (B)] As the
　thermoplastic resin (B), various known thermoplastic resins other than the thermoplastic elastomer (A) can be used, and even if one type is used alone, two or more types can be used. A thermoplastic resin may be used in combination.
[0080]
　The thermoplastic resin (B) is a resin-like polymer different from the thermoplastic elastomer (A), and is usually a crystalline polymer having a melting point (Tm) of 100 ° C. or higher, or a glass transition temperature of 100 ° C. It is the above-mentioned amorphous polymer. As the thermoplastic resin (B), a crystalline thermoplastic resin is preferable.
[0081]
　Among the thermoplastic resins (B), when a spunbonded non-woven fabric obtained by a known production method is used, the maximum point elongation is 50% or more, preferably 70% or more, more preferably 100% or more, and elastic. A thermoplastic resin (extensible thermoplastic resin) having a property of having almost no recovery is preferable. The non-woven fabric laminate produced by using the mixed fiber spunbonded non-woven fabric obtained by mixing the long fibers of the thermoplastic resin (B) with the long fibers of the thermoplastic elastomer (A) has a bulky feeling due to the stretching process. It develops, improves the tactile sensation, and can impart a non-stretching function to the non-woven fabric laminate. The upper limit of the maximum point elongation of the spunbonded nonwoven fabric made of the thermoplastic resin (B) is not necessarily limited, but is usually 300% or less.
[0082]
　Specifically, the thermoplastic resin (B) is an α-olefin alone or a copolymer such as ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, and 1-octene. High-pressure method Low-density polyethylene, linear low-density polyethylene (so-called LLDPE), high-density polyethylene (so-called HDPE), polypropylene (propylene homopolymer), polypropylene random copolymer, poly1-butene, poly4-methyl-1- Polyethylene such as penten, ethylene / propylene random copolymer, ethylene / 1-butene random copolymer, propylene / 1-butene random copolymer, polyester (polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, etc.), polyamide ( Nylon-6, Nylon-66, Polymethaxylene adipamide, etc.), Polyvinyl chloride, Polyethylene, Ethylene-vinyl acetate copolymer, Ethylene-vinyl acetate-Vinyl alcohol copolymer, Ethylene- (meth) acrylic acid Examples thereof include polymers, ethylene-acrylic acid ester-carbon monoxide copolymers, polyacrylonitrile, polycarbonates, polystyrenes, ionomers, and mixtures of these thermoplastic resins. Of these, polyolefins, polyethylene terephthalates and polyamides are preferred.
[0083]
　Among these thermoplastic resins (B), polyolefin is more preferable from the viewpoint of spinning stability during molding and stretchability of the non-woven fabric, such as high-pressure low-density polyethylene, linear low-density polyethylene (so-called LLDPE), and high-density polyethylene. , Polyethylene, polypropylene random copolymer and other propylene-based polymers are more preferable.
[0084]
　Examples of the propylene-based polymer include a homopolymer of propylene having a melting point (Tm) of 155 ° C. or higher, preferably 157 ° C. to 165 ° C., or a propylene and a very small amount of ethylene, 1-butene, 1-pentene, 1 -Hexene, 1-octene, 4-methyl-1-pentene, etc. having 2 or more carbon atoms (excluding 3 carbon atoms), preferably 2 to 8 carbon atoms (excluding 3 carbon atoms). Polymers with more than one species of α-olefin are preferred.
[0085]
　The melt flow rate (MFR: ASTM D-1238, 230 ° C., load 2160 g) of the propylene-based polymer is not particularly limited as long as it can be melt-spun, but it is usually 1 g / 10 minutes to 1000 g / 10 minutes, preferably. It is in the range of 5 g / 10 minutes to 500 g / 10 minutes, more preferably 10 g / 10 minutes to 100 g / 10 minutes. The ratio Mw / Mn of the weight average molecular weight (Mw) and the number average molecular weight (Mn) of the propylene-based polymer is usually 1.5 to 5.0. Mw / Mn is preferably in the range of 1.5 to 3.0 in that fibers having good spinnability and excellent fiber strength can be obtained. Mw and Mn can be measured by a known method by GPC (gel permeation chromatography).
[0086]
　From the viewpoint of further improving the stretchability of the obtained nonwoven fabric laminate, it is preferable that the thermoplastic resin (B) is an olefin polymer composition obtained by adding HDPE to a propylene polymer. In this case, the ratio of HDPE to 100% by mass of the total of the propylene-based polymer and HDPE is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 15% by mass, and 4% by mass. It is more preferably% to 10% by mass.
[0087]
　The type of HDPE added to the propylene-based polymer is not particularly limited, but the density is usually 0.94 g / cm 3 to 0.97 g / cm 3 , preferably 0.95 g / cm 3 to 0.97 g / cm 3. , More preferably in the range of 0.96 g / cm 3 to 0.97 g / cm 3 . The melt flow rate of HDPE (MFR: ASTM D-1238, 190 ° C., load 2160 g) is usually 0.1 g / 10 minutes or more from the viewpoint of exhibiting extensibility, although it is not particularly limited as long as it has spinnability. It is in the range of 100 g / 10 minutes, preferably 0.5 g / 10 minutes to 50 g / 10 minutes, more preferably 1 g / 10 minutes to 30 g / 10 minutes. In the present disclosure, good spinnability means that yarn breakage does not occur during ejection from the spinning nozzle and during drawing, and filament fusion does not occur.
[0088]
(Additives) If
　necessary, various stabilizers such as heat-resistant stabilizers, weather-resistant stabilizers, and antioxidants, antistatic agents, slip agents, antifogging agents, lubricants, dyes, etc. Pigments, natural oils, synthetic oils, waxes and the like can be added.
[0089]
(Other Layers)
　The nonwoven fabric laminate of the present disclosure may have one or two or more layers other than the elastic nonwoven fabric and the mixed fiber spunbonded nonwoven fabric, depending on the intended use.
[0090]
　Specific examples of the other layer include knitted fabrics, woven fabrics, non-woven fabrics other than elastic non-woven fabrics and mixed fiber spunbonded non-woven fabrics, natural fibers such as cotton, and films. The method of further laminating (bonding) other layers to the non-woven fabric laminate of the present disclosure is not particularly limited, and is heat-embossing, a heat-sealing method such as ultrasonic fusion, and mechanical entanglement such as needle punching and water jet. Various methods such as a method, a method using an adhesive such as a hot melt adhesive and a urethane adhesive, and an extruded laminate can be adopted.
[0091]
　When the non-woven fabric laminate of the present disclosure has a non-woven fabric other than the elastic non-woven fabric and the mixed fiber spunbonded non-woven fabric, the non-woven fabric includes spunbonded non-woven fabric, melt blown non-woven fabric, wet non-woven fabric, dry non-woven fabric, dry pulp non-woven fabric, flash-spun non-woven fabric, and spread fiber non-woven fabric. Various known non-woven fabrics such as, etc. can be mentioned. These non-woven fabrics may be stretchable non-woven fabrics or non-stretchable non-woven fabrics. Here, the non-stretchable non-woven fabric means a non-woven fabric that does not generate stress during recovery after being stretched in MD (flow direction of the non-woven fabric, vertical direction) or CD (direction perpendicular to the flow direction of the non-woven fabric, horizontal direction).
[0092]
　When the nonwoven fabric laminate of the present disclosure has a film, a breathable (moisture permeable) film is preferable from the viewpoint of maintaining the breathability and hydrophilicity that are the characteristics of the nonwoven fabric laminate of the present disclosure. As the breathable film, a film made of a thermoplastic elastomer such as a moisture-permeable polyurethane elastomer, a polyester elastomer, or a polyamide elastomer, or a film made of a thermoplastic resin containing inorganic fine particles or organic fine particles is stretched and made porous. Examples thereof include various known breathable films such as a porous film. As the thermoplastic resin used for the porous film, polyolefins such as high-pressure low-density polyethylene, linear low-density polyethylene (so-called LLDPE), high-density polyethylene, polypropylene, polypropylene random copolymer, and a combination thereof are preferable. However, when it is not necessary to maintain the breathability and hydrophilicity of the non-woven fabric laminate, a thermoplastic resin film such as polyethylene, polypropylene, or a combination thereof may be used.
[0093]
(Method for Producing Non-woven Laminate) In the non-woven laminate of the
　present disclosure, the ratio (E40 / E23) of the storage elastic modulus E40 at 40 ° C. and the storage elastic modulus E23 at 23 ° C., which is the raw material of the elastic non-woven fabric, is 37% or more. A method for producing a known non-woven fabric using a certain α-olefin copolymer, a thermoplastic elastomer (A) and a thermoplastic resin (B) as raw materials for a mixed fiber spunbonded non-woven fabric, and an additive used as needed. Can be manufactured by
[0094]
　As an example of a method for producing a nonwoven fabric laminate, a method using a nonwoven fabric manufacturing apparatus equipped with at least two rows of spinning apparatus will be described below.
[0095]
　First, the thermoplastic elastomer (A) and the thermoplastic resin (B) are melted by an extruder provided in the first row spinning apparatus, and a mouthpiece (die) having a large number of spinning holes (nozzles) is provided, if necessary. It is introduced into a spinning hole having a core-sheath structure and discharged. Then, the long fibers made of the melt-spun thermoplastic elastomer (A) and the long fibers made of the thermoplastic resin (B) are introduced into the cooling chamber, cooled by the cooling air, and then the long fibers are drawn (drawn) by the drawn air. ), And deposit the mixed fiber spunbonded non-woven fabric on the moving collection surface.
[0096]
　On the other hand, an α-olefin copolymer in which the ratio (E40 / E23) of the storage elastic modulus E40 at 40 ° C. to the storage elastic modulus E23 at 23 ° C. is 37% or more in the extruder provided in the second row spinning apparatus. Is melted and introduced into a spinning hole having a mouthpiece (die) equipped with a large number of spinning holes (nozzles), and the ratio (E40 / E23) of the storage elastic modulus E40 at 40 ° C. to the storage elastic modulus E23 at 23 ° C. The α-olefin copolymer of 37% or more is discharged. After that, long fibers made of an α-olefin copolymer having a ratio (E40 / E23) of the melt-spun storage elastic modulus E40 at 40 ° C. and the storage elastic modulus E23 at 23 ° C. being 37% or more were introduced into the cooling chamber. Then, after cooling with cooling air, the long fibers are stretched (towed) by stretched air and deposited on the mixed fiber spunbonded non-woven fabric to form an elastic non-woven fabric.
[0097]
　If desired, a mixed fiber spunbonded non-woven fabric may be deposited on the elastic non-woven fabric using a third row spinning apparatus.
[0098]
　The melting temperature of the polymer used as the raw material of the elastic non-woven fabric and the mixed fiber spunbonded non-woven fabric is not particularly limited as long as it is equal to or higher than the softening temperature or melting temperature of each polymer and lower than the thermal decomposition temperature. The temperature of the base depends on the type of polymer used, but for example, a thermoplastic polyurethane-based elastomer or an olefin-based copolymer elastomer is used as the thermoplastic elastomer (A), and a propylene-based polymer or a propylene-based polymer is used as the thermoplastic resin (B). When the olefin-based polymer composition of the propylene-based polymer and HDPE is used, the temperature can be usually set to 180 ° C. to 240 ° C., preferably 190 to 230 ° C., and more preferably 200 to 225 ° C.
[0099]
　The temperature of the cooling air is not particularly limited as long as it is the temperature at which the polymer solidifies, but is usually in the range of 5 ° C. to 50 ° C., preferably 10 ° C. to 40 ° C., and more preferably 15 ° C. to 30 ° C. The wind speed of the stretched air is usually in the range of 100 m / min to 10,000 m / min, preferably 500 m / min to 10,000 m / min.
[0100]
　The non-woven fabric laminate of the present disclosure preferably has a structure in which at least a part of an elastic non-woven fabric and at least a part of a mixed fiber spunbonded non-woven fabric are heat-sealed. At this time, before heat-sealing at least a part of the elastic non-woven fabric and at least a part of the mixed fiber spunbonded non-woven fabric, it may be compacted by using a nip roll.
[0101]
　The method of heat fusion is not particularly limited and can be selected from various known methods. For example, a method using means such as ultrasonic waves, a method using thermal embossing using an embossing roll, a method using hot air through, and the like can be exemplified as prebonding. Above all, heat embossing is preferable from the viewpoint that the long fibers are efficiently drawn when drawn, and the temperature range thereof is preferably 60 ° C. to 115 ° C.
[0102]
　When a part of the laminate is heat-sealed by heat embossing, the embossed area ratio is usually 5% to 30%, preferably 5% to 20%, and the non-embossed unit area is 0.5 mm 2 or more, preferably. It is in the range of 4 mm 2 to 40 mm 2 . The non-embossed unit area is the maximum area of ​​a quadrangle inscribed in embossing in the smallest unit non-embossed portion surrounded by embossed portions on all sides. Examples of the shape of the engraving include a circle, an ellipse, an oval, a square, a rhombus, a square, a square, and a continuous shape based on these shapes.
[0103]
　
　The stretchable nonwoven fabric laminate of the present disclosure is a non-woven fabric laminate having elasticity obtained by stretching the nonwoven fabric laminate.
[0104]
　The stretchable nonwoven fabric laminate of the present disclosure can be obtained by stretching the nonwoven fabric laminate. The method of stretching is not particularly limited, and conventionally known methods can be applied. The method of stretching may be a method of partially stretching or a method of totally stretching. Further, it may be a method of uniaxial stretching or a method of biaxial stretching. Examples of the method of stretching in the flow direction (MD) of the machine include a method of passing mixed fibers partially fused to two or more nip rolls. At this time, the partially fused nonwoven fabric laminate can be stretched by increasing the rotation speed of the nip roll in the order of the flow direction of the machine. Further, the gear stretching process can also be performed using the gear stretching device shown in FIG.
[0105]
　The draw ratio is preferably 50% or more, more preferably 100% or more, still more preferably 200% or more, and preferably 1000% or less, more preferably 400% or less.
[0106]
　In the case of uniaxial stretching, it is preferable that either the stretching ratio in the flow direction (MD) of the machine or the direction perpendicular to the stretching ratio (CD) satisfies the stretching ratio. In the case of biaxial stretching, it is preferable that at least one of the flow direction (MD) of the machine and the direction perpendicular to the flow direction (CD) satisfies the stretching ratio.
[0107]
　By stretching at such a draw ratio, both the elastic non-woven fabric and the (long) fibers forming the mixed fiber spunbonded non-woven fabric are stretched, but the long fibers forming the mixed fiber spunbonded non-woven fabric layer are plastically deformed. Then, it is stretched (that is, lengthened) according to the stretching ratio.
[0108]
　Therefore, when the stress is released after stretching the non-woven fabric laminate, the (long) fibers forming the elastic non-woven fabric recover elastically, and the long fibers forming the mixed fiber spunbonded non-woven fabric bend without recovering elasticity. , The non-woven fabric laminate gives a feeling of bulkiness. Moreover, the long fibers forming the mixed fiber spunbonded non-woven fabric tend to be thin. Therefore, it is considered that the flexibility and the tactile sensation are improved, and the function of stopping the elongation can be imparted.
[0109]
　
　The textile products of the present disclosure include the nonwoven fabric laminates of the present disclosure or the stretchable nonwoven fabric laminates. Textile products are not particularly limited, and examples thereof include disposable diapers, absorbent articles such as sanitary products, sanitary articles such as sanitary masks, medical articles such as bandages, clothing materials, and packaging materials. The textile products of the present disclosure preferably include the non-woven fabric laminate or the stretchable non-woven fabric laminate of the present disclosure as elastic members.
Example
[0110]
　Hereinafter, the present invention will be described in more detail based on Examples, but the present invention is not limited to these Examples. The materials, amounts used, proportions, treatment procedures, etc. shown in the following examples can be appropriately changed as long as they do not deviate from the gist of the present disclosure. Physical property values ​​and the like in Examples and Comparative Examples were measured and evaluated by the following methods.
[0111]
(1) Metsuke [g / m 2 ]
　Six test pieces of 200 mm (flow direction: MD) × 50 mm (horizontal direction: CD) were collected from the non-woven fabric alone or the non-woven fabric laminate. The collection locations were arbitrary 3 locations for both MD and CD (6 locations in total). Next, the mass (g) of each of the collected test pieces was measured using a precision electronic balance (manufactured by Kensei Kogyo Co., Ltd.). The average value of the mass of each test piece was calculated. The calculated average value was converted into mass (g) per 1 m 2 , and the second decimal place was rounded off to obtain the basis weight [g / m 2 ] of each sample .
[0112]
(2) Spinnability
　When manufacturing the non-woven fabrics of each example, visually observe the spinning condition near the nozzle surface of the spunbonded non-woven fabric manufacturing apparatus, and determine the number of yarn breaks per 5 minutes (unit: times / 5 minutes). I counted. When the number of yarn breaks was 0 times / 5 minutes, it was evaluated as "A", and when the yarn breakage occurred and the non-woven fabric could not be collected, it was evaluated as "C" (Table 1).
[0113]
(3) Extrusion property
　20 kg of the raw material was put into an extruder having a diameter of 75 mm, and extrusion stability was confirmed for 30 minutes.
　　A: Stable extruded state for 30 minutes.
　　C: A state in which the raw material is blocked at the root of the extruder during 30 minutes.
[0114]
(4) Maximum load [N / 50 mm], maximum load elongation [%]
　Five test pieces of 50 mm (MD) × 200 mm (CD) were collected from the non-woven fabric laminate. In addition, the collection place was arbitrary 5 places. Next, each of the collected test pieces was subjected to a tensile test using a universal tensile tester (manufactured by Intesco, IM-201 type) under the conditions of a chuck distance of 100 mm and a tensile speed of 100 mm / min, and the load at the maximum load point was obtained. (Maximum load [N / 50 mm]) and elongation (maximum load elongation [%]) were determined. For the maximum load and the maximum load elongation, the average value was calculated for the above five points, and the second decimal place was rounded off.
[0115]
(5) Residual strain [%], 50% stress during elongation [N / 50 mm], stress during 50% recovery [N / 50 mm], and stretch characteristics
　50 mm (MD) x 200 mm (CD) test pieces from the non-woven fabric laminate Five points were collected. In addition, the collection place was arbitrary 5 places. Next, each of the collected test pieces was stretched using a universal tensile tester (manufactured by Intesco, IM-201 type) under the conditions of a chuck distance of 100 mm, a tensile speed of 100 mm / min, and a draw ratio of 100%, and then immediately the same. It recovered to the original length at a speed. This operation was carried out for two cycles, and the elongation at which the stress began to rise in the second cycle was measured and used as the residual strain [%]. Next, the stress when the draw ratio becomes 50% at the time of extension in the second cycle is set as the stress at 50% elongation, and the stress when the draw ratio becomes 50% at the time of recovery in the second cycle is set as the stress at 50% recovery. And said. In addition, the value of [50% elongation stress ÷ 50% recovery stress] in the second cycle was measured and used as a measure of expansion and contraction characteristics. The smaller the residual strain and [50% elongation stress ÷ 50% recovery stress], the better the expansion and contraction characteristics. For the residual strain and expansion / contraction characteristics, the average value was calculated for the above five points, and the third decimal place was rounded off. When the expansion / contraction characteristic was 3.0 or less, it was evaluated as "A", and when it was more than 3.0, it was evaluated as "C".
[0116]
　In addition, Table 1 shows the results of measuring the ratio of the storage elastic modulus and the storage elastic modulus at each temperature in each example by the above-mentioned measuring method. When the ratio (E40 / E23) of the storage elastic modulus E40 at 40 ° C. and the storage elastic modulus E23 at 23 ° C. is 37% or more, it is evaluated as stress retention “A”, and when it is less than 37%, it is evaluated as “C”. I evaluated it.
[0117]
[Example 1]

　Polyester polyol having a number average molecular weight of 1932: 71.7 parts by mass, 1,4-butanediol (hereinafter, abbreviated as "BD"): 4. 8 parts by mass, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate] (hereinafter abbreviated as "antioxidant-1"): 0.3 parts by mass, poly Carboxylimide: 0.3 parts by mass was mixed, MDI: 22.9 parts by mass was added, and the mixture was stirred and mixed at a sufficiently high speed. Then, the reaction was carried out at 160 ° C. for 1 hour. After pulverizing this reaction product, ethylene bisstearic amide: 0.8 parts by mass, triethylene glycol-bis- [3- (3,5-di-t-butyl), relative to 100 parts by mass of the pulverized product. -4v hydroxyphenyl) propionate] (hereinafter abbreviated as "antioxidant-2"): 0.5 parts by mass, ethylene bisoleic acid amide (hereinafter abbreviated as "EOA"): 0.8 parts by mass Mixed. Then, it was melt-kneaded and granulated with an extruder (set temperature: 210 ° C.) to obtain a thermoplastic polyurethane elastomer [TPU (A-1)].
　The physical characteristics of the obtained TPU (A-1) were hardness: 81, melt viscosity: 1.1, and flow start temperature of 155 ° C.
[0118]

　MFR (measured at 230 ° C. and 2.16 kg load according to ASTM D1238) 60 g / 10 minutes, density 0.91 g / cm 3 , melting point 160 92 parts by mass of propylene homopolymer (hereinafter abbreviated as "PP-1") at ° C, MFR (measured at a temperature of 190 ° C and a load of 2.16 kg according to ASTMD1238) 5 g / 10 minutes, density 0.97 g / A thermoplastic resin composition (B-1) was prepared by mixing 8 parts by mass of high-density polyethylene (hereinafter abbreviated as “HDPE”) having a cm size of 3 and a melting point of 134 ° C.
[0119]
<α-olefin copolymer for elastic non-woven fabric> For the
　elastic non-woven fabric, a product name "Vistamaxx TM 6202" (ethylene-propylene copolymer) manufactured by ExxonMobil Co., Ltd. was used. MFR (230 ° C, 2.16 kg load): 20 g / 10 min, ethylene content: 15 mass%, tensile modulus: 9.8 MPa, storage modulus at 23 ° C: 12.0 MPa, storage modulus at 40 ° C: 6. It was 55 MPa, melting point: 110.4 ° C., heat of fusion: 5.89 mJ / mg, glass transition temperature: -32.6 ° C.
[0120]
　
　The TPU (A-1) and the thermoplastic resin composition (B-1) prepared above were independently melted by using an extruder having a diameter of 50 mm and an extruder having a diameter of 75 mm, respectively. Then, using a spunbonded non-woven fabric molding machine having a spinneret (length in the direction perpendicular to the flow direction of the machine on the collection surface: 800 mm), both the resin temperature and the die temperature were 205 ° C., and the cooling air temperature was 20 ° C. A mixed length containing long fibers A made of TPU (A-1) and long fibers B made of a thermoplastic resin composition (B-1) by melt-spinning by a spunbond method under the condition of a stretched air air velocity of 3200 m / min. A web of fibers was deposited on the collection surface.
[0121]
　Specifically, a nozzle pattern in which TPU (A-1) discharge holes and B-1 discharge holes are alternately arranged is used as the spinneret, and a nozzle of TPU (A-1) (long fiber A) is used. The diameter is 0.75 mmφ, the nozzle diameter of B-1 (long fiber B) is 0.6 mmφ, the nozzle pitch is 8 mm in the vertical direction and 11 mm in the horizontal direction, and the ratio of the number of nozzles is the nozzle for long fiber A. : Nozzle for long fiber B = 1: 1.45. The single-hole discharge amount of the long fiber A is 0.82 g / (minutes / holes), the single-hole discharge amount of the long fibers B is 0.56 g / (minutes / holes), and the spunbonded non-woven fabric made of mixed long fibers is collected. It was deposited on the surface as the first layer.
[0122]
　Next, an elastic non-woven fabric was deposited as a second layer on the mixed-fiber spunbonded non-woven fabric. Specifically, the above Vistamax x 6202 was melted using a single-screw extruder having a screw diameter of 75 mmφ. Then, using a spunbonded non-woven fabric molding machine having a spinneret (length in the direction perpendicular to the flow direction of the machine on the collection surface: 800 mm), both the resin temperature and the die temperature were 290 ° C., and the cooling air temperature was 20 ° C. , The stretched air was melt-spun by the spunbond method under the condition of a wind speed of 2888 m / min, and deposited as the second layer.
[0123]
　Next, a mixed fiber spunbonded nonwoven fabric similar to that of the first layer was deposited on the elastic nonwoven fabric as the third layer by the same method as that of the first layer to prepare a three-layer structure deposit. This deposit was heat-pressed with an embossing roll (embossing area ratio 18%, embossing temperature 80 ° C.) to give a total basis weight of 65.0 g / m 2 , and the basis weight of the first layer and the third layer. A non-woven laminate having a basis weight of 20.0 g / m 2 and a basis weight of the second layer of 25.0 g / m 2 was produced.
　The extrudability of Vistamaxx 6202 was good. Table 1 shows the results of measuring the physical characteristics of the obtained non-woven fabric laminate.
[0124]
[Example 2]
　Using ExxonMobile's product name "Vistamaxx TM 7050FL" (ethylene / propylene copolymer) for the elastic non-woven fabric, the resin temperature and die temperature of Vistamaxx7050FL were both changed to 215 ° C and the embossing temperature was changed to 90 ° C. A non-woven fabric laminate was prepared in the same manner as in Example 1 except for the above.
Vistamaxx 7050FL has MFR (230 ° C, 2.16 kg load): 48 g / 10 min, ethylene content: 13 mass%, tensile modulus: 14.4 MPa, storage modulus at 23 ° C: 17.4 MPa, storage modulus at 40 ° C. The modulus was 8.77 MPa, the melting point was 60.9 ° C., the amount of heat of fusion was 19 mJ / mg, and the glass transition temperature was -30.3 ° C.
　The extrudability of Vistamaxx 7050FL was good. Table 1 shows the results of measuring the physical characteristics of the obtained non-woven fabric laminate.
[0125]
　[Comparative Example 1]
　Using the low crystallinity polypropylene described below as the elastic non-woven fabric, the resin temperature and die temperature of the low crystallinity polypropylene are both 215 ° C., the embossing temperature is 90 ° C., and the grain size of the second layer is 20. A non-woven fabric laminate was prepared in the same manner as in Example 1 except that the total grain size was changed to 0 g / m 2 (total grain size was 60.0 g / m 2 ).
[0126]
In a stainless steel reactor
　with an internal volume of 0.2 m 3 equipped with a stirrer , n-heptane at 20 L / h, triisobutylaluminum at 15 mmol / h, and dimethyl. Anilinium tetrakispentafluorophenylborate, (1,2'-dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, triisobutylaluminum and propylene are pre-contacted. The obtained catalyst component was continuously supplied at 6 μmol / h per zirconium.
[0127]
　Propylene and hydrogen were continuously supplied at a polymerization temperature of 70 ° C., keeping the hydrogen concentration in the gas phase at 8 mol% and maintaining the total pressure in the reactor at 0.7 MPa · G.
　A propylene polymer was obtained by adding SUMILIZER GP (manufactured by Sumitomo Chemical Co., Ltd.) to the obtained polymerization solution so as to have a concentration of 1000 ppm and removing the solvent.
[0128]
　The mass average molecular weight (Mw) of the obtained propylene polymer was 1.2 × 10 4 , Mw / Mn = 2. Further, [mmmm] determined from NMR measurement was 46 mol%, [rrrr] / (1- [mmmm]) was 0.038, [rmrm] was 2.7 mol%, and [mm] × [rr] / [ mr] 2 was 1.5 and the tensile elastic modulus was 32.9 MPa.
　Low crystalline polypropylene has a storage elastic modulus at 23 ° C.: 49.3 MPa, a storage elastic modulus at 40 ° C.: 17.8 MPa, a melting point: 56.1 ° C., a calorific value for melting: 30.0 mJ / mg, and a glass transition temperature: -7. It was 0.3 ° C.
[0129]
　The extrudability of low crystalline polypropylene was poor due to blocking. Table 1 shows the results of measuring the physical characteristics of the obtained non-woven fabric laminate.
[0130]
　In Examples 1 and 2, as can be seen from the comparison with Comparative Example 1, the stretch characteristics (50% stretch stress / 50% recovery stress) were reduced and the stretchability was improved. Further, in Examples 1 and 2, the ratio (E40 / E23) of the storage elastic modulus E40 at 40 ° C. and the storage elastic modulus E23 at 23 ° C. is high, and compared with Comparative Example 1, under a temperature change environment ( It can be seen that the decrease in elastic modulus of the elastic nonwoven fabric is easily suppressed at 40 ° C. to 23 ° C.). That is, the nonwoven fabric laminate according to the present disclosure is a nonwoven fabric laminate having excellent expansion and contraction characteristics and excellent stress maintenance.
[0131]
[table 1]

[0132]
　The disclosure of Japanese Patent Application No. 2018-068200 filed on March 30, 2018 is incorporated herein by reference in its entirety.
　All documents, patent applications, and technical standards described herein are to the same extent as if the individual documents, patent applications, and technical standards were specifically and individually stated to be incorporated by reference. Incorporated herein by reference.
The scope of the claims
[Claim 1]
　An elastic non-woven fabric containing an α-olefin copolymer having a ratio (E40 / E23) of a storage elastic ratio E40 at 40 ° C. and a storage elastic ratio E23 at 23 ° C. is arranged on at least one side of the elastic non-woven fabric. The long fibers of the thermoplastic elastomer (A) and the long fibers of the thermoplastic resin (B) other than the thermoplastic elastomer (A) are 10% by mass to 90% by mass: 90% by mass to 10% by mass. A non-woven laminate having a mixed fiber spunbonded non-woven fabric contained in a ratio (((A): (B), where (A) + (B) = 100% by mass)).
[Claim 2]
　The nonwoven fabric laminate according to claim 1, wherein the storage elastic modulus E23 of the α-olefin copolymer at 23 ° C. is 45 MPa or less.
[Claim 3]
　The non-woven laminate according to claim 1 or 2, wherein the α-olefin copolymer contains a copolymer of ethylene and propylene.
[Claim 4]
　The nonwoven fabric laminate according to any one of claims 1 to 3, wherein the α-olefin copolymer has a tensile elastic modulus of 30 MPa or less.
[Claim 5]
　The nonwoven fabric laminate according to any one of claims 1 to 4, wherein the long fibers of the thermoplastic resin (B) have a maximum point elongation of 50% or more when made into a spunbonded nonwoven fabric.
[Claim 6]
　The nonwoven fabric laminate according to any one of claims 1 to 5, wherein the thermoplastic elastomer (A) is a thermoplastic polyurethane elastomer.
[Claim 7]
　The nonwoven fabric laminate according to claim 6, wherein the thermoplastic polyurethane-based elastomer is a thermoplastic polyurethane-based elastomer satisfying the following relational expression (I).
　　a / (a ​​+ b) ≤ 0.8 (I)
(In the formula, a represents the total amount of heat of fusion obtained from the endothermic peaks in the range of 90 ° C. to 140 ° C. measured by DSC, and b is DSC. It represents the total heat of fusion calculated from the endothermic peaks in the range of more than 140 ° C and 220 ° C or less measured by.
[Claim 8]
　The nonwoven fabric laminate according to any one of claims 1 to 7, wherein the thermoplastic resin (B) is a polyolefin.
[Claim 9]
　The nonwoven fabric laminate according to any one of claims 1 to 7, wherein the thermoplastic resin (B) is a propylene-based polymer.
[Claim 10]
　The nonwoven fabric laminate according to any one of claims 1 to 9, wherein the thermoplastic resin (B) is composed of 99 to 80% by mass of a propylene-based polymer and 1 to 20% by mass of high-density polyethylene.
[Claim 11]
　A stretchable nonwoven fabric laminate obtained by stretching the nonwoven fabric laminate according to any one of claims 1 to 10.
[Claim 12]
　A textile product containing the nonwoven fabric laminate according to any one of claims 1 to 10 or the stretchable nonwoven fabric laminate according to claim 11.
[Claim 13]
　An absorbent article comprising the nonwoven fabric laminate according to any one of claims 1 to 10 or the stretchable nonwoven fabric laminate according to claim 11.
[Claim 14]
　A sanitary mask comprising the nonwoven fabric laminate according to any one of claims 1 to 10 or the stretchable nonwoven fabric laminate according to claim 11.