WO2016143834A1 - 不織布積層体、伸縮性不織布積層体、繊維製品、吸収性物品及び衛生マスク - Google Patents
不織布積層体、伸縮性不織布積層体、繊維製品、吸収性物品及び衛生マスク Download PDFInfo
- Publication number
- WO2016143834A1 WO2016143834A1 PCT/JP2016/057462 JP2016057462W WO2016143834A1 WO 2016143834 A1 WO2016143834 A1 WO 2016143834A1 JP 2016057462 W JP2016057462 W JP 2016057462W WO 2016143834 A1 WO2016143834 A1 WO 2016143834A1
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- WO
- WIPO (PCT)
- Prior art keywords
- nonwoven fabric
- fabric laminate
- stretchable
- mass
- laminate according
- Prior art date
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/02—Synthetic macromolecular fibres
- B32B2262/0253—Polyolefin fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
- B32B2262/12—Conjugate fibres, e.g. core/sheath or side-by-side
- B32B2262/124—Non-woven fabric
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/54—Yield strength; Tensile strength
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/718—Weight, e.g. weight per square meter
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/726—Permeability to liquids, absorption
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2555/00—Personal care
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2555/00—Personal care
- B32B2555/02—Diapers or napkins
Definitions
- the present invention relates to a nonwoven fabric laminate, a stretchable nonwoven fabric laminate, a textile product, an absorbent article, and a sanitary mask.
- nonwoven fabrics have been widely used for various applications because of their excellent breathability and flexibility. For this reason, the nonwoven fabric is required to have various properties according to its use and to improve the properties.
- non-woven fabrics used for sanitary materials such as disposable diapers and sanitary napkins, and base fabrics for poultices are required to have water resistance and excellent moisture permeability.
- base fabrics for poultices are required to have stretchability, bulkiness and wearability.
- thermoplastic elastomer as a raw material of a spunbond nonwoven fabric
- low crystalline polypropylene eg, a special material
- Japanese Patent Application Laid-Open No. 2009-62667 or Japanese Patent Application Laid-Open No. 2009-79341 proposes adding a high crystalline polypropylene or a release agent to low crystalline polypropylene in order to improve the stickiness of a spunbonded nonwoven fabric.
- International Publication No. 2012/070518 discloses a laminate of a non-crystalline polypropylene-containing nonwoven fabric and an extensible spunbonded nonwoven fabric.
- the stretchability is maintained by laminating the low crystalline polypropylene and the stretchable spunbond nonwoven fabric, but further improvement in stretchability is strongly demanded. . At the same time, it is also required to realize good tactile sensation, wearability and roll blocking resistance.
- roll blocking means that when a nonwoven fabric laminate is stored for a long time in a roll state, the overlapped nonwoven fabric laminates adhere to each other due to storage environment temperature, pressure applied to the nonwoven fabric laminate, etc., and the roll is hardened. Means a phenomenon.
- the nonwoven fabric laminate using the low crystalline polypropylene described in International Publication No. 2012/070518 is required to improve blocking resistance when stored at a high temperature for a long period of time.
- Means for solving the above problems include the following embodiments. ⁇ 1> an elastic nonwoven fabric and an extensible spunbonded nonwoven fabric which is disposed on at least one side of the elastic nonwoven fabric and has a maximum load elongation in at least one direction of 50% or more, and the following (1) and (2 A nonwoven fabric laminate satisfying (1)
- the elastic nonwoven fabric includes a low crystalline polypropylene satisfying the following (a) to (f), a structural unit derived from ethylene and a structural unit derived from propylene, and has a melting point of 100 ° C. or higher and is crystallized. And an ⁇ -olefin copolymer A having a degree of 15% or less.
- the resin composition contains 5 to 50 parts by mass of ⁇ -olefin copolymer A with respect to 100 parts by mass of the resin composition.
- [mmmm] 20-60 mol%
- B [rrrr] / (1- [mmmm]) ⁇ 0.1
- C [rmrm]> 2.5 mol%
- D [mm] ⁇ [rr] / [mr] 2 ⁇ 2.0
- Mw / Mn ⁇ 4
- [mmmm] is a mesopentad fraction
- [rrrr] is a racemic pentad fraction
- [rmrm] is a racemic meso-racemic mesopentad fraction
- [mm], [Rr] and [mr] are triad fractions, respectively.
- ⁇ 2> The nonwoven fabric laminate according to ⁇ 1>, wherein the resin composition includes 95 to 50 parts by mass of the low crystalline polypropylene with respect to 100 parts by mass of the resin composition.
- ⁇ 3> The nonwoven fabric laminate according to ⁇ 1> or ⁇ 2>, wherein the ⁇ -olefin copolymer A has a tensile modulus of 100 MPa or less.
- ⁇ 4> The nonwoven fabric laminate according to any one of ⁇ 1> to ⁇ 3>, wherein the ⁇ -olefin copolymer A is a copolymer containing structural units derived from ethylene, propylene, and butene.
- ⁇ 5> The nonwoven fabric laminate according to any one of ⁇ 1> to ⁇ 4>, wherein the stretchable spunbonded nonwoven fabric is disposed on both sides of the elastic nonwoven fabric.
- ⁇ 6> The nonwoven fabric laminate according to any one of ⁇ 1> to ⁇ 5>, wherein the elastic nonwoven fabric is a nonwoven fabric obtained by a spunbond method.
- the stretchable spunbonded nonwoven fabric is a low MFR propylene-based polymer having an MFR in the range of 1 g / 10 min to 200 g / 10 min in the core portion, and an MFR of 16 g / 10 min to 215 g / in in the sheath portion.
- a high MFR propylene polymer in the range of 10 minutes, and the difference in MFR between the low MFR propylene polymer and the high MFR propylene polymer is 15 g / 10 min or more.
- the nonwoven fabric laminate according to any one of ⁇ 1> to ⁇ 6>, which is an extensible spunbonded nonwoven fabric composed of core-sheath type composite fibers.
- the stretchable spunbond nonwoven fabric is composed of an olefin polymer composition containing 80% by mass to 99% by mass of a crystalline propylene polymer and 20% by mass to 1% by mass of high-density polyethylene ⁇ 1
- ⁇ 9> Any one of ⁇ 1> to ⁇ 8>, wherein a basis weight ratio of the elastic nonwoven fabric to the stretchable spunbond nonwoven fabric (elastic nonwoven fabric: stretchable spunbond nonwoven fabric) is in the range of 10:90 to 90:10.
- a stretchable nonwoven fabric laminate obtained by stretching the nonwoven fabric laminate according to any one of ⁇ 1> to ⁇ 9>.
- a fiber product comprising the nonwoven fabric laminate according to any one of ⁇ 1> to ⁇ 9> or the stretchable nonwoven fabric laminate according to ⁇ 10>.
- An absorbent article comprising the nonwoven fabric laminate according to any one of ⁇ 1> to ⁇ 9> or the stretchable nonwoven fabric laminate according to ⁇ 10>.
- a sanitary mask comprising the nonwoven fabric laminate according to any one of ⁇ 1> to ⁇ 9> or the stretchable nonwoven fabric laminate according to ⁇ 10>.
- the nonwoven fabric laminated body which is excellent in the moldability at the time of manufacture, stretchability, tactile sensation, mounting property, and roll blocking resistance, and a stretchable nonwoven fabric laminated body, a textile product, an absorbent article, and hygiene using the same A mask is provided.
- FIG. 1 is a schematic view of a gear stretching apparatus.
- FIG. 2 is a schematic view of the preheating device.
- the term “process” is not only an independent process, but is included in this term if the purpose of the process is achieved even if it cannot be clearly distinguished from other processes.
- a numerical range indicated using “to” indicates a range including the numerical values described before and after “to” as the minimum value and the maximum value, respectively.
- the content of each component in the composition is such that when there are a plurality of substances corresponding to each component in the composition, the plurality of substances present in the composition unless otherwise specified. Means the total amount.
- the nonwoven fabric laminate of the present invention comprises an elastic nonwoven fabric and an extensible spunbonded nonwoven fabric that is disposed on at least one side of the elastic nonwoven fabric and has a maximum load elongation in at least one direction of 50% or more. Satisfy 1) and (2).
- the elastic nonwoven fabric includes a low crystalline polypropylene satisfying the following (a) to (f), a structural unit derived from ethylene and a structural unit derived from propylene, and has a melting point of 100 ° C. or higher and is crystallized. And an ⁇ -olefin copolymer A having a degree of 15% or less.
- the resin composition contains 5 to 50 parts by mass of ⁇ -olefin copolymer A with respect to 100 parts by mass of the resin composition.
- [mmmm] 20-60 mol%
- B [rrrr] / (1- [mmmm]) ⁇ 0.1
- C [rmrm]> 2.5 mol%
- D [mm] ⁇ [rr] / [mr] 2 ⁇ 2.0
- Mw / Mn ⁇ 4
- [mmmm] is a mesopentad fraction
- [rrrr] is a racemic pentad fraction
- [rmrm] is a racemic meso-racemic mesopentad fraction
- [mm], [Rr] and [mr] are triad fractions, respectively.
- the nonwoven fabric laminate of the present invention since the stretchable spunbond nonwoven fabric is disposed on at least one side of the elastic nonwoven fabric, the nonwoven fabric laminate adheres to members of various rotating devices in the apparatus used in the embossing process and the like. It can be prevented and has excellent moldability and productivity. Moreover, since the spunbond nonwoven fabric has extensibility, the excellent stretchability of the elastic nonwoven fabric is maintained. Furthermore, since an elastic nonwoven fabric consists of a specific resin composition, the residual distortion of a nonwoven fabric laminated body is small, and the elasticity is improved rather than the conventional nonwoven fabric laminated body. Furthermore, tactile sensation, wearability and roll blocking resistance are also good.
- the nonwoven fabric laminate of the present invention preferably has a structure in which at least a stretchable spunbond nonwoven fabric is disposed on the surface on the side in contact with the rotating device attached to the nonwoven fabric production apparatus. It is more preferable to have a structure in which a bond nonwoven fabric is arranged.
- the nonwoven fabric laminate of the present invention 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. / M 2 within the range.
- the basis weight can be measured by the method used in Examples described later.
- the composition ratio of the elastic nonwoven fabric and the stretchable spunbond nonwoven fabric can be appropriately determined according to various uses.
- the elastic nonwoven fabric: extensible spunbonded nonwoven fabric (weight ratio) 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 80-50: 50.
- the basis weight of the elastic nonwoven fabric (or stretchable spunbond nonwoven fabric) is a total of two or more.
- the nonwoven fabric laminate of the present invention usually has a residual strain in at least one direction of 26% or less, preferably 25% or less. If the residual strain in at least one direction is 26% or less, the stretchability is good. Residual strain can be measured by the method used in Examples described later.
- the nonwoven fabric laminate of the present invention usually has a maximum load elongation in at least one direction of 205% or more, preferably 230% or more.
- the maximum load elongation can be measured by the method used in Examples described later.
- the residual embossing ratio after stretching is preferably 60% or more, more preferably 65% or more, and further preferably 70% or more.
- the tactile sensation is good when the emboss remaining rate after the stretching process is 60% or more.
- the emboss remaining rate can be measured by the method used in Examples described later.
- the nonwoven fabric laminate of the present invention preferably has a peel strength of 10 N or less, more preferably 9 N or less, and even more preferably 8 N or less after two nonwoven fabric laminates are stacked and stored in an oven. .
- the peel strength is 10 N or less, the roll blocking resistance is good.
- the peel strength can be measured by the method used in Examples described later.
- the elastic nonwoven fabric constituting the nonwoven fabric laminate of the present invention comprises a low crystalline polypropylene satisfying the following (a) to (f) (hereinafter also simply referred to as low crystalline polypropylene), a structural unit derived from ethylene, and propylene. It comprises a resin composition comprising an ⁇ -olefin copolymer A containing a derived structural unit, having a melting point of 100 ° C. or more and a crystallinity of 15% or less.
- the elastic nonwoven fabric refers to a nonwoven fabric having a property of recovering by elasticity when stress is released after stretching.
- Elastic nonwoven fabrics can be produced by various known methods. Specific examples include a spun bond method, a melt blow method, and a flash spinning method. Among elastic nonwoven fabrics, a spunbond nonwoven fabric obtained by a spunbond method or a meltblown nonwoven fabric obtained by a meltblowing method is preferable.
- 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 . Is in range.
- the fiber constituting the elastic nonwoven fabric usually has a fiber diameter of 50 ⁇ m or less, preferably 40 ⁇ m or less, and more preferably 30 ⁇ m or less.
- the total content of the ⁇ -olefin copolymer A and the low crystalline polypropylene in the total mass of the resin composition is preferably 80% by mass or more, and 90% by mass. % Or more, more preferably 95% by mass or more.
- the ⁇ -olefin copolymer A includes a structural unit derived from ethylene and a structural unit derived from propylene, has a melting point of 100 ° C. or higher, and a crystallinity of 15% or lower.
- the ⁇ -olefin copolymer A is not particularly limited as long as it satisfies the above conditions, and may further include one or more structural units derived from an ⁇ -olefin other than ethylene or propylene.
- Examples of ⁇ -olefins other than ethylene or propylene include 1-butene, 1-hexene, 4methyl-1-pentene, 1-octene and the like.
- the total proportion of the structural units derived from ethylene and the structural units derived from propylene in all the structural units of the ⁇ -olefin copolymer A is 80 mol% or more. It is preferably 85 mol% or more, more preferably 90 mol% or more.
- the melting point of the ⁇ -olefin copolymer A is a melting endothermic curve obtained by using a differential scanning calorimeter (DSC) by holding at ⁇ 40 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min. Is defined as the peak top of the peak observed on the hottest side.
- DSC-7 differential scanning calorimeter
- a sample of 5 mg was held at ⁇ 40 ° C. for 5 minutes in a nitrogen atmosphere, and then heated at 10 ° C./min. It can be determined as the peak top of the peak observed on the highest temperature side of the obtained melting endotherm curve.
- the melting point of the ⁇ -olefin copolymer A is preferably 130 ° C. or higher, more preferably 150 ° C. or higher.
- the crystallinity of ⁇ -olefin copolymer A is preferably 10% or less, more preferably 8% or less.
- the ⁇ -olefin copolymer A preferably has a tensile modulus of elasticity of 100 MPa or less, more preferably 40 MPa or less, and preferably 25 MPa or less, as measured by a method according to JIS K7161 (2011 version). Further preferred.
- the low crystalline polypropylene is a polymer that satisfies the following requirements (a) to (f).
- (A) [mmmm] 20 to 60 mol%: When the mesopentad fraction [mmmm] of the low crystalline polypropylene is 20 mol% or more, the occurrence of stickiness is suppressed, and when it is 60 mol% or less, the degree of crystallinity does not become too high. Becomes better.
- the mesopentad fraction [mmmm] is preferably 30 to 50 mol%, more preferably 40 to 50 mol%.
- the mesopentad fraction [mmmm], the racemic pentad fraction [rrrr] and the racemic mesoraced mesopendad fraction [rmrm], which will be described later, are described in “Macromolecules, 6, 925 (1973)” by A. Zambelli et al.
- the mesopentad fraction [mmmm] increases, the stereoregularity increases.
- triad fractions [mm], [rr] and [mr] described later are also calculated by the above method.
- the 13 C-NMR spectrum can be measured according to the following equipment and conditions in accordance with the attribution of peaks proposed by “Macromolecules, 8, 687 (1975)” by A. Zambelli et al. it can.
- 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) of 1,2,4-trichlorobenzene and heavy benzene Mixed solvent temperature: 130 ° C
- Pulse width 45 °
- Pulse repetition time 4 seconds Integration: 10,000 times
- the racemic meso racemic meso fraction [rmrm] of the low crystalline polypropylene is a value exceeding 2.5 mol%, the randomness of the low crystalline polypropylene increases, and the elastic recoverability of the elastic nonwoven fabric is further improved.
- [Rmrm] is preferably 2.6 mol% or more, and more preferably 2.7 mol% or more.
- the upper limit is usually about 10 mol%.
- Weight average molecular weight (Mw) 10,000 to 200,000 If the weight average molecular weight of the low crystalline polypropylene is 10,000 or more, the viscosity of the low crystalline polypropylene is not too low and is moderate, so that yarn breakage during the production of the elastic nonwoven fabric is suppressed. Moreover, when the weight average molecular weight is 200,000 or less, the viscosity of the low crystalline polypropylene is not too high, and the spinnability is improved.
- the weight average molecular weight is preferably 30,000 to 150,000, more preferably 50,000 to 150,000. A method for measuring this weight average molecular weight will be described later.
- the low crystalline polypropylene preferably further satisfies the following (g).
- G Using a differential scanning calorimeter (DSC), observed at the highest temperature side of the melting endotherm curve obtained by holding at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere and then raising the temperature at 10 ° C./min.
- the melting point (Tm-D) defined as the peak top of the peak is 0 ° C. to 120 ° C.
- the melting point (Tm-D) was determined by using a differential scanning calorimeter (manufactured by Perkin Elmer, DSC-7) and holding 10 mg of a sample at ⁇ 10 ° C. for 5 minutes in a nitrogen atmosphere, then 10 ° C./min. It can be determined as the peak top of the peak observed on the highest temperature side of the melting endothermic curve obtained by raising the temperature at.
- the low crystalline polypropylene can be synthesized by using a homogeneous catalyst called a so-called metallocene catalyst, as described in, for example, WO2003 / 087172.
- the resin composition, the ⁇ -olefin copolymer A and the low crystalline polypropylene are optional components as long as they do not impair the purpose of the present invention, and include antioxidants, heat stabilizers, weather stabilizers, antistatic agents, slip agents, Various known additives such as antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils and waxes may be included.
- the stretchable spunbonded 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 5 g / m. It is in the range of m 2.
- the fibers constituting the stretchable spunbonded nonwoven fabric usually have a fiber diameter of 50 ⁇ m or less, preferably 40 ⁇ m or less, and more preferably 30 ⁇ m or less.
- Nonwoven fabrics obtained using olefin polymers include (1) two or more types of olefin polymers (high melting point propylene polymer and low melting point propylene having a difference in flow-induced crystallization induction period of 100 seconds or more.
- a spunbond nonwoven fabric made of a core-sheath composite fiber can be used.
- a spunbonded nonwoven fabric obtained by using an olefin polymer composition comprising 80% by mass to 99% by mass of a propylene homopolymer and 20% by mass to 1% by mass of high-density polyethylene, 2) A high melting point propylene polymer having the same or different MFR and a melting point in the range of 157 ° C. to 165 ° C., preferably a propylene homopolymer and a low melting point in the range of 130 ° C. to 150 ° C.
- the stretchable spunbonded non-woven fabric has the following features: (1)
- the core part has a MFR of 10 g / 10 min to 200 g / 10 min, a melting point of 157 ° C. to 165 ° C.
- the olefin polymers include ethylene, propylene, 1-butene, 1-hexene, 4-methyl-1-pentene, Examples thereof include homopolymers or copolymers of ⁇ -olefins such as 1-octene, ethylene polymers, propylene polymers, and crystalline polymers.
- the ethylene polymer include ethylene homopolymer ethylene / ⁇ -olefin random copolymer such as high-pressure low-density polyethylene, linear low-density polyethylene (so-called LLDPE), and high-density polyethylene (so-called HDPE).
- propylene polymers include propylene such as polypropylene (propylene homopolymer), propylene / 1-butene random copolymer, propylene / ethylene random copolymer, propylene / ethylene / 1-butene random copolymer, and the like. -Alpha olefin random copolymer etc. are mentioned.
- Specific examples of the crystalline polymer include poly-1-butene and poly-4-methyl-1-pentene.
- propylene polymer The above-mentioned propylene-based polymer is a crystalline resin that is usually produced and sold under the name of polypropylene. Specifically, a propylene homopolymer having a melting point (Tm) of 155 ° C. or higher, preferably 157 ° C. to 165 ° C.
- Tm melting point
- Tm melting point
- 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)
- copolymers of two or more ⁇ -olefins include a random copolymer and a block copolymer.
- the melt flow rate (MFR: ASTM D-1238, 230 ° C., load 2160 g) is not particularly limited. Usually, it is within the range of 1 g / 10 minutes to 1000 g / 10 minutes, preferably within the range of 5 g / 10 minutes to 500 g / 10 minutes, and more preferably within the range of 10 g / 10 minutes to 100 g / 10 minutes. It is.
- the extensible spunbond nonwoven fabric according to the present invention is preferably formed from an olefin polymer composition containing an ethylene polymer and a propylene polymer.
- the ethylene polymer contained in the olefin polymer composition is not particularly limited, but preferably has a density of 0.94 g / cm 3 to 0.97 g / cm 3 , more preferably 0.95 g / cm 3 to 0.97 g. / Cm 3 , more preferably high density polyethylene in the range of 0.96 g / cm 3 to 0.97 g / cm 3 .
- melt flow rate (MFR: ASTM D-1238, 190 ° C., load 2160 g) of the ethylene-based polymer is usually 0.1 g / The range is from 10 minutes to 100 g / 10 minutes, more preferably from 0.5 g / 10 minutes to 50 g / 10 minutes, still more preferably from 1 g / 10 minutes to 30 g / 10 minutes.
- olefin polymer ethylene polymer and propylene polymer are optional components as long as they do not impair the object of the present invention.
- Antioxidants, heat stabilizers, weather stabilizers, antistatic agents, slip agents Further, various known additives such as an antifogging agent, a lubricant, a dye, a pigment, a natural oil, a synthetic oil, a wax, and a hydrophilic agent may be included.
- the nonwoven fabric laminate of the present invention may have one or more layers other than the elastic nonwoven fabric and the stretchable spunbond nonwoven fabric depending on the application.
- the other layers include nonwoven fabrics other than knitted fabrics, woven fabrics, elastic nonwoven fabrics, and stretchable spunbond nonwoven fabrics, films, and the like.
- the method for further laminating (bonding) other layers to the nonwoven fabric laminate of the present invention is not particularly limited, and thermal entanglement, thermal fusion methods such as ultrasonic fusion, mechanical punching such as needle punch, water jet, etc.
- thermal fusion methods such as ultrasonic fusion
- mechanical punching such as needle punch, water jet, etc.
- Various methods such as a method, a method using an adhesive such as a hot-melt adhesive, a urethane-based adhesive, and extrusion lamination can be employed.
- nonwoven fabric when the nonwoven fabric laminate of the present invention has a nonwoven fabric other than the elastic nonwoven fabric and the stretchable spunbond nonwoven fabric, the spunbond nonwoven fabric, the melt blown nonwoven fabric, the wet nonwoven fabric, the dry nonwoven fabric, the dry pulp nonwoven fabric, the flash spinning nonwoven fabric, and the spread nonwoven fabric And various known nonwoven fabrics.
- These nonwoven fabrics may be stretchable nonwoven fabrics or non-stretchable nonwoven fabrics.
- the non-stretchable nonwoven fabric refers to a material that does not generate a return stress after stretching in MD (non-woven fabric flow direction, longitudinal direction) or CD (direction perpendicular to the non-woven fabric flow direction, transverse direction).
- 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 invention.
- a film made of a thermoplastic elastomer such as a polyurethane elastomer, a polyester elastomer or a polyamide elastomer having moisture permeability
- a film made of a thermoplastic resin containing inorganic fine particles or organic fine particles is stretched to be porous.
- Various known breathable films, such as a porous film can be mentioned.
- thermoplastic resin used for the porous film polyolefins such as high pressure method low density polyethylene, linear low density polyethylene (so-called LLDPE), high density polyethylene, polypropylene, polypropylene random copolymer, and combinations thereof are preferable.
- LLDPE linear low density polyethylene
- polypropylene polypropylene random copolymer
- a film of thermoplastic resin such as polyethylene, polypropylene, or a combination thereof may be used.
- the nonwoven fabric laminate of the present invention comprises a low crystalline polypropylene and ⁇ -olefin copolymer A that are raw materials for elastic nonwoven fabric, an olefin polymer that is a raw material for stretchable spunbond nonwoven fabric, and additives that are used as necessary. And can be produced by a known method for producing a nonwoven fabric.
- a method using a nonwoven fabric production apparatus having at least two rows of spinning devices will be described below.
- an olefin polymer is melted in an extruder provided in the spinning device in the first row, and if necessary, two or more extruders, and if necessary, two or more olefin polymers are melted to obtain a large number of spinning holes.
- a die (die) having a (nozzle) is introduced into a spinning hole having a core-sheath structure as necessary, and discharged.
- the long fiber containing the melt-spun olefin polymer is introduced into the cooling chamber, cooled by cooling air, and then drawn (pulled) by the drawn air, and the stretchable spunbond nonwoven fabric is moved and collected. Deposit on top.
- a resin composition containing low crystalline polypropylene and ⁇ -olefin copolymer A is melted with an extruder provided in the second row spinning device, and a die having a large number of spinning holes (nozzles) is formed. It introduce
- the long fiber containing the melt-spun resin composition is introduced into the cooling chamber, cooled by cooling air, and then stretched (pulled) by the stretched air, and deposited on the stretchable spunbond nonwoven fabric.
- An elastic nonwoven fabric is formed. If necessary, an extensible spunbond nonwoven fabric may be deposited on the elastic nonwoven fabric using a third row spinning device.
- the melting temperature of the polymer used as a raw material for the elastic nonwoven fabric and the stretchable spunbonded nonwoven fabric is not particularly limited as long as it is not lower than the softening temperature or melting temperature of each polymer and lower than the thermal decomposition temperature.
- the temperature of the die depends on the type of polymer used. For example, when a propylene-based polymer is used, the temperature is usually 180 ° C. to 240 ° C., preferably 190 to 230 ° C., more preferably 200 to 225 ° C. Can be set to
- the temperature of the cooling air is not particularly limited as long as it is a temperature at which the polymer solidifies, but is usually in the range of 5 ° C to 50 ° C, preferably 10 ° C to 40 ° C, 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.
- the nonwoven fabric laminate of the present invention preferably has a structure in which at least a part of the elastic nonwoven fabric and at least a part of the stretchable spunbond nonwoven fabric are heat-sealed. At this time, at least a part of the elastic nonwoven fabric and at least a part of the stretchable spunbond nonwoven fabric may be pressed and hardened using a nip roll before heat fusion.
- the method of heat sealing is not particularly limited, and can be selected from various known methods.
- a method using means such as ultrasonic waves, a hot embossing process using an embossing roll, a method using hot air through, etc. can be exemplified as prebonding.
- hot embossing is preferred from the viewpoint of efficiently drawing the long fibers during drawing, and the temperature range is preferably 60 ° C. to 115 ° C.
- 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 quadrilateral inscribed in the embossed portion in the smallest unit of the non-embossed portion surrounded on all four sides by the embossed portion. Examples of the shape of the marking include a circle, an ellipse, an ellipse, a square, a rhombus, a rectangle, a square, and a continuous shape based on these shapes.
- the stretchable nonwoven fabric laminate of the present invention is a stretchable nonwoven fabric laminate obtained by stretching the nonwoven fabric laminate.
- the stretchable nonwoven fabric laminate of the present invention can be obtained by stretching the nonwoven fabric laminate.
- the method for stretching is not particularly limited, and conventionally known methods can be applied.
- the stretching method may be a partially stretching method or a generally stretching method. Further, it may be a uniaxial stretching method or a biaxial stretching method. Examples of a method of stretching in the machine flow direction (MD) include a method of passing mixed fibers partially fused to two or more nip rolls. At this time, the partially laminated nonwoven fabric laminate can be stretched by increasing the rotational speed of the nip rolls in the order of the machine flow direction. Further, gear stretching can be performed using the gear stretching apparatus shown in FIG.
- 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.
- the (long) fibers forming the elastic nonwoven fabric and the stretchable spunbond nonwoven fabric are both stretched, but the long fibers forming the stretchable spunbond nonwoven fabric layer are plastically deformed. Then, the film is stretched (lengthened) according to the stretching ratio.
- the (long) fibers forming the elastic nonwoven fabric recover elastically, and the long fibers forming the stretchable spunbond nonwoven fabric are bent without elastic recovery.
- a bulky feeling appears in the nonwoven fabric laminate.
- the long fibers forming the stretchable spunbonded nonwoven fabric are thinned, the flexibility and tactile sensation are improved, and an anti-elongation function can be imparted.
- the textile product of the present invention includes the nonwoven fabric laminate or the stretchable nonwoven fabric laminate of the present invention.
- the textile product is not particularly limited, and examples thereof include disposable diapers, absorbent articles such as sanitary products, hygiene articles such as sanitary masks, medical articles such as bandages, clothing materials, and packaging materials.
- the fiber product of the present invention preferably includes the nonwoven fabric laminate or the stretchable nonwoven fabric laminate of the present invention as a stretchable member.
- the gear rolls mounted on the gear processing machine each have a diameter of 200 mm and a gear pitch of 2.5 mm, and the meshing depth of both rolls is 5.5 mm. Adjusted as follows. About the nonwoven fabric laminated body by which the gear extension was obtained as mentioned above, 10 evaluators confirmed the touch and evaluated the tactile sensation according to the following criteria. 3: 10 out of 10 people evaluated that there was no roughness. 2: 9-7 out of 10 people evaluated that there was no roughness. 1: Six to three out of ten people evaluated that there was no roughness. 0: 2 to 0 out of 10 people evaluated that there was no roughness.
- Emboss remaining rate [%]
- the gear-stretched nonwoven fabric laminate obtained by the same method as the tactile sensation evaluation was subjected to morphological observation by SEM to evaluate the residual ratio of embossing. The higher the emboss residual rate, the better the tactile sensation.
- the emboss residual rate was calculated using the following formula.
- Emboss remaining rate number of embosses not destroyed / number of embosses observed ⁇ 100 It should be noted that the embossed portion in which the perforation at the embossed portion, the detachment of the fibers at the embossed portion, and the fiber breakage at the boundary between the embossed portion and the boundary thereof were not confirmed by the observation of the embossed portion by the SEM of the nonwoven fabric laminate stretched by the gears. No embossing ".
- Diaper wearability A test piece having a flow direction (MD) of 250 mm and a transverse direction (CD) of 200 mm was cut out from the nonwoven fabric laminate. The test piece was inserted so that the CD direction coincided with the roll rotation direction of the preheating device as shown in FIG. 2 to obtain a preheated nonwoven fabric laminate. The obtained nonwoven fabric laminate is immediately inserted so that the roll rotation direction of the gear processing machine and the CD direction coincide with each other as shown in FIG. 1, and the nonwoven fabric laminate is gear-stretched in the MD direction (flow direction of the nonwoven fabric laminate). Got. The preheating is adjusted so that the roll surface temperature is 60 ° C.
- the gear rolls mounted on the gear processing machine each have a diameter of 200 mm and a gear pitch of 2.5 mm, and the meshing depth of both rolls is 3.5 mm. Adjusted as follows.
- the nonwoven fabric was peeled off from a commercially available diaper, and the gear stretched nonwoven fabric laminate obtained as described above was affixed, and 10 evaluators were worn, and the wearability was evaluated according to the following criteria. 3: Evaluation of 10 out of 10 people without deviation. 2: Evaluation of 9-7 out of 10 people without deviation. 1: Six to three out of ten people rated no deviation. 0: Evaluation of 2 to 0 out of 10 people without deviation.
- peel strength [N] peel blocking resistance
- a weight of 4 kg (10 cm ⁇ 10 cm square) was placed on the non-woven fabric laminate obtained by superimposing two sheets, and stored in an oven at 90 ° C. for 2 hours. After storage for 2 hours, the peel strength of the nonwoven fabric laminate taken out from the oven was measured. This measurement was used as an index of the ease of blocking due to storage environment temperature, pressure, etc. when the nonwoven fabric laminate was stored in a roll state. That is, the smaller the peel strength, the harder it is to block and the higher the blocking resistance.
- the peel strength was measured by the following method.
- Two test pieces having a flow direction (MD) of 10.0 cm and a transverse direction (CD) of 5.0 cm were collected from the laminated nonwoven fabric laminate taken out from the oven.
- cut 15.0 cm of the gum tape “Teraoka Seisakusho Co., Ltd., cloth tape No. 159, 50 mm wide” and the flow direction (MD) of the test piece coincides with the long side direction of the gum tape with respect to the entire surface of the test piece. I stuck together.
- the gum tape was bonded to both sides of the test piece to produce a three-layer structure of gum tape / laminated nonwoven laminate / gum tape.
- Example 1 ⁇ Synthesis of low crystalline polypropylene> To a stainless steel reactor with a stirrer and an internal volume of 0.2 m 3 , n-heptane at 20 L / h, triisobutylaluminum at 15 mmol / h, dimethylanilinium tetrakispentafluorophenylborate and (1,2 ′ -Dimethylsilylene) (2,1'-dimethylsilylene) -bis (3-trimethylsilylmethylindenyl) zirconium dichloride, triisobutylaluminum, and propylene were previously contacted with a catalyst component at 6 ⁇ mol / h per zirconium. Continuous supply.
- Propylene and hydrogen were continuously supplied at a polymerization temperature of 70 ° C. while maintaining the gas phase hydrogen concentration at 8 mol% and the total pressure in the reactor at 0.7 MPa ⁇ G.
- SUMILIZER GP manufactured by Sumitomo Chemical Co., Ltd.
- SUMILIZER GP manufactured by Sumitomo Chemical Co., Ltd.
- a toluene solution containing 0.001 mmol of dimethylmethylene (3-tert-butyl-5-methylcyclopentadienyl) fluorenylzirconium dichloride and 0.3 mmol of methylaluminoxane (produced by Tosoh Finechem) in terms of aluminum was added into the polymerization vessel. Thereafter, polymerization was carried out for 20 minutes while maintaining the internal temperature at 40 ° C. and the internal pressure at 0.8 MPa by introducing ethylene. Thereafter, 20 ml of methanol was added to terminate the polymerization. After depressurization, the polymer was precipitated from the polymerization solution in 2 liters of methanol and dried under vacuum at 130 ° C. for 12 hours.
- the resulting polymer had a propylene content of 78 mol%, an ethylene content of 16 mol%, and a 1-butene content of 6 mol%.
- the melting point was 161 ° C.
- the crystallinity was 6%
- the tensile modulus was 23.5 MPa.
- the propylene / ethylene / 1-butene (C2 / C3 / C4) copolymer obtained as described above is referred to as PEB-1.
- MFR (according to ASTM D1238, measured at a temperature of 230 ° C. and a load of 2.16 kg) 8.5 g / 10 min, a density of 0.91 g / cm 3 , a melting point of 160 ° C. (hereinafter referred to as “polymer I”) ))
- polymer I a melting point of 160 ° C.
- polymer II (hereinafter referred to as “polymer II”) was melted using a 75 mm ⁇ extruder. Thereafter, a spunbond nonwoven fabric molding machine having a spinneret (die, number of holes: 2887 holes) capable of forming a concentric core-sheath composite fiber in which “Polymer I” is a core and “Polymer II” is a sheath. (Length in the direction perpendicular to the flow direction of the machine on the collecting surface: 800 mm), both the resin temperature and the die temperature are 250 ° C., the cooling air temperature is 20 ° C., and the span of the stretched air is 3750 m / min.
- a spinneret die, number of holes: 2887 holes
- an elastic nonwoven fabric was deposited as a second layer on the deposition surface of the stretchable spunbond nonwoven fabric.
- the raw material in which the low crystalline polypropylene synthesized in the above step and PEB-1 were previously blended at a mass ratio of 95: 5 was melted using a single screw extruder having a screw diameter of 75 mm ⁇ . Thereafter, the melted raw material was measured using a spunbond nonwoven fabric molding machine having a spinneret (die, 808 holes) (length in the direction perpendicular to the machine flow direction on the collecting surface: 800 mm) and the resin temperature and Both the die temperature was 215 ° C., the cooling air temperature was 20 ° C., and the stretched air wind speed was 3750 m / min.
- a core-sheath type composite fiber similar to the first layer is deposited as a third layer on the second layer made of an elastic nonwoven fabric by the same method as the first layer, thereby depositing a three-layer structure.
- a product was made. This deposit was heat-pressed with an embossing roll (embossing area ratio 18%, embossing temperature 70 ° C.), the total basis weight was 30.0 g / m 2 , and the basis weights of the first and third layers were 10 respectively. .0g / m 2, 2-layer basis weight were prepared nonwoven laminate is 10.0g / m 2 (33.3% mass fraction occupied for the entire elastic nonwoven layer).
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate. The maximum load, maximum load elongation and residual strain of the obtained nonwoven fabric laminate were all good.
- Example 2 A nonwoven fabric laminate was prepared in the same manner as in Example 1 except that the low crystalline polypropylene synthesized in Example 1 and PEB-1 were blended at a mass ratio of 90:10 and the embossing temperature was changed to 75 ° C. .
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate. The maximum load, maximum load elongation and residual strain of the obtained nonwoven fabric laminate were all good.
- Example 3 A non-woven fabric laminate was produced in the same manner as in Example 1 except that the low crystalline polypropylene synthesized in Example 1 and PEB-1 were blended at a mass ratio of 80:20 and the embossing temperature was changed to 80 ° C. .
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate.
- the evaluation of the maximum load, the maximum load elongation, the residual strain, the emboss residual rate, the tactile sensation, and the wearability of the obtained nonwoven fabric laminate were all good. Also, the evaluation of roll blocking resistance was good because the test piece could be peeled without breaking (material breakage) during the test.
- Example 4 A non-woven fabric laminate was prepared in the same manner as in Example 1 except that the low crystalline polypropylene synthesized in Example 1 and PEB-1 were blended at a mass ratio of 60:40 and the embossing temperature was changed to 95 ° C. .
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate.
- the maximum load, maximum load elongation and residual strain of the obtained nonwoven fabric laminate were all good. Also, the roll blocking resistance evaluation was good because the test piece could be peeled without breaking (material breakage) during the test.
- Example 5 A nonwoven fabric laminate was prepared in the same manner as in Example 1 except that the low crystalline polypropylene synthesized in Example 1 and PEB-1 were blended at a mass ratio of 50:50 and the embossing temperature was changed to 105 ° C. .
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate. The maximum load, maximum load elongation and residual strain of the obtained nonwoven fabric laminate were all good.
- Example 6 PEB-1 synthesized in Example 1 was made into Vistamaxx 2120 (manufactured by ExxonMobil: ethylene-propylene (C2 / C3) copolymer, melting point 162 ° C., crystallinity 10%, tensile elastic modulus 30.9 MPa).
- a nonwoven fabric laminate was produced in the same manner as in Example 1 except that the low crystalline polypropylene synthesized in Example 1 and Vistamaxx 2120 were blended at a mass ratio of 60:40 and the embossing temperature was changed to 105 ° C.
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate. The maximum load, maximum load elongation and residual strain of the obtained nonwoven fabric laminate were all good.
- Example 1 A nonwoven fabric laminate was produced in the same manner as in Example 1 except that the second layer was changed to a layer composed only of the low crystalline polypropylene synthesized in Example 1.
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate. Although the maximum load and maximum load elongation of the obtained nonwoven fabric laminate were good, the residual strain was large, the emboss residual rate was low, and the tactile evaluation was low. Moreover, the test piece was torn during the roll blocking resistance test (material breakage: 11 N or more), resulting in poor roll blocking resistance.
- Example 2 A non-woven fabric laminate was produced in the same manner as in Example 1 except that the low crystalline polypropylene synthesized in Example 1 and PEB-1 were blended at a mass ratio of 40:60 and the embossing temperature was changed to 120 ° C. .
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate. Although the maximum load and residual strain of the obtained nonwoven fabric laminate were good, the nonwoven fabric had a small maximum load elongation.
- the obtained polymer had an ethylene content of 88 mol% and a 1-butene content of 12 mol%.
- the melting point was 70 ° C., the crystallinity was 24%, and the tensile modulus was 23.5 MPa.
- the ethylene / 1-butene (C2 / C4) copolymer obtained as described above is designated as EB-2.
- Example 1 ⁇ Manufacture of nonwoven fabric laminate> The second layer was formed except that the low crystalline polypropylene synthesized in Example 1 and PB-3 synthesized in the above process were blended at a mass ratio of 60:40 and the embossing temperature was changed to 105 ° C.
- a nonwoven fabric laminate was produced in the same manner as in Example 1.
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate.
- the obtained nonwoven fabric laminate had a small maximum load elongation and a large residual strain.
- Example 5 For the second layer, the low crystalline polypropylene synthesized in Example 1 and affinity PL 1850 (manufactured by Dow Chemical Company: ethylene / 1-octene (C2 / C8) copolymer, melting point 100 ° C., crystallinity 35%, A nonwoven fabric laminate was prepared in the same manner as in Example 1 except that the tensile modulus (75.4 MPa) was blended at a mass ratio of 95: 5 and the embossing temperature was changed to 80 ° C.
- affinity PL 1850 manufactured by Dow Chemical Company: ethylene / 1-octene (C2 / C8) copolymer, melting point 100 ° C., crystallinity 35%
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate.
- the obtained nonwoven fabric laminate had a large residual strain.
- Example 6 Low crystalline polypropylene synthesized in Example 1 for the formation of the second layer and affinity PL 1850 (manufactured by Dow Chemical Co .: ethylene / 1-octene (C2 / C8) copolymer, melting point 100 ° C., crystallinity) 35% and tensile elastic modulus of 75.4 MPa) were blended at a mass ratio of 60:40, but the spinnability was remarkably poor and a nonwoven fabric laminate could not be obtained.
- affinity PL 1850 manufactured by Dow Chemical Co .: ethylene / 1-octene (C2 / C8) copolymer, melting point 100 ° C., crystallinity) 35% and tensile elastic modulus of 75.4 MPa
- Example 7 Low crystalline polypropylene synthesized in Example 1 for the formation of the second layer and Engage 8407 (manufactured by Dow Chemical Company: ethylene / 1-octene (C2 / C8) copolymer, melting point 63 ° C., crystallinity 26) %, Tensile elastic modulus 8.2 MPa) was blended at a mass ratio of 60:40, but the spinnability was remarkably poor and a nonwoven fabric laminate could not be obtained.
- Engage 8407 manufactured by Dow Chemical Company: ethylene / 1-octene (C2 / C8) copolymer, melting point 63 ° C., crystallinity 26) %, Tensile elastic modulus 8.2 MPa
- Example 8 For the second layer, the low crystalline polypropylene synthesized in Example 1 and Prime Polypro S119 (manufactured by Prime Polymer Co., Ltd .: polypropylene (C3) homopolymer, melting point 160 ° C., crystallinity 50%, tensile modulus 1570 MPa) A nonwoven fabric laminate was produced in the same manner as in Example 1 except that the composition was blended at a mass ratio of 80:20 and the embossing temperature was changed to 85 ° C.
- Prime Polypro S119 manufactured by Prime Polymer Co., Ltd .: polypropylene (C3) homopolymer, melting point 160 ° C., crystallinity 50%, tensile modulus 1570 MPa
- the nonwoven fabric laminate obtained as described above had almost no adhesion to the surface of the metal roll in the embossing process, and the moldability was good. Moreover, when the nonwoven fabric laminate was wound into a roll state, roll blocking did not occur, and it could be pulled out easily.
- Table 1 shows the results of measuring physical properties of the obtained nonwoven fabric laminate.
- the obtained nonwoven fabric laminate had a low maximum load elongation, a large residual strain, and a poor touch feeling.
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Abstract
Description
<1>弾性不織布と、前記弾性不織布の少なくとも片面側に配置され、少なくとも一方向の最大荷重伸度が50%以上である伸長性スパンボンド不織布と、を有し、下記(1)及び(2)を満たす不織布積層体。
(1)前記弾性不織布は、下記(a)~(f)を満たす低結晶性ポリプロピレンと、エチレンに由来する構成単位及びプロピレンに由来する構成単位を含み、融点が100℃以上であり、結晶化度が15%以下であるαオレフィン共重合体Aと、を含む樹脂組成物からなる。
(2)前記樹脂組成物は、前記樹脂組成物100質量部に対してαオレフィン共重合体Aを5質量部~50質量部含む。
(a)[mmmm]=20~60モル%
(b)[rrrr]/(1-[mmmm])≦0.1
(c)[rmrm]>2.5モル%
(d)[mm]×[rr]/[mr]2≦2.0
(e)重量平均分子量(Mw)=10,000~200,000
(f)分子量分布(Mw/Mn)<4
(a)~(d)中、[mmmm]はメソペンタッド分率であり、[rrrr]はラセミペンタッド分率であり、[rmrm]はラセミメソラセミメソペンタッド分率であり、[mm]、[rr]及び[mr]はそれぞれトリアッド分率である。
本発明の不織布積層体は、弾性不織布と、前記弾性不織布の少なくとも片面側に配置され、少なくとも一方向の最大荷重伸度が50%以上である伸長性スパンボンド不織布と、を有し、下記(1)及び(2)を満たす。
(1)前記弾性不織布は、下記(a)~(f)を満たす低結晶性ポリプロピレンと、エチレンに由来する構成単位及びプロピレンに由来する構成単位を含み、融点が100℃以上であり、結晶化度が15%以下であるαオレフィン共重合体Aと、を含む樹脂組成物からなる。
(2)前記樹脂組成物は、前記樹脂組成物100質量部に対してαオレフィン共重合体Aを5質量部~50質量部含む。
(a)[mmmm]=20~60モル%
(b)[rrrr]/(1-[mmmm])≦0.1
(c)[rmrm]>2.5モル%
(d)[mm]×[rr]/[mr]2≦2.0
(e)重量平均分子量(Mw)=10,000~200,000
(f)分子量分布(Mw/Mn)<4
(a)~(d)中、[mmmm]はメソペンタッド分率であり、[rrrr]はラセミペンタッド分率であり、[rmrm]はラセミメソラセミメソペンタッド分率であり、[mm]、[rr]及び[mr]はそれぞれトリアッド分率である。
本発明の不織布積層体を構成する弾性不織布は、後述する(a)~(f)を満たす低結晶性ポリプロピレン(以下、単に低結晶性ポリプロピレンともいう)と、エチレンに由来する構成単位及びプロピレンに由来する構成単位を含み、融点が100℃以上、結晶化度が15%以下であるαオレフィン共重合体Aと、を含む樹脂組成物からなる。
弾性不織布を構成する繊維は、通常、繊維径が50μm以下であり、好ましくは40μm以下であり、より好ましくは30μm以下である。
弾性不織布を構成する樹脂組成物は、樹脂組成物100質量部に対して、αオレフィン共重合体Aを5質量部~50質量部含む。さらに、樹脂組成物は、樹脂組成物100質量部に対して、低結晶性ポリプロピレンを95質量部~50質量部含むことが好ましい。このような樹脂組成物からなる弾性不織布を有する不織布積層体は、残留歪が小さく、伸縮性に優れ、最大荷重伸度が高く、触感、装着性及び耐ロールブロッキング性に優れる。樹脂組成物は、樹脂組成物100質量部に対してαオレフィン共重合体Aを5質量部~45質量部含み、低結晶性ポリプロピレンを95質量部~55質量部含むことがより好ましい。
αオレフィン共重合体Aは、エチレンに由来する構成単位及びプロピレンに由来する構成単位を含み、融点が100℃以上であり、結晶化度が15%以下である。
αオレフィン共重合体Aは、上記条件を満たすものであれば特に制限されず、エチレン又はプロピレン以外のαオレフィンに由来する構成単位の1種以上をさらに含んでもよい。エチレン又はプロピレン以外のαオレフィンとしては、1-ブテン、1-ヘキセン、4メチル-1-ペンテン、1-オクテン等が挙げられる。
結晶化度=ΔH/ΔH0×100(%)
低結晶性ポリプロピレンは、下記(a)~(f)の要件を満たす重合体である。
(a)[mmmm]=20~60モル%:
低結晶性ポリプロピレンのメソペンタッド分率[mmmm]が20モル%以上であると、べたつきの発生が抑制され、60モル%以下であると、結晶化度が高くなりすぎることがないので、弾性回復性が良好となる。このメソペンタッド分率[mmmm]は、好ましくは30~50モル%であり、より好ましくは40~50モル%である。
方法:プロトン完全デカップリング法
濃度:220mg/ml
溶媒:1,2,4-トリクロロベンゼンと重ベンゼンの90:10(容量比)混合溶媒
温度:130℃
パルス幅:45°
パルス繰り返し時間:4秒
積算:10000回
M=m/S×100
R=γ/S×100
S=Pββ+Pαβ+Pαγ
S:全プロピレン単位の側鎖メチル炭素原子のシグナル強度
Pββ:19.8~22.5ppm
Pαβ:18.0~17.5ppm
Pαγ:17.5~17.1ppm
γ:ラセミペンタッド連鎖:20.7~20.3ppm
m:メソペンタッド連鎖:21.7~22.5ppm
[rrrr]/[1-mmmm]の値は、上記のペンタッド単位の分率から求められ、低結晶性ポリプロピレンの規則性分布の均一さを示す指標である。この値が大きくなると、既存触媒系を用いて製造される従来のポリプロピレンのように高規則性ポリプロピレンとアタクチックポリプロピレンの混合物となり、べたつきの原因となる。
低結晶性ポリプロピレンにおいて、[rrrr]/(1-[mmmm])が0.1以下であると、得られる弾性不織布におけるべたつきが抑制される。このような観点から、[rrrr]/(1-[mmmm])は、好ましくは0.05以下であり、より好ましくは0.04以下である。
低結晶性ポリプロピレンのラセミメソラセミメソ分率[rmrm]が2.5モル%を超える値であると、該低結晶性ポリプロピレンのランダム性が増加し、弾性不織布の弾性回復性がさらに向上する。[rmrm]は、好ましくは2.6モル%以上であり、より好ましくは2.7モル%以上である。その上限は、通常10モル%程度である。
[mm]×[rr]/[mr]2は、低結晶性ポリプロピレンのランダム性の指標を示し、この値が2.0以下であると、弾性不織布は十分な弾性回復性が得られ、かつべたつきも抑制される。[mm]×[rr]/[mr]2は、0.25に近いほどランダム性が高くなる。上記十分な弾性回復性を得る観点から、[mm]×[rr]/[mr]2は、好ましくは0.25を超え1.8以下であり、より好ましくは0.5~1.5である。
低結晶性ポリプロピレンにおいて重量平均分子量が10,000以上であると、該低結晶性ポリプロピレンの粘度が低すぎず適度のものとなるため、弾性不織布の製造時の糸切れが抑制される。また、重量平均分子量が200,000以下であると、上記低結晶性ポリプロピレンの粘度が高すぎず、紡糸性が向上する。この重量平均分子量は、好ましくは30,000~150,000であり、より好ましくは50,000~150,000である。この重量平均分子量の測定法については後述する。
低結晶性ポリプロピレンにおいて、分子量分布(Mw/Mn)が4未満であると、弾性不織布のべたつきの発生が抑制される。この分子量分布は、好ましくは3以下である。
上記重量平均分子量(Mw)は、ゲルパーミエイションクロマトグラフィ(GPC)法により、下記の装置及び条件で測定したポリスチレン換算の重量平均分子量であり、上記分子量分布(Mw/Mn)は、同様にして測定した数平均分子量(Mn)及び上記重量平均分子量(Mw)より算出した値である。
カラム :TOSO GMHHR-H(S)HT
検出器 :液体クロマトグラム用RI検出器 WATERS 150C
[測定条件]
溶媒 :1,2,4-トリクロロベンゼン
測定温度 :145℃
流速 :1.0ml/分
試料濃度 :2.2mg/ml
注入量 :160μl
検量線 :Universal Calibration
解析プログラム:HT-GPC(Ver.1.0)
(g)示差走査型熱量計(DSC)を用いて、窒素雰囲気下-10℃で5分間保持した後10℃/分で昇温させることにより得られた融解吸熱カーブの最も高温側に観測されるピークのピークトップとして定義される融点(Tm-D)が0℃~120℃である。
本発明の不織布積層体を構成する伸長性スパンボンド不織布は、少なくとも一方向の最大荷重伸度が50%以上であり、好ましくは70%以上であり、より好ましくは100%以上であり、更に好ましくは弾性回復が殆どない性質を有する不織布である。
オレフィン系重合体を用いて得られる不織布としては、(1)流動誘起結晶化誘導期の差が100秒以上の二種以上のオレフィン系重合体(高融点のプロピレン系重合体と低融点のプロピレン系重合体)からなる芯鞘型複合繊維、並列型複合繊維(サイド・バイ・サイド型複合繊維)又は捲縮複合繊維からなるスパンボンド不織布、(2)プロピレン系重合体とエチレン系重合体とからなる芯鞘型複合繊維、並列型複合繊維又は捲縮複合繊維からなるスパンボンド不織布、(3)芯部をメルトフローレート(以下MFRともいう。ASTMD-1238、230℃、荷重2160g)が1g/10分~1000g/10分の範囲にある低MFRのプロピレン系重合体とし、鞘部をMFRが1g/10分~1000g/10分の範囲にある高MFRのプロピレン系重合体とし、且つ、MFRの差が1g/10分以上、好ましくは15g/10分以上、より好ましくは30g/10分以上、更に好ましくは40g/10分以上である同芯の芯鞘複合繊維からなるスパンボンド不織布等が挙げられる。
伸長性スパンボンド不織布がオレフィン系重合体の1種又は2種以上から形成される場合、オレフィン系重合体としては、エチレン、プロピレン、1-ブテン、1-ヘキセン、4-メチル-1-ペンテン、1-オクテン等のαオレフィンの単独重合体又は共重合体であるエチレン系重合体、プロピレン系重合体、結晶性の重合体等が挙げられる。
エチレン系重合体として具体的には、高圧法低密度ポリエチレン、線状低密度ポリエチレン(所謂LLDPE)、高密度ポリエチレン(所謂HDPE)等のエチレン単独重合体エチレン・αオレフィンランダム共重合体等が挙げられる。
プロピレン系重合体として具体的には、ポリプロピレン(プロピレン単独重合体)、プロピレン・1-ブテンランダム共重合体、プロピレン・エチレンランダム共重合体、プロピレン・エチレン・1-ブテンランダム共重合体等のプロピレン・αオレフィンランダム共重合体などが挙げられる。
結晶性の重合体として具体的には、ポリ1-ブテン、ポリ4-メチル-1-ペンテン等が挙げられる。
上述したプロピレン系重合体は、通常、ポリプロピレンの名称で、製造・販売されている結晶性樹脂である。具体的には、通常、融点(Tm)が155℃以上、好ましくは157℃~165℃の範囲にあるプロピレンの単独重合体又はプロピレンを主成分とし、エチレン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、4-メチル-1-ペンテン等の炭素数2以上(但し炭素数3を除く)、好ましくは炭素数2~8(但し炭素数3を除く)である1種若しくは2種以上のα-オレフィンを共重合成分とする共重合体、及び、通常、融点(Tm)が130℃~155℃未満、好ましくは130℃~150℃の範囲にあるプロピレンとエチレン、1-ブテン、1-ペンテン、1-ヘキセン、1-オクテン、4-メチル-1-ペンテン等の炭素数2以上(但し炭素数3を除く)、好ましくは炭素数2~8(但し炭素数3を除く)である1種若しくは2種以上のαオレフィンとの共重合体が挙げられる。共重合体としては、ランダム共重合体、ブロック共重合体等が挙げられる。
本発明に係る伸長性スパンボンド不織布は、エチレン系重合体と、プロピレン系重合体とを含むオレフィン系重合体組成物から形成されることが好ましい。オレフィン系重合体組成物は、プロピレン系重合体を通常は80質量%~99質量%含み、好ましくは84質量%~96質量%含み、エチレン系重合体を通常は20質量%~1質量%含み、好ましくは16質量%~4質量%含む(但し、プロピレン系重合体+エチレン系重合体=100質量%)。
本発明の不織布積層体は、用途に応じて弾性不織布及び伸長性スパンボンド不織布以外の他の層を1又は2以上有していてもよい。
本発明の不織布積層体は、弾性不織布の原料となる低結晶性ポリプロピレン及びαオレフィン共重合体A、伸長性スパンボンド不織布の原料となるオレフィン系重合体、並びに必要に応じて用いられる添加剤を用いて、公知の不織布の製造方法により製造し得る。
まず、一列目の紡糸装置に備えられた押出機、必要に応じて二個以上の押出機でオレフィン系重合体、必要に応じて二種以上のオレフィン系重合体を溶融し、多数の紡糸孔(ノズル)を備えた口金(ダイ)、必要に応じて芯鞘構造を有する紡糸孔に導入し、吐出する。その後、溶融紡糸されたオレフィン系重合体を含む長繊維を冷却室に導入し、冷却風により冷却した後、延伸エアにより長繊維を延伸(牽引)し、伸長性スパンボンド不織布を移動捕集面上に堆積させる。
他方、二列目の紡糸装置に備えられた押出機で低結晶性ポリプロピレンとαオレフィン共重合体Aを含む樹脂組成物を溶融し、多数の紡糸孔(ノズル)を備えた口金(ダイ)を有する紡糸孔に導入し、樹脂組成物を吐出する。その後、溶融紡糸された樹脂組成物を含む長繊維を冷却室に導入し、冷却風により冷却した後、延伸エアにより長繊維を延伸(牽引)し、伸長性スパンボンド不織布上に堆積させて、弾性不織布を形成する。
必要に応じて、三列目の紡糸装置を用いて、伸長性スパンボンド不織布を弾性不織布上に堆積させてもよい。
本発明の伸縮性不織布積層体は、前記不織布積層体を延伸することによって得られる、伸縮性を有する不織布積層体である。
本発明の繊維製品は、本発明の不織布積層体又は伸縮性不織布積層体を含む。繊維製品は特に制限されず、使い捨ておむつ、生理用品等の吸収性物品、衛生マスク等の衛生物品、包帯等の医療物品、衣料素材、包装材などが挙げられる。本発明の繊維製品は、本発明の不織布積層体又は伸縮性不織布積層体を伸縮部材として含むことが好ましい。
不織布積層体から流れ方向(MD)が200mm、横方向(CD)が50mmの試験片を6枚採取した。なお、採取場所はMD、CDともに任意の3箇所とした(計6箇所)。次いで、採取した各試験片の質量(g)を、上皿電子天秤(研精工業社製)を用いてそれぞれ測定した。各試験片の質量の平均値を求めた。求めた平均値から1m2当たりの質量(g)に換算し、小数点第1位を四捨五入して、目付〔g/m2〕とした。
不織布積層体から、流れ方向(MD)が200mm、横方向(CD)が50mmの試験片を5枚採取した。この試験片について、定速伸長型引張試験機を用いて、チャック間100mm、引張速度100mm/分の条件で引張試験を行った。試験片に掛かる最大の荷重〔N/50mm〕を測定した。また、最大荷重における試験片の伸び率〔%〕を測定した。5枚の試験片の平均値を求め、それぞれ、最大荷重、最大荷重伸度とした。伸張性スパンボンド不織布の最大荷重伸度〔%〕は、上記と同じ方法で測定することによって求めた。
不織布積層体から、流れ方向(MD)が200mm、横方向(CD)が50mmの試験片を5枚採取した。この試験片について、定速伸長型引張り試験機を用いて、チャック間100mm、引張速度100mm/分、延伸倍率100%の条件で延伸した後、直ちに同じ速度で原長まで回復させた。さらに直ちに同じ速度で延伸倍率100%の条件で延伸し
た後、直ちに同じ速度で原長まで回復させて、回復時の歪を測定した。5枚の不織布積層体についての平均値を残留歪(単位:%)として評価した。
スパンボンド不織布製造装置のノズル面近傍の紡糸状況を目視で観察し、5分あたりの糸切れ回数(単位:回/5分)を数えた。糸切れ回数が0回/5分であれば「○」、糸切れが発生し不織布採取に至らない場合は「×」と評価した。
エンボス工程にて、金属ロールを5分間走行させ、不織布積層体がエンボスロールを通過する際に生じる付着状態を評価した。
○:目視にて付着が全く確認されない状態。
△:目視にて付着が殆ど確認されない状態。
×:目視にて付着が確認される状態、又はエンボスロールに巻付く状態。
不織布積層体から、流れ方向(MD)が250mm、横方向(CD)が200mmの試験片を1枚採取した。この試験片を、CD方向が図2に示すような予熱装置のロール回転方向と一致するように挿入し、予熱された不織布積層体を得た。得られた不織布積層体を直ちに図1に示すようなギア加工機のロール回転方向とCD方向が一致するように挿入し、MD方向(不織布積層体の流れ方向)にギア延伸された不織布積層体を得た。なお予熱はロール表面温度が60℃となるように調整し、ギア加工機に搭載されるギアロールは各々直径が200mm、ギアピッチが2.5mmであり、両ロールの噛み合い深さを5.5mmとなるように調整した。上記のようにして得たギア延伸された不織布積層体について、評価者10人が手触りを確認し、触感を下記基準で評価した。
3:10人の内10人がザラツキが無いと評価。
2:10人の内9~7人がザラツキが無いと評価。
1:10人の内6~3人がザラツキが無いと評価。
0:10人の内2~0人がザラツキが無いと評価。
触感評価と同様の方法で得たギア延伸された不織布積層体について、SEMによる形態観察を行い、エンボスの残存率を評価した。エンボス残存率が高いほど、触感が良好であるとした。エンボス残存率は下記の式を用いて算出した。
エンボス残存率=破壊されていないエンボス数/観察されたエンボス数×100
なお、ギア延伸された不織布積層体のSEMによるエンボス部の観察により、エンボス部での孔あきや繊維の脱離、エンボス部とその境界における繊維切れが確認されなかったエンボス部を「破壊されていないエンボス」とした。
不織布積層体から、流れ方向(MD)が250mm、横方向(CD)が200mmの試験片を切り取った。この試験片を、CD方向が図2に示すような予熱装置のロール回転方向と一致するように挿入し、予熱された不織布積層体を得た。得られた不織布積層体を直ちに図1に示すようなギア加工機のロール回転方向とCD方向が一致するように挿入し、MD方向(不織布積層体の流れ方向)にギア延伸された不織布積層体を得た。なお予熱はロール表面温度が60℃となるように調整し、ギア加工機に搭載されるギアロールは各々直径が200mm、ギアピッチが2.5mmであり、両ロールの噛み合い深さを3.5mmとなるように調整した。市販のオムツから不織布を剥がし、上記のようにして得たギア延伸された不織布積層体を貼り付け、評価者10人が装着し、装着性を下記基準で評価した。
3:10人の内10人がズレ無しの評価。
2:10人の内9~7人がズレ無しの評価。
1:10人の内6~3人がズレ無しの評価。
0:10人の内2~0人がズレ無しの評価。
不織布積層体の耐ロールブロッキング性を以下の方法で評価した。
2枚重ね合せた不織布積層体に、重り4kg(10cm×10cm角)を載せ、90℃のオーブンに2時間保管した。2時間の保管後、オーブンより取り出した不織布積層体の剥離強度を測定した。この測定により、不織布積層体をロール状態で保管した場合の、保管環境温度や圧力などによるブロッキングのしやすさの指標とした。つまり、剥離強度が小さいほど、ブロッキングしにくく、耐ブロッキング性が高いことになる。剥離強度は以下の方法で測定した。
オーブンから取り出した重ね合せた不織布積層体から、流れ方向(MD)が10.0cm、横方向(CD)が5.0cmの試験片2枚を採取した。次に、ガムテープ「(株)寺岡製作所、布テープNo.159、50mm巾」を15.0cm切り取り、上記試験片の全面に対し、試験片の流れ方向(MD)とガムテープの長辺方向が一致するように貼り合わせた。ガムテープは試験片の両面に貼り合わせ、ガムテープ/重ね合せた不織布積層体/ガムテープという三層構造を作製した。次に、上記三層構造体の両面それぞれのガムテープを低速伸長型引張試験機のチャック上下にそれぞれ取付け、チャック間50mm、引張速度100mm/分の条件で引っ張ることにより、重ね合せた不織布積層体の剥離強度〔N〕を測定した。剥離強度は、2枚の試験片の平均値を少数点第三位で四捨五入し、剥離強度とした。重ね合せた不織布積層体の剥離強度が、基材破壊を起こす程度に強固に固定されている場合は、「材破」とした。
<低結晶性ポリプロピレンの合成>
攪拌機付き、内容積0.2m3のステンレス製反応器に、n-ヘプタンを20L/hで、トリイソブチルアルミニウムを15mmol/hで、さらに、ジメチルアニリニウムテトラキスペンタフルオロフェニルボレートと(1,2’-ジメチルシリレン)(2,1’-ジメチルシリレン)-ビス(3-トリメチルシリルメチルインデニル)ジルコニウムジクロライドとトリイソブチルアルミニウムとプロピレンとを事前に接触させて得られた触媒成分をジルコニウムあたり6μmol/hで連続供給した。
得られた重合溶液に、SUMILIZER GP(住友化学社製)を1000ppmになるように添加し、溶媒を除去することにより、プロピレン重合体を得た。
充分に窒素置換した容量2000mlの重合装置に、833mlの乾燥ヘキサンと、100gの1-ブテンと、トリイソブチルアルミニウム(1.0mmol)とを常温で仕込んだ。その後、重合装置の内温を40℃に昇温し、プロピレンを導入して加圧した。その後、エチレンを導入して系内圧力を0.8MPaに調整した。
MFR(ASTM D1238に準拠して、温度230℃、荷重2.16kgで測定)8.5g/10分、密度0.91g/cm3、融点160℃のプロピレン単独重合体(以下、「重合体I」という)を50mmφの押出機を用いて溶融し、それとは独立してMFR(ASTM D1238に準拠して、温度230℃、荷重2.16kgで測定)60g/10分、密度0.91g/cm3、融点160℃のプロピレン単独重合体(以下、「重合体IIという」)を75mmφの押出機を用いて溶融した。その後、「重合体I」が芯、「重合体II」が鞘となるような同芯の芯鞘複合繊維の成形が可能な紡糸口金(ダイ、孔数2887ホール)を有するスパンボンド不織布成形機(捕集面上の機械の流れ方向に垂直な方向の長さ:800mm)を用いて、樹脂温度とダイ温度がともに250℃、冷却風温度20℃、延伸エアー風速3750m/分の条件でスパンボンド法により複合溶融紡糸を行い、芯部と鞘部の質量比が10/90の同芯の芯鞘型複合繊維からなる伸長性スパンボンド不織布を捕集面上に第一層目として堆積させた。
実施例1で合成した低結晶性ポリプロピレンとPEB-1を質量比90:10の割合でブレンドし、エンボス温度を75℃に変更した以外は、実施例1と同様にして不織布積層体を作製した。
実施例1で合成した低結晶性ポリプロピレンとPEB-1を質量比80:20の割合でブレンドし、エンボス温度を80℃に変更した以外は、実施例1と同様にして不織布積層体を作製した。
実施例1で合成した低結晶性ポリプロピレンとPEB-1を質量比60:40の割合でブレンドし、エンボス温度を95℃に変更した以外は、実施例1と同様にして不織布積層体を作製した。
実施例1で合成した低結晶性ポリプロピレンとPEB-1を質量比50:50の割合でブレンドし、エンボス温度を105℃に変更した以外は、実施例1と同様にして不織布積層体を作製した。
実施例1で合成したPEB-1を、Vistamaxx 2120(ExxonMobil社製:エチレン・プロピレン(C2/C3)共重合体、融点162℃、結晶化度10%、引張り弾性率30.9MPa)とし、実施例1で合成した低結晶性ポリプロピレンとVistamaxx 2120を質量比60:40の割合でブレンドし、エンボス温度を105℃に変更した以外は、実施例1と同様にして不織布積層体を作製した。
第2層目を実施例1で合成した低結晶性ポリプロピレンのみからなる層に変更した以外は、実施例1と同様にして不織布積層体を作製した。
実施例1で合成した低結晶性ポリプロピレンとPEB-1を質量比40:60の割合でブレンドし、エンボス温度を120℃に変更した以外は、実施例1と同様にして不織布積層体を作製した。
<エチレン・1-ブテン共重合体の製造>
(触媒溶液の調製)
トリフェニルカルベニウム(テトラキスペンタフルオロフェニル)ボレートを18.4mg採り、トルエンを5ml加えて溶解させ、濃度が0.004ミリモル/mlのトルエン溶液を調製した。また、〔ジメチル(t-ブチルアミド)(テトラメチル-η5-シクロペンタジエニル)シラン〕チタンジクロライドを1.8mg採り、トルエンを5ml加えて溶解させ、濃度が0.001ミリモル/mlのトルエン溶液を調製した。
重合開始時においては、トリフェニルカルベニウム(テトラキスペンタフルオロフェニル)ボレートのトルエン溶液を0.38ml、〔ジメチル(t-ブチルアミド)(テトラメチル-η5-シクロペンタジエニル)シラン〕チタンジクロライドのトルエン溶液を0.38ml採り、さらに希釈用のトルエンを4.24ml加えて、トリフェニルカルベニウム(テトラキスペンタフルオロフェニル)ボレートがB換算で0.002ミリモル/リットルに、〔ジメチル(t-ブチルアミド)(テトラメチル-η5-シクロペンタジエニル)シラン〕チタンジクロライドがTi換算で0.0005ミリモル/リットルとなるトルエン溶液を5ml調製し、触媒溶液とした。
充分に窒素置換した容量1.5リットルの撹拌翼付きSUS製オートクレーブに、23℃でヘプタン750mlを導入した。このオートクレーブに、撹拌翼を回し、かつ氷冷しながら1-ブテン6g、水素150mlを導入した。次に、このオートクレーブを100℃まで加熱し、更に全圧が6kg/cm2となるように、エチレンで加圧した。オートクレーブの内圧が6kg/cm2になったところで、トリイソブチルアルミニウム(TIBA)の1.0ミリモル/mlヘキサン溶液1.0mlを窒素で圧入した。続いて、上記触媒のトルエン溶液5mlを窒素でオートクレーブに圧入して重合を開始した。その後、5分間、オートクレーブを内温が100℃になるように温度調節し、かつ圧力が6kg/cm2となるように直接的にエチレンの供給を行った。重合を開始してから5分後に、オートクレーブにポンプでメタノール5mlを装入して重合を停止させ、オートクレーブを大気圧まで脱圧した。反応溶液に3リットルのメタノールを撹拌しながら注いだ。得られた溶媒を含む重合体を130℃、13時間、600Torr(80000Pa)で乾燥した。得られたポリマーのエチレン含量は88モル%であり、1-ブテン含量は12モル%であった。融点は70℃、結晶化度は24%、引張り弾性率は23.5MPaであった。上記のようにして得られたエチレン・1-ブテン(C2/C4)共重合体をEB-2とする。
第2層目の形成のために実施例1で合成した低結晶性ポリプロピレンと上記工程で合成したEB-2を質量比60:40の割合でブレンドしたが、紡糸性が著しく悪く、不織布積層体を得るに至らなかった。
<プロピレン・1-ブテン共重合体の製造>
充分に窒素置換した2リットルのオートクレーブに、ヘキサンを900ml、1-ブテンを90g仕込み、トリイソブチルアルミニウムを1ミリモル加え、70℃に昇温した。その後、プロピレンを供給して全圧7kg/cm2Gにし、メチルアルミノキサン0.30ミリモル、上記PEB-1の製造例と同様の方法で製造されたrac-ジメチルシリレン-ビス{1-(2-メチル-4-フェニルインデニル)}ジルコニウムジクロライドをZr原子に換算して0.001ミリモル加え、プロピレンを連続的に供給して全圧を7kg/cm2Gに保ちながら30分間重合を行った。重合後、脱気して大量のメタノール中でポリマーを回収し、110℃で12時間減圧乾燥した。得られたポリマーのプロピレン含量は74モル%であり、1-ブテン含量は26モル%であった。融点は77℃、結晶化度は19%、引張り弾性率は217.3MPaであった。上記のようにして得られたプロピレン・1-ブテン(C3/C4)共重合体をPB-3とする。
第2層目を、実施例1で合成した低結晶性ポリプロピレンと上記工程で合成したPB-3を質量比60:40の割合でブレンドし、エンボス温度を105℃に変更して形成した以外は、実施例1と同様にして不織布積層体を作製した。
第2層目を、実施例1で合成した低結晶性ポリプロピレンとアフィニティーPL 1850(Dow Chemical社製:エチレン・1-オクテン(C2/C8)共重合体、融点100℃、結晶化度35%、引張り弾性率75.4MPa)を質量比95:5の割合でブレンドし、エンボス温度を80℃に変更して形成した以外は、実施例1と同様にして不織布積層体を作製した。
第2層目の形成のために実施例1で合成した低結晶性ポリプロピレンとアフィニティーPL 1850(Dow Chemical社製:エチレン・1-オクテン(C2/C8)共重合体、融点100℃、結晶化度35%、引張り弾性率75.4MPa)を質量比60:40の割合でブレンドしたが、紡糸性が著しく悪く、不織布積層体を得るに至らなかった。
第2層目の形成のために実施例1で合成した低結晶性ポリプロピレンとエンゲージ8407(Dow Chemical社製:エチレン・1-オクテン(C2/C8)共重合体、融点63℃、結晶化度26%、引張り弾性率8.2MPa)を質量比60:40の割合でブレンドしたが、紡糸性が著しく悪く、不織布積層体を得るに至らなかった。
第2層目を、実施例1で合成した低結晶性ポリプロピレンと、プライムポリプロS119(プライムポリマー社製:ポリプロピレン(C3)単独重合体、融点160℃、結晶化度50%、引張り弾性率1570MPa)とを質量比80:20の割合でブレンドし、エンボス温度を85℃に変更して形成した以外は、実施例1と同様にして不織布積層体を作製した。
Claims (13)
- 弾性不織布と、前記弾性不織布の少なくとも片面側に配置され、少なくとも一方向の最大荷重伸度が50%以上である伸長性スパンボンド不織布と、を有し、下記(1)及び(2)を満たす不織布積層体。
(1)前記弾性不織布は、下記(a)~(f)を満たす低結晶性ポリプロピレンと、エチレンに由来する構成単位及びプロピレンに由来する構成単位を含み、融点が100℃以上であり、結晶化度が15%以下であるαオレフィン共重合体Aと、を含む樹脂組成物からなる。
(2)前記樹脂組成物は、前記樹脂組成物100質量部に対してαオレフィン共重合体Aを5質量部~50質量部含む。
(a)[mmmm]=20~60モル%
(b)[rrrr]/(1-[mmmm])≦0.1
(c)[rmrm]>2.5モル%
(d)[mm]×[rr]/[mr]2≦2.0
(e)重量平均分子量(Mw)=10,000~200,000
(f)分子量分布(Mw/Mn)<4
(a)~(d)中、[mmmm]はメソペンタッド分率であり、[rrrr]はラセミペンタッド分率であり、[rmrm]はラセミメソラセミメソペンタッド分率であり、[mm]、[rr]及び[mr]はそれぞれトリアッド分率である。 - 前記樹脂組成物は、前記樹脂組成物100質量部に対して、前記低結晶性ポリプロピレンを95質量部~50質量部含む請求項1に記載の不織布積層体。
- 前記αオレフィン共重合体Aは、引張り弾性率が100MPa以下である請求項1又は請求項2に記載の不織布積層体。
- 前記αオレフィン共重合体Aは、エチレン、プロピレン及びブテンに由来する構成単位を含む共重合体である請求項1~請求項3のいずれか1項に記載の不織布積層体。
- 前記弾性不織布の両面側に前記伸長性スパンボンド不織布が配置されている請求項1~請求項4のいずれか1項に記載の不織布積層体。
- 前記弾性不織布は、スパンボンド法により得られる不織布である請求項1~請求項5のいずれか1項に記載の不織布積層体。
- 前記伸長性スパンボンド不織布が、芯部をMFRが1g/10分~200g/10分の範囲にある低MFRのプロピレン系重合体とし、鞘部をMFRが16g/10分~215g/10分の範囲にある高MFRのプロピレン系重合体とし、且つ、前記低MFRのプロピレン系重合体と前記高MFRのプロピレン系重合体のMFRの差が15g/10分以上である、同芯の芯鞘型複合繊維からなる伸長性スパンボンド不織布である請求項1~請求項6のいずれか1項に記載の不織布積層体。
- 前記伸長性スパンボンド不織布が、結晶性プロピレン系重合体80質量%~99質量%と、高密度ポリエチレン20質量%~1質量%と、を含むオレフィン系重合体組成物からなる請求項1~請求項7のいずれか1項に記載の不織布積層体。
- 前記弾性不織布と前記伸長性スパンボンド不織布との目付比(弾性不織布:伸長性スパンボンド不織布)が10:90~90:10の範囲にある請求項1~請求項8のいずれか1項に記載の不織布積層体。
- 請求項1~請求項9のいずれか1項に記載の不織布積層体を、延伸加工して得られる伸縮性不織布積層体。
- 請求項1~請求項9のいずれか1項に記載の不織布積層体又は請求項10に記載の伸縮性不織布積層体を含む繊維製品。
- 請求項1~請求項9のいずれか1項に記載の不織布積層体又は請求項10に記載の伸縮性不織布積層体を含む吸収性物品。
- 請求項1~請求項9のいずれか1項に記載の不織布積層体又は請求項10に記載の伸縮性不織布積層体を含む衛生マスク。
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JP2022508205A (ja) * | 2018-11-23 | 2022-01-19 | ライフェンホイザー・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンデイトゲゼルシャフト・マシイネンファブリーク | 圧縮性及び復元性を高めた嵩高不織布 |
JP7582943B2 (ja) | 2018-11-23 | 2024-11-13 | ライフェンホイザー・ゲゼルシャフト・ミト・ベシュレンクテル・ハフツング・ウント・コンパニー・コマンデイトゲゼルシャフト・マシイネンファブリーク | 圧縮性及び復元性を高めた嵩高不織布 |
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JP7318237B2 (ja) | 2019-03-08 | 2023-08-01 | 三井化学株式会社 | 不織布、積層体、被覆シート、及び不織布の製造方法 |
JP2022518334A (ja) * | 2019-03-15 | 2022-03-15 | ファイバーテクス・パーソナル・ケア・アクティーゼルスカブ | 弾性不織布シート及びその製造方法 |
JP7074933B2 (ja) | 2019-03-15 | 2022-05-24 | ファイバーテクス・パーソナル・ケア・アクティーゼルスカブ | 弾性不織布シート及びその製造方法 |
Also Published As
Publication number | Publication date |
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JPWO2016143834A1 (ja) | 2017-08-10 |
EP3269861B1 (en) | 2019-12-18 |
KR20170117121A (ko) | 2017-10-20 |
DK3269861T3 (da) | 2020-02-03 |
JP6346372B2 (ja) | 2018-06-20 |
CN107407029A (zh) | 2017-11-28 |
CN107407029B (zh) | 2019-10-25 |
EP3269861A1 (en) | 2018-01-17 |
TWI723008B (zh) | 2021-04-01 |
EP3269861A4 (en) | 2018-10-17 |
KR101891456B1 (ko) | 2018-08-23 |
US20180038025A1 (en) | 2018-02-08 |
TW201641768A (zh) | 2016-12-01 |
US10842682B2 (en) | 2020-11-24 |
MY185393A (en) | 2021-05-17 |
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