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WO2010044169A1 - Water-resistant and high air permeability composite sheet and process for producing the water-resistant and high air permeability sheet - Google Patents

Water-resistant and high air permeability composite sheet and process for producing the water-resistant and high air permeability sheet Download PDF

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Publication number
WO2010044169A1
WO2010044169A1 PCT/JP2008/068883 JP2008068883W WO2010044169A1 WO 2010044169 A1 WO2010044169 A1 WO 2010044169A1 JP 2008068883 W JP2008068883 W JP 2008068883W WO 2010044169 A1 WO2010044169 A1 WO 2010044169A1
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WO
WIPO (PCT)
Prior art keywords
layer
resin
mfc
water
nonwoven fabric
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2008/068883
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French (fr)
Japanese (ja)
Inventor
磨 鈴木
好夫 平井
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Japan Absorbent Technology Institute
Tomoegawa Co Ltd
Original Assignee
Japan Absorbent Technology Institute
Tomoegawa Paper Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Japan Absorbent Technology Institute, Tomoegawa Paper Co Ltd filed Critical Japan Absorbent Technology Institute
Priority to JP2010533767A priority Critical patent/JP5502742B2/en
Priority to PCT/JP2008/068883 priority patent/WO2010044169A1/en
Publication of WO2010044169A1 publication Critical patent/WO2010044169A1/en
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • B32B5/24—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer
    • B32B5/26—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed one layer being a fibrous or filamentary layer another layer next to it also being fibrous or filamentary
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers of the pads
    • A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
    • A61F13/51401—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by the material
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers of the pads
    • A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
    • A61F13/51456—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties
    • A61F13/51458—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its properties being air-pervious or breathable
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A61F13/15—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators
    • A61F13/51—Absorbent pads, e.g. sanitary towels, swabs or tampons for external or internal application to the body; Supporting or fastening means therefor; Tampon applicators characterised by the outer layers of the pads
    • A61F13/514—Backsheet, i.e. the impermeable cover or layer furthest from the skin
    • A61F13/51474—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its structure
    • A61F13/51478—Backsheet, i.e. the impermeable cover or layer furthest from the skin characterised by its structure being a laminate, e.g. multi-layered or with several layers
    • 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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/02—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by structural features of a fibrous or filamentary layer
    • B32B5/022—Non-woven fabric
    • 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
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/22—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by the presence of two or more layers which are next to each other and are fibrous, filamentary, formed of particles or foamed
    • 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
    • B32B2262/06—Vegetal fibres
    • B32B2262/062—Cellulose fibres, e.g. cotton
    • 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
    • B32B2307/724—Permeability to gases, adsorption
    • 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
    • B32B2307/7265—Non-permeable
    • 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
    • B32B2535/00—Medical equipment, e.g. bandage, prostheses or catheter
    • 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

Definitions

  • the present invention relates to a water-resistant and highly breathable composite sheet and a method for producing the same.
  • a sheet-like or film-like material used for hygiene or medical products requires a certain degree of breathability while not leaking liquid.
  • the plastic film has a function not to leak the liquid because it is difficult to permeate the liquid, but does not have air permeability because the tissue is dense. That is, by mixing a hydrophobic film such as polyethylene with a filler such as calcium carbonate and a heterogeneous polymer as a sheet material such as a back sheet (non-contact side with a human body) of a diaper that requires both water resistance and air permeability.
  • Patent Document 1 proposes an invention of a sheet material composed of microfibrous cellulose and a nonwoven fabric.
  • the fine fibrous cellulose an extremely thin fibrous cellulose having an average fiber length of 0.3 mm or less and a water retention of 15 mL / g or more is used.
  • fibrous cellulose examples include those obtained by making a pulp or cotton fiber slurry into fine fibers by mechanical treatment, and those called bacterial cellulose produced by bacteria.
  • mechanical treatment method examples include a method using a high-pressure homogenizer, a grinder, a refiner, and the like.
  • a thin layer is formed by applying a dispersion obtained by dispersing the fine fibrous cellulose in a solvent on a nonwoven fabric, and the sheet material is prepared by removing the solvent from the thin layer.
  • the sheet material Since the sheet material is thin, it has good ventilation, and has dust resistance and bacteria barrier properties. Therefore, it is an excellent material for sanitary or medical use. However, it has not been put to practical use as absorbent products such as women's products, diapers for children and adults, because the prevention of leakage of liquids such as urine is insufficient.
  • a desired function such as water repellency and deodorizing property
  • a method of incorporating various resin components made of a synthetic polymer can be mentioned. It is difficult to exhibit such a desired function while maintaining the properties, and the actual situation is that it has not yet reached a practically usable level (Patent Document 2).
  • the present invention has been made in view of the above-described conventional problems, and is a sheet-like composite of fine cellulose fibers and a nonwoven fabric that can exhibit desired characteristics while maintaining high water resistance and high air permeability.
  • An object of the present invention is to provide a water-resistant and highly breathable composite sheet obtained by processing a resin on a body and a method for producing this water-resistant and highly breathable composite sheet.
  • the water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of an MFC layer composed of a finely divided cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer.
  • the resin layer (A), resin / MFC coexistence layer (B), MFC ⁇ It consists of 4 layer structure of a nonwoven fabric coexistence layer (C) and a nonwoven fabric layer (D), It is characterized by the above-mentioned. Thereby, a water-resistant and highly breathable composite sheet in which water resistance and breathability are balanced can be obtained.
  • the water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of an MFC layer composed of a finely divided cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer.
  • MFC finely divided cellulose fiber
  • the resin layer (A), resin / MFC coexistence layer (B), resin It has a four-layer structure of an MFC / nonwoven fabric coexisting layer (E) and a nonwoven fabric layer (D).
  • the water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of an MFC layer composed of a finely divided cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer.
  • MFC finely divided cellulose fiber
  • the resin layer (A), resin / MFC coexistence layer (B), resin It has a four-layer structure of an MFC / nonwoven fabric coexisting layer (E) and a resin / nonwoven fabric coexisting layer (F).
  • the water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of an MFC layer composed of a finely divided cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer.
  • MFC finely divided cellulose fiber
  • the resin layer (A), resin / MFC coexistence layer (B), resin It has a five-layer structure of an MFC / nonwoven fabric coexisting layer (E), an MFC / nonwoven fabric coexisting layer (C), and a non-woven fabric layer (D).
  • the water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of an MFC layer composed of a finely divided cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer.
  • MFC finely divided cellulose fiber
  • the resin layer (A), resin / MFC coexistence layer (B), resin It has a five-layer structure of an MFC / nonwoven fabric coexisting layer (E), a resin / nonwoven fabric coexisting layer (F), and a non-woven fabric layer (D).
  • a refined cellulose fiber / nonwoven fabric composite having a three-layer structure consisting of an MFC layer composed of a refined cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer
  • MFC surface is the upper surface
  • the nonwoven fabric surface is the lower back surface, which is obtained by applying resin processing to the body, the resin layer (A) that exists on the MFC surface on the front surface, and further under the nonwoven fabric surface on the back surface And a resin layer (A) and two resin layers (A) above and below.
  • the water-resistant and highly breathable composite sheet according to the present invention is characterized in that a water repellent material layer (R) is further formed on the upper surface of the A layer.
  • R water repellent material layer
  • the layer A is a resin / water repellent material coexisting layer (S) containing a resin and a water repellent material.
  • the water-resistant and highly breathable composite sheet according to the present invention is characterized by having both a water-repellent material layer (R) and a resin / water-repellent material coexisting layer (S). Thereby, in addition to water resistance and breathability, a water-resistant highly breathable composite sheet having water repellency can be obtained.
  • the water-resistant and highly breathable composite sheet according to the present invention is characterized in that a solid powder component is supported on any one of the B, C, D, E, and F layers. Thereby, in addition to water resistance and air permeability, a water resistant and highly air permeable composite sheet having desired characteristics derived from the solid powder component can be obtained.
  • the solid powder component is a deodorizer (odor adsorbent).
  • odor adsorbent odor adsorbent
  • the refined cellulose fiber is combined with a deodorizer.
  • a water-resistant and highly breathable composite sheet with further improved deodorization can be obtained.
  • the air permeability measured by the Gurley method is 10 seconds / 100 mL to 150 seconds / 100 mL, and the durability is such that leakage does not occur for 6 hours or more in a ring test at a water depth of 10 mm. It is characterized by having water resistance. Thereby, water resistance is further stabilized.
  • the absorbent product according to the present invention is characterized by using the above water-resistant and highly breathable composite sheet as a leak preventer. Thereby, an absorbent product having both high water resistance and air permeability can be obtained.
  • the method for producing a water-resistant and highly breathable composite sheet according to the present invention is: A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of Resin treatment (all-layer resin treatment) such that the resin component reaches at least the MFC layer of the composite; Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite; The composite is subjected to resin processing in combination. Thereby, a water-resistant and highly breathable composite sheet in which water resistance and breathability are balanced can be obtained.
  • MFC micronized cellulose fibers
  • the method for producing a water-resistant and highly breathable composite sheet according to the present invention is: A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of Resin treatment (all-layer resin treatment) in which the resin component reaches at least the MFC layer and the MFC / nonwoven fabric coexisting layer of the composite, Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite; The composite is subjected to resin processing in combination. Thereby, a water-resistant and highly breathable composite sheet in which water resistance and breathability are balanced can be obtained.
  • MFC micronized cellulose fibers
  • the method for producing a water-resistant and highly breathable composite sheet according to the present invention is: A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of Resin treatment in which the resin component spreads over at least the three layers of the composite (all layer resin treatment); Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite; The composite is subjected to resin processing in combination. As a result, a water-resistant and highly breathable composite sheet having a good balance between water resistance and breathability can be obtained.
  • MFC micronized cellulose fibers
  • the all-layer resin treatment is performed first, and then the surface layer resin treatment is performed. Thereby, stable water resistance can be imparted.
  • the surface resin treatment is performed first, and then the all-layer resin treatment is performed. Thereby, stable water resistance can be imparted.
  • the processing using a water repellent material is further performed. Thereby, more stable water resistance can be imparted.
  • the surface resin treatment is performed by mixing a water repellent material with the resin. This simplifies the process and provides stable water resistance.
  • the composite is characterized in that a deodorant layer is previously formed in the composite. Thereby, a deodorizer layer can be stably carried inside.
  • the all-layer resin treatment is performed by mixing a deodorizer with the resin.
  • the all-layer resin treatment is performed using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 8% or less.
  • the surface resin treatment is performed using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 10% or more. Thereby, a stable surface resin layer can be formed.
  • the all-layer resin treatment is performed on the back surface of the composite using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 8% or less. It is characterized by that. Thereby, the stability of water resistance can be further improved.
  • the all-layer resin treatment is performed using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 1% to 5%, and a solid content of 3% to 8%. % Using a water-based emulsion of thermoplastic synthetic resin. Thereby, uniform resin processing without unevenness can be performed.
  • the processing using the water-repellent material is performed using an aqueous emulsion of the water-repellent material.
  • the water repellent material can be stably fixed to the surface.
  • the surface resin treatment is performed using a mixed emulsion in which an aqueous emulsion of a water-repellent material is mixed with an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 10% or more. It is characterized by being. Thereby, a process can be simplified and a water repellent material layer can be formed in a surface layer site
  • the water-resistant highly breathable composite sheet by this invention, Comprising: Resin layer (A), Resin / MFC coexistence layer (B), Resin / MFC / nonwoven fabric coexistence layer (E), MFC / nonwoven fabric coexistence layer
  • the water-resistant highly breathable composite sheet which has 5 layer structure which consists of (C) and a nonwoven fabric layer (D) is shown.
  • the water-resistant highly breathable composite sheet by this invention, Comprising: Resin layer (A), Resin / MFC coexistence layer (B), Resin / MFC / nonwoven fabric coexistence layer (E), Resin / nonwoven fabric coexistence layer
  • the water-resistant highly breathable composite sheet which has 5 layer structure which consists of (F) and a nonwoven fabric layer (D) is shown.
  • the water-resistant highly breathable composite sheet by this invention Comprising: Resin layer (A), Resin / MFC coexistence layer (B), Resin / MFC / nonwoven fabric coexistence layer (E), Nonwoven fabric layer (D) And a water-resistant and highly breathable composite sheet having a five-layer structure comprising a resin layer (A).
  • Examples of the water-resistant and highly breathable composite sheet according to the present invention wherein (1) is a resin layer (A), a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), A water-resistant and highly breathable composite sheet having a water repellent material layer (R) in a four-layer structure comprising a nonwoven fabric layer (D), (2) is a resin layer (A) and a resin / MFC coexisting layer ( B), a resin / MFC / nonwoven fabric coexisting layer (E), a resin / nonwoven fabric coexisting layer (F), and a non-woven fabric layer (D) having a water-repellent material layer (R)
  • the highly breathable composite sheet is shown respectively.
  • Examples of the water-resistant and highly breathable composite sheet according to the present invention wherein (1) is a resin layer (A), a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), A water-resistant and highly breathable composite sheet having a four-layer structure composed of a nonwoven fabric layer (D), and having a resin / water-repellent material coexisting layer (S) in which a water-repellent material R is supported on the resin layer (A)
  • Aspect (2) includes a resin layer (A), a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), a resin / nonwoven fabric coexistence layer (F), and a nonwoven fabric layer ( D) is a water-resistant and highly breathable composite sheet having a five-layer structure, and has a resin / water-repellent material coexisting layer (S) in which a water-repellent material R is supported on the resin layer (A
  • Examples of the water-resistant and highly breathable composite sheet according to the present invention wherein (1) is a resin layer (A), a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), A water-resistant and highly breathable composite sheet having a four-layer structure comprising a nonwoven fabric layer (D) and a water-repellent material layer (R), wherein the resin layer (A) carries the water-repellent material R.
  • a mode having a water repellent coexisting layer (S), (2) is a resin layer (A), a resin / MFC coexisting layer (B), a resin / MFC / nonwoven coexisting layer (E), and a resin / nonwoven coexisting layer
  • a mode having a resin / water-repellent material coexisting layer (S) on which is supported is shown.
  • a water-resistant and highly breathable composite sheet Comprising: From resin layer (A), resin and MFC coexistence layer (B), MFC and nonwoven fabric coexistence layer (C), and nonwoven fabric layer (D)
  • a water-resistant and highly breathable composite sheet having a water repellent material layer (R) in a four-layer structure, wherein (1) is deodorized in the resin / MFC coexistence layer (B) and the MFC / nonwoven fabric coexistence layer (C) (2) shows an embodiment in which a deodorizing agent is carried on the MFC / nonwoven fabric coexisting layer (C) and the nonwoven fabric layer (D), respectively.
  • Resin layer (A), Resin / MFC coexistence layer (B), Resin / MFC / nonwoven fabric coexistence layer (E), Nonwoven fabric layer (D) (1) is an embodiment in which a deodorant is supported on the resin / MFC / nonwoven fabric coexisting layer (E), (2) A mode in which a deodorizing agent is supported on the resin / MFC / nonwoven fabric coexisting layer (E) and the resin / nonwoven fabric coexisting layer (F) is shown.
  • An example of a water-resistant and highly breathable composite sheet according to the present invention obtained by using a finely divided cellulose fiber / nonwoven fabric composite in which a deodorizer is bonded to finely divided cellulose fibers, the resin layer (A), A water-resistant and highly breathable composite sheet having a four-layer structure comprising an MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), and a nonwoven fabric layer (D), and a water repellent material layer (R).
  • MFC coexistence layer B
  • E resin / MFC / nonwoven fabric coexistence layer
  • D nonwoven fabric layer
  • R water repellent material layer
  • System flow 1 It is a flowchart which shows the example which performs the impregnation process by the organic solvent type melted resin of a refined cellulose fiber and a nonwoven fabric composite.
  • System flow 2 It is a flowchart which shows the example which performs the process twice by SBR aqueous emulsion of a refined cellulose fiber and a nonwoven fabric composite.
  • System flow 3 It is a flowchart showing an example in which a treatment with an SBR aqueous emulsion in which zeolite of a fine cellulose fiber / nonwoven fabric complex is co-dispersed and a treatment with a single SBR aqueous emulsion are combined.
  • System flow 4 It is a flowchart which shows the example which performs the process by SBR aqueous emulsion twice to the refined cellulose fiber and nonwoven fabric composite which carry
  • System flow 5 It is a flowchart which shows the example which manufactures refined cellulose fiber and a nonwoven fabric composite, and SBR latex process continuously.
  • System flow 6 It is a flowchart which shows the example which performs manufacture of a refined cellulose fiber and nonwoven fabric composite, and the process by an acrylic acid emulsion and a water repellent material continuously.
  • the schematic sectional drawing of the apparatus used for evaluation of the wettability of a surface, a diffusivity, and the permeability is shown.
  • permeation movement state of water is shown.
  • production state of the leak under pressure is shown.
  • Example 2 it is a flowchart which shows schematically the manufacturing step of the water-resistant highly breathable composite sheet by this invention.
  • 6 is a flowchart schematically showing steps for producing a water-resistant and highly breathable composite sheet according to the present invention in Example 3.
  • 6 is a flowchart schematically showing steps for producing a water-resistant and highly breathable composite sheet according to the present invention in Example 3.
  • 6 is a flowchart schematically showing steps for producing a water-resistant and highly breathable composite sheet according to the present invention in Example 4.
  • 6 is a flowchart schematically showing steps for producing a water-resistant and highly breathable composite sheet according to the present invention in Example 4.
  • the water-resistant and highly breathable composite sheet according to the present invention further appropriately binds a resin to a refined cellulose fiber / nonwoven fabric composite (also referred to as an MFC / nonwoven fabric composite) composed of a refined cellulose fiber (MFC) and a nonwoven fabric. ⁇ It was made to coexist. The specific method of resin processing will be described later in detail according to the method for producing a water-resistant and highly breathable composite sheet according to the present invention.
  • FIG. 1 is a schematic view showing a refined cellulose fiber / nonwoven fabric composite in the present invention.
  • the refined cellulose fiber / nonwoven fabric composite (MFC / nonwoven fabric composite) in the present invention includes an MFC single layer (hereinafter also referred to as MFC layer) 1 made of fine cellulose fiber, and a single layer of nonwoven fabric (hereinafter referred to as MFC layer). 3) and an MFC / nonwoven fabric coexisting layer 2 in which the MFC layer and the nonwoven fabric layer are combined.
  • the micronized cellulose fiber is a fibrous cellulose that has been micronized to a so-called microfibril unit, and is generally referred to as MFC (Microfibrillated Cellulose).
  • MFC Microfibrillated Cellulose
  • this refined cellulose fiber has specific performance such as hydrogen bonding performance and solid powder adsorption performance due to the fine size and strong hydration property of the fiber.
  • the dispersion When dispersed in water, the dispersion exhibits a large non-Newtonian viscosity.
  • MFC finely divided cellulose fiber
  • a porous nonwoven fabric made of a finely divided cellulose fiber (hereinafter abbreviated as MFC) having such properties by using a porous nonwoven fabric as a support and filling and coating the porous portion with MFC.
  • MFC finely divided cellulose fiber
  • This composite has various specific performances, one of which is a uniform and stable microporous structure.
  • the microporous structure of the composite sheet resulting from this MFC is due to its strong hydrophilicity, when it comes into contact with a large amount of water, the MFC hydrates and swells and the composite structure is destroyed.
  • the MFCs are bonded to each other, the MFC and the nonwoven fabric are bonded with a filling resin, and the microporous structure is fixed, so that liquid water does not pass but water vapor and air easily pass through.
  • the inventors of the present invention have found that a composite sheet that functions extremely effectively as a water-resistant barrier having air permeability, combined with “water resistance” can be obtained.
  • the performance of the raw material MFC / nonwoven fabric composite varies depending on the following conditions.
  • Lamination and heat-sealing method This is a method in which an MFC layer and a non-woven fabric layer composed of a fiber web containing heat-fusible fibers are separately molded, and both layers are overlapped and integrated by thermocompression bonding. .
  • the MFC layer and the non-woven fabric layer still occupy the majority, but since the heat-sealing fibers penetrate into the MFC layer, the ratio of the MFC / non-woven fabric coexisting layer increases.
  • MFC slurry coating method In this method, a nonwoven fabric is used as a base material, and an MFC water dispersion slurry is coated on the upper surface of the non-woven fabric and integrated by pressure bonding. At this time, the MFC slurry concentration is about 0.8% to 3%, and the MFC layer is in the nonwoven fabric composition. The proportion of coexistence layers is greatly increased.
  • Table 1 below compares the proportions of the MFC layer, the MFC / nonwoven fabric coexisting layer, and the non-woven fabric layer in a state of being combined with the MFC layer 15 g / m 2 and the non-woven fabric layer 15 g / m 2 .
  • the nonwoven fabric used as the base material was an SMS nonwoven fabric manufactured by Avgor.
  • a dry air-through nonwoven fabric made of Kuraray PE / PET fibers was used as the nonwoven fabric.
  • the PE component is melted by heat treatment after drying.
  • the numerical value displayed in Table 1 was described by the weight ratio (%) of each layer when the total weight of the refined cellulose fiber / nonwoven fabric composite was 100%.
  • the MFC layer is 50%
  • the coexistence layer is 0%
  • the nonwoven fabric layer is 50%.
  • the MFC layer is 30%
  • the coexistence layer is 35%
  • the nonwoven fabric layer is 35%.
  • the coexisting layer 35% means that it is composed of 20% MFC and 15% nonwoven fabric.
  • the MFC layer is firmly formed, but delamination is likely to occur at the interface between the MFC layer and the nonwoven fabric layer.
  • delamination hardly occurs, but the formation state of the MFC layer tends to be nonuniform.
  • Refined cellulose fiber 1) Properties of refined cellulose fiber
  • the refined cellulose fiber is generally a mechanically refined cellulose fiber such as wood pulp, cotton, sugar millet, sugar beet, etc. It is called microfibrillated cellulose MFC (Microfibrillated Cellulose). Those produced by bacteria such as acetic acid bacteria are called bacterial cellulose or biocellulose.
  • MFC is disclosed in Patent Document 3, and Biocellulose is disclosed in Non-Patent Document 1. All of them have a short fiber length, an ultrafine diameter of nano units of around 100 nm, and are rich in hydration.
  • the refined cellulose fiber used in the present invention has an average fiber length of 0.3 mm or less, preferably 0.2 mm or less. If the thickness is 0.3 mm or more, the fibers are entangled and it becomes easy to form a non-uniform mass. It is preferable that the water retention that is a measure of hydration is 15 mL / g or more. If it is less than 15 mL / g, a slurry that produces a stable dispersion state cannot be obtained, and the hydrogen bonding force also decreases.
  • the micronized cellulose fiber is hereinafter represented by MFC.
  • the highly breathable structure of the water-resistant and highly breathable composite sheet according to the present invention depends on the microporous structure between the fine fibers of MFC filled with the porous portion of the nonwoven fabric. Therefore, in the MFC / nonwoven fabric composite used for the production of the water-resistant and highly breathable composite sheet, the amount of MFC necessary for the composite needs to be appropriately selected.
  • the amount of MFC is influenced by the density and basis weight of the nonwoven fabric, but is preferably in the range of 1 g / m 2 to 30 g / m 2 , more preferably 2 g / m 2 to 20 g / m 2 . If it is less than 1 g / m 2 , it is insufficient as an amount for filling the nonwoven fabric structure, and it is difficult to form a uniform layer. If it exceeds 30 g / m 2 , the MFC layer is likely to be made into paper, is hardened and loses flexibility, and at the same time, many surface cracks occur.
  • Non-woven fabric used as substrate 1 Properties of non-woven fabric
  • the nonwoven fabric of the present invention is flexible, has a uniform structure, has a basis weight of 8 g / m 2 to 40 g / m 2 and a thickness of 0.5 mm or less, and has a relatively low basis weight and is a thin nonwoven fabric.
  • Nonwoven fabric constituent fibers Polyethylene, polypropylene, polyester, acrylic, P.I. V.
  • Synthetic fibers such as PE / PET, PE / PP, EVA / PE and other fusible composite fibers, wood pulp, cotton, rayon, lyocell, acetate and other cellulose fibers, and mixtures thereof can be used.
  • synthetic fibers such as PE / PET, PE / PP, EVA / PE and other fusible composite fibers, wood pulp, cotton, rayon, lyocell, acetate and other cellulose fibers, and mixtures thereof can be used.
  • the synthetic fiber-based hydrophobic fibers are relatively easy to impart water resistance by resin processing.
  • SMS spunbond / meltblown composite
  • the water-resistant and highly breathable composite sheet according to the present invention is obtained by appropriately combining and coexisting a resin with the above-mentioned refined cellulose fiber / nonwoven fabric composite as described at the beginning. These show the example of the water-resistant highly breathable composite sheet by this invention.
  • the water-resistant and highly breathable composite sheet is obtained by resin processing on the upper surface of the MFC layer of the fine cellulose fiber / nonwoven fabric composite. Depending on the depth of the resin processing, various modes can be taken.
  • the water-resistant and highly breathable composite sheet according to the present invention includes, for example, as shown in FIG. 3, a resin layer (A) composed only of a resin, a resin / MFC coexisting layer (B) composed of a resin and an MFC layer, and an MFC. And a non-woven fabric coexisting layer (C) and a non-woven fabric layer (D).
  • a resin layer (A) composed only of a resin
  • a resin / MFC coexisting layer B
  • a non-woven fabric coexisting layer C
  • D non-woven fabric layer
  • the MFC layer is processed into a resin / MFC coexisting layer (B) composed of a resin and an MFC layer
  • the MFC / nonwoven fabric coexisting layer is a resin / MFC / nonwoven fabric coexisting layer (E) composed of a resin, MFC and a non-woven fabric.
  • / or the nonwoven fabric layer is processed into a resin / nonwoven fabric coexisting layer (F) comprising a resin and a nonwoven fabric.
  • the layer obtained according to the grade of resin will comprise each layer of a water-resistant highly air permeable composite sheet. Therefore, all the structures obtained according to the degree of resin processing (that is, resin layer (A), resin / MFC coexistence layer (B), MFC / nonwoven fabric coexistence layer (C), nonwoven fabric layer (D), resin / Any combination of the MFC / nonwoven fabric coexisting layer (E) and the resin / nonwoven fabric coexisting layer (F)) is also included in the scope of the present invention.
  • the surface of the refined cellulose fiber / nonwoven fabric composite subjected to resin processing may be performed from the side where the MFC layer exists, or from the side where the nonwoven fabric layer exists.
  • FIGS. 1 to 7 show examples obtained by performing resin processing from the side where the MFC layer is present
  • FIG. 8 shows an example obtained by performing resin processing from the nonwoven fabric layer side.
  • FIG. 8 is an example of a water-resistant and highly breathable composite sheet according to the present invention, which is a resin layer (A), a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), and a non-woven fabric.
  • the water-resistant highly breathable composite sheet which has a 5 layer structure which consists of a layer (D) and a resin layer (A) is shown.
  • a water-repellent material layer (R) made of a water-repellent material is further provided on a water-resistant and highly breathable composite sheet obtained by coexisting a resin with a fine cellulose fiber / nonwoven fabric composite. Also good.
  • This mode is shown in (1) and (2) of FIG.
  • FIG. 9 is an example of a water-resistant and highly breathable composite sheet according to the present invention.
  • (1) is a resin layer (A), a resin / MFC coexistence layer (B), and a resin / MFC / nonwoven fabric coexistence layer ( E) and a non-woven fabric layer (D) having a four-layer structure and a water-resistant and highly breathable composite sheet having a water-repellent material layer (R).
  • (2) is a resin layer (A), The water-repellent material layer (R) has a five-layer structure comprising an MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), a resin / nonwoven fabric coexistence layer (F), and a nonwoven fabric layer (D).
  • the water-resistant and highly breathable composite sheet having) is shown respectively.
  • the water-repellent material is contained in the water-resistant and highly breathable composite sheet, it may be provided as the water-repellent material layer (R) made of the water-repellent material as described above.
  • the layer provided as the water repellent material layer (R) and the mode contained in the desired layer position may be appropriately combined.
  • (1) and (2) in FIG. 10 show that the water-repellent material is water-resistant and highly ventilated by providing a resin / water-repellent material coexisting layer (S) in which a water-repellent material coexists with a resin layer (A) made of resin.
  • the water-resistant and highly breathable composite sheet obtained by allowing the resin to coexist with the fine cellulose fiber / nonwoven fabric composite may further contain a solid powder component such as a deodorant.
  • a solid powder component such as a deodorant.
  • the deodorizer may be contained in any layer constituting the water-resistant and highly breathable composite sheet, but has a strong hydrophilic composition, and when such a hydrophilic solid is present on the surface, the liquid infiltrates.
  • a resin / MFC coexistence layer (B) and an MFC / nonwoven fabric coexistence layer (C) may contain a deodorizer, as shown in (2) of FIG.
  • the deodorizer is bonded to the fine cellulose fiber. May be. This mode is shown in FIG. FIG.
  • a water-resistant and highly breathable composite sheet obtained by using a finely divided cellulose fiber / nonwoven fabric composite in which a deodorizing agent is bonded to finely divided cellulose fibers, and a resin layer (A) And a water / repellent material layer (R) in a four-layer structure comprising a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), and a nonwoven fabric layer (D).
  • a breathable composite sheet is shown.
  • the water-resistant and highly breathable composite sheet composed of the highly breathable resin, MFC, and nonwoven fabric imparted with the water resistance of the present invention is used for sterilization wrap, food wrapping materials, paper diapers, and leak-proof back sheets for feminine sanitary products, etc. Therefore, it is essential that no leakage occurs during use, and water resistance under pressure is also required.
  • Step of generating liquid leakage when using a composite sheet For example, the case where the composite sheet of the present invention is used as a back sheet of a disposable diaper will be described as an example.
  • urine aqueous liquid
  • urine is subjected to the following process. It becomes.
  • Step 1 Wetting of the outermost surface layer of aqueous liquid and diffusion / penetration of liquid into the surface layer ⁇
  • Step 2 Generation of swelling due to water swelling of MFC layer ⁇
  • Step 3 Permeation transfer from MFC layer to MFC / nonwoven fabric layer ⁇
  • Step 4 Permeation of liquid from the lowermost nonwoven fabric layer (generation of leakage)
  • the product of the present invention when used as a back sheet of a paper diaper, first, when body fluid such as urine comes into contact with the uppermost surface of the back sheet, if the water repellency of the back sheet surface is large, (2) and ( If the water repellency is weak as shown in 3), it becomes a half moon as shown in (1) of FIG. 15 and stays on the surface.
  • bleed to the lower surface occurs from any spot even after elapse of at least 30 minutes, preferably 2 hours or more, by the test by the 5-spot method. It is assumed that there is no.
  • a ring type seal test is performed.
  • a stainless steel ring with an inner diameter of 80 mm ⁇ is filled with a dyed physiological saline, and a water pool with a water depth of 10 mm is placed on the composite sheet. It is a method of analysis.
  • the surface state of the composite sheet does not change greatly and the generation of moisture does not occur even after 24 hours after 6 hours.
  • the resin processing is insufficient, MFC on the surface layer swells, a crumpled "fluff" occurs, and partial delamination occurs, passes through the MFC layer and MFC / nonwoven fabric coexisting layer, reaches the nonwoven fabric layer, and exudes to the lower part. Become.
  • the leak test under pressure is an extremely severe test, and such a load test is not necessary for normal use, but the water-resistant and highly breathable composite sheet according to the present invention is preferably 30 minutes or more, The goal is not to detect the occurrence of leaks.
  • a saline solution colored in blue is used as a saturated solution, and white filter paper is used as detection paper, so that sensitive and delicate moisture can be detected.
  • the water-resistant and highly breathable composite sheet according to the present invention has water permeability and high breathability.
  • the air permeability mentioned here has a property that liquid water does not permeate but air and water vapor permeate.
  • the air permeability required for the composite of the present invention is less than 300 seconds / 100 mL, preferably 200 seconds / 100 mL or less, more preferably 20 seconds / 100 mL to 150 seconds / 100 mL, when expressed by the air permeability of the Gurley method. More preferably, it is very high of 10 to 100 seconds / 100 mL, and the level of air permeability is very different from that of a conventional so-called PE film-based highly breathable and water-resistant sheet. Is.
  • Table 2 shows a water-resistant and highly breathable composite sheet manufactured according to the method of manufacturing a water-resistant and highly breathable composite sheet according to the present invention (a product of the present invention), and a so-called Micro Porous Film made of PE that has been conventionally used. This is a comparison of the ventilation performance.
  • the air permeability is very low (300 seconds / 100 mL or more), so the moisture permeability is a standard.
  • the air permeability by the Gurley method is used as a main measure.
  • the thickness of the product of the present invention is very thick, 5 to 10 times, compared with film-like Polum and Espoir is because the product of the present invention is a nonwoven fabric composite.
  • the method for producing a water-resistant and highly breathable composite sheet according to the present invention is: A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of Resin treatment (all-layer resin treatment) in which the resin component reaches at least the MFC layer and the MFC / nonwoven fabric coexisting layer of the composite, Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite; The composite is subjected to resin processing in combination.
  • MFC micronized cellulose fibers
  • the method for producing a water-resistant and highly breathable composite sheet according to the present invention has a three-layer structure of an MFC single layer (1), an MFC / nonwoven fabric coexisting layer (2) and a non-woven fabric single layer (3) as shown in FIG.
  • a refined cellulose fiber / nonwoven fabric composite (MFC / nonwoven fabric composite) is processed using a resin such as a thermoplastic resin. The purpose is to impart water resistance while maintaining the high air permeability.
  • the uppermost surface of the MFC layer is filled and repaired with large and small cracks and defects existing on the upper surface of the MFC layer, and the resin alone layer (A) ( Hereinafter, it is also simply referred to as a resin layer).
  • the MFC layer For the inside of the MFC layer, it penetrates into the MFC layer, coats the surface of each fine MFC fiber to make it hydrophobic, fills and bonds the gaps between the MFC fibers, and combines the resin / MFC coexisting layer (B ).
  • a resin / MFC / nonwoven fabric coexisting layer (E) is formed by coating the surface of the non-woven fabric as well as the MFC surface and adding resin.
  • nonwoven fabric layer it is desirable to form a resin / nonwoven fabric coexistence layer (F) by bonding and covering the lowermost nonwoven fabric layer.
  • the nonwoven fabric when the nonwoven fabric is a spun melt nonwoven fabric of PE or PP, the nonwoven fabric itself has strong hydrophobicity and water repellency, and therefore it is not always necessary to provide a resin / nonwoven fabric coexistence layer.
  • the MFC layer and the MFC / nonwoven fabric coexisting layer maintain a uniform porous structure with as little resin as possible. It is necessary to hydrophobize the surface of the MFC to prevent moisture penetration.
  • a so-called multi-stage treatment method which is a combination of the treatments (1) and (2) described below, is desirable.
  • Resin treatment in which the resin component reaches at least the entire MFC layer, preferably the MFC layer and the MFC / nonwoven fabric coexisting layer, more preferably the MFC layer, the MFC / nonwoven fabric coexisting layer, and the nonwoven fabric layer. (This will be referred to as a full-layer resin treatment); and (2) A treatment in which the resin component is kept only on the upper surface layer of the MFC and the resin component is mainly disposed on the upper surface of the MFC layer (this is called It is called a surface layer resin treatment).
  • Method of performing surface layer resin treatment after performing all layer resin treatment (2) The method can be broadly classified into either method of performing full layer resin treatment after first performing surface layer resin treatment. .
  • the hydrophobization of MFC and the MFC are combined with each other.
  • Resin / MFC coexistence layer is formed, MFC and non-woven fabric are combined to form resin / MFC / non-woven fabric coexistence layer, and further, the surface of non-woven fabric constituent fiber is made hydrophobic to form resin / non-woven fabric coexistence layer It does not fill all the voids existing between MFCs and non-woven fabrics.
  • the all-layer resin treatment is not particularly limited as long as it is a method for distributing the resin to the MFC / nonwoven fabric composite in the above-described manner, but may be performed by the following methods (1) to (4), for example. .
  • a method of increasing the amount of the liquid by spreading a thinner resin liquid twice from the MFC surface on the upper surface and spreading it over the entire layer For example, in the first time, the concentration is 3% to 4%.
  • the treatment may be performed with the resin diluent, and the second treatment may be performed from the MFC surface with the resin diluent having a concentration of 5% to 6% so that the resin solution can be distributed uniformly throughout the entire layer.
  • the first resin treatment is carried out from the MFC surface of the upper surface with a resin diluent having a concentration of 3% to 4%, and then the second resin treatment is carried out from the nonwoven fabric surface on the lower back surface to 5% to 6%.
  • the first resin treatment is performed from the nonwoven fabric surface of the lower back surface with a resin diluent having a concentration of 3% to 4%, and then the second resin treatment is performed from the MFC surface of the upper surface to 5% to 6%.
  • a resin diluent having a concentration of 3% to 4%
  • the second resin treatment is performed from the MFC surface of the upper surface to 5% to 6%.
  • the coating amount of the resin necessary for the all-layer resin treatment is 10 g / m 2 or less, preferably 8 g / m 2 to 1 g / m 2 , more preferably 5 g / m 2 to 2 g / m 2 . If it exceeds 10 g / m 2 , it will be in a filled state and the entire sheet will become hard and at the same time the air permeability will be reduced, and of course the cost will also increase. When it is less than 1 g / m 2 , the coating effect is not exhibited.
  • Surface resin treatment is a means for treating the uppermost surface of the MFC, and partly coexists with the MFC, but most of it is for forming the resin single layer (A), and therefore a relatively dense resin. It is necessary to form a thin film as much as possible using the liquid.
  • the thickness of the resin layer (A) is at least 10 ⁇ m or less, preferably 5 ⁇ m to 1 ⁇ m, more preferably 4 ⁇ m to 2 ⁇ m. Expressed in terms of basis weight, it is 10 g / m 2 or less, preferably 5 g / m 2 to 1 g / m 2 , more preferably 4 g / m 2 to 2 g / m 2 . If it exceeds 10 g / m 2 , the air permeability is greatly lowered, and the sheet itself is cured and the cost is increased. When it is less than 1 g / m 2 , film formation becomes difficult.
  • a method for surface layer resin treatment for example, when using a resin raw material such as SBR aqueous latex, acrylic resin aqueous suspension, polyurethane resin solvent solution, etc., a relatively thick water diluted resin of 10% to 30% is used.
  • surface coating may be performed using a coating roll such as gravure, flexo, or micro gravure on the surface using a solvent diluted resin.
  • hydrophobization by resin treatment is an essential condition for imparting water resistance, but further imparting water repellency is not necessarily required.
  • a treatment using a water repellent material may be further added. The purpose of the treatment using this water repellent material is as follows.
  • the following methods (1) to (3) may be mentioned as a method for performing the treatment using a water repellent material for the above purpose.
  • the water repellent material used for the above purpose is not particularly limited, and for example, olefin water repellents, paraffin water repellents, silicone water repellents, Teflon water repellents and the like are appropriately used. Used.
  • the formation of the resin film may be hindered by the addition of the water repellent material, it is necessary to pay close attention to the addition rate and the selection of the water repellent material.
  • an aqueous emulsion of a wax-based water repellent material is mixed with SBR latex at a ratio of approximately 1: 1 and used as a surface layer resin treatment liquid
  • the resin component used for this invention and its form are demonstrated.
  • the resin used for the treatment of the composite is not particularly limited as long as it is used for the above purpose, and includes the following (1) to (4).
  • thermoplastic resin component is dispersed or emulsified in a medium such as water or an organic solvent using a dispersant or an emulsifier, such as an acrylic acid and its derivative emulsion, an EVA emulsion, a synthetic rubber such as SBR Latex, PE and PP fine particle suspension.
  • a dispersant or an emulsifier such as an acrylic acid and its derivative emulsion, an EVA emulsion, a synthetic rubber such as SBR Latex, PE and PP fine particle suspension.
  • thermoplastic polymer such as PE, PP, EVA powder or granular material. Although these are difficult to handle, they are used for both surface layer resin treatment and full layer resin treatment.
  • water-dispersed SBR latex used for water resistance treatment such as normal paper processing has the following composition, for example.
  • Addition of a cross-linking agent in the above system is to make hydrophilic monomer components such as acrylic acid and MMA coexisting with SBR to be hydrophobized and kept at a temperature of 50 to 60 ° C. for about 6 hours. Need to be cured.
  • the latex having such a composition contains a hydrophilic component such as an emulsifier, a hydrophilic monomer, and a penetrating agent in an antifoaming agent in addition to the hydrophobic resin as a main component.
  • a hydrophilic component such as an emulsifier, a hydrophilic monomer, and a penetrating agent in an antifoaming agent in addition to the hydrophobic resin as a main component.
  • the addition amount of the emulsifier and the addition amount of the acrylic acid monomer are reduced so that the water resistance can be exhibited without performing the crosslinking treatment. It is necessary to select conditions such as an antifoaming agent that does not contain.
  • an antifoaming agent that does not contain.
  • the emulsifier it is also desirable to use a reactive surfactant that reacts after use to extinguish the surfactant effect.
  • Table 3 compares the case where a relatively large amount of hydrophilic component is included with the case where the amount of hydrophilic component is decreased.
  • Table 3 shows the SBR system shown above in which the hydrophilic component in the latex composition is removed as much as possible (No. 1), and the hydrophilic component is mixed in acrylic acid, an emulsifier, and an antifoaming agent. The comparison of the water resistance before hardening (No. 2) and after hardening (No. 3) at the time of processing using latex as a resin material is shown.
  • the air permeability exceeds 200 seconds / 100 mL.
  • the air permeability does not increase so much even if the amount of resin is large.
  • the surface resin treatment amount is relatively larger than the total layer resin treatment amount, the air permeability is significantly increased.
  • the MFC amount is around 10 g / m 2
  • the total layer resin treatment amount is 3 g / m 2 to 6 / m 2
  • the surface layer resin treatment amount is 2 g / m 2 to 4 g / m. 2 is preferable. In such a range, stable water resistance and appropriate air permeability can be obtained.
  • Table 5 shows that the MFC amount is changed from 5 g / m 2 to 15 g / m 2 , the total resin amount is changed from 5 g / m 2 to 15 g / m 2 , and the total resin treatment amount and the surface resin treatment amount are further changed. This shows the influence on the air permeability when the ratio is changed.
  • the MFC amount is around 10 g / m 2
  • the total layer resin treatment amount is 3 g / m 2 to 5 g / m 2
  • the surface layer resin treatment amount is 2 g / m 2 to it is preferably 3 g / m 2. In such a range, appropriate water resistance and air permeability can be obtained.
  • Table 6 examines the influence on the air permeability and water resistance when the resin is diluted.
  • the resin concentration for performing all layer resin treatment and surface layer resin treatment is 3% to 20%. The effect of resin concentration when changed to% is shown.
  • the resin concentration in the all-layer resin treatment is at least 10% or less, preferably 8% or less.
  • the resin concentration in the surface layer resin treatment may be 10% or more, but it is preferable that the resin amount used in the all layer resin treatment is larger than the resin amount used in the surface layer resin treatment. By doing in this way, it becomes the performance with which air permeability and water resistance were balanced.
  • the water-resistant and highly breathable composite sheet according to the present invention has an odor, an absorbing / adsorbing agent such as a coloring component, a heat generating agent, a hygroscopic agent, a desiccant, a conductive material, or defects such as pinholes and crazes in a sheet-like composite.
  • an absorbing / adsorbing agent such as a coloring component, a heat generating agent, a hygroscopic agent, a desiccant, a conductive material, or defects such as pinholes and crazes in a sheet-like composite.
  • solid powder components such as solid particles and powder may be added and combined.
  • additives include both cases of inorganic substances and organic substances.
  • calcium carbonate, kaolin, zeolite, activated carbon, silica gel, iron powder, copper powder, etc. are used for inorganic substances, and wood powder, cellulose powder, wheat flour, starch, CMC, polyethylene cotton fiber (trade name: Chemibest) for organic substances. (Registered trademark) (manufactured by Mitsui Chemicals, Inc.), cyclodextrin in which metal ions such as SAP or Zn, Cu, and silver ions are included, zeolite that supports metal ions, and the like.
  • An inclusion body such as cyclodextrin and zeolite loaded with metal ions have strong antibacterial properties, and they have two functions of deodorizing effect and antibacterial effect.
  • (2) Refined cellulose fiber / nonwoven fabric. A method in which a solid powder component is mixed and dispersed in a resin at the time of resin treatment of the composite, and added and compounded simultaneously with the resin treatment.
  • zeolite Materials that impair or color when exposed to the surface, or strongly hydrophilic materials that affect water resistance, such as zeolite, calcium carbonate, silica gel, activated carbon, Fe powder, Cu powder, etc. It is desirable to add and combine in advance with the cellulose oxide / nonwoven fabric composite so that it is confined as much as possible inside the sheet, particularly in the lower layer portion.
  • the whole layer resin treatment is performed by dispersing in a diluted latex resin solution. By carrying out, it can carry
  • the manufacturing system of a water-resistant and highly breathable composite sheet according to the present invention comprises the basic processes as described below.
  • the starting raw material of the water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite (MFC / nonwoven fabric) shown in FIG. Complex).
  • MFC / nonwoven fabric fine cellulose fiber / nonwoven fabric composite
  • the case is roughly divided into two cases: a case where the sheet-like composite is prepared in advance, and a case where a process for preparing the sheet-like composite is also included in the manufacturing system.
  • FIGS. 16 to 19 As examples of manufacturing systems, as shown in FIGS. 16 to 19, four examples from system flow 1 to system flow 4 are examples using a pre-prepared fine cellulose fiber / nonwoven fabric composite. Further, as shown in FIGS. 20 to 21, the system flow 5 and the system flow 6 are examples in which the preparation process of the fine cellulose fiber / nonwoven fabric composite is also included in the system. Each system flow in FIGS. 16 to 21 will be described later.
  • the MFC / nonwoven fabric composite supplied to the resin treatment process contains an air layer in the dry state, so that the resin penetrates into the interior as in all-layer resin treatment. In such a case, the air layer easily disturbs the resin to cause a non-uniform distribution.
  • the organic solvent resin solution is used, the organic solvent is used, and if an aqueous emulsion is used, the aqueous medium is replaced with an aqueous medium.
  • Such a preliminary process is referred to as a “precoat process” or a “saturation process”.
  • such a preliminary treatment is not necessarily required in the case of the surface resin treatment in which the surface is processed with a relatively thick resin liquid.
  • Resin treatment method Various resin treatment methods can be employed depending on the properties, concentration, viscosity and other fluidity of the resin. For example, impregnation method, spray method, coating method (gravure, offset gravure, micro gravure, flexo, reverse roll, blade, die, etc.).
  • These treatment methods can be the same method, but they can be used separately for all-layer resin treatment and surface resin treatment.
  • a system that employs an impregnation method or a spray method for a process corresponding to a full-layer resin treatment, and a coating method for a surface resin treatment.
  • a thin concentration resin solution is applied by a micro gravure method
  • a high concentration resin solution is applied by a flexo method. It is desirable to select and combine optimal processes according to the required specifications.
  • Solvent removal and drying methods Various choices can be considered depending on the adhesion of the treated resin to the surface of the drying roll, the degree of drying shrinkage, the need for surface smoothness, the need for a soft finish, etc. Since the water-resistant and highly breathable composite sheet according to the invention is highly breathable, it is relatively air permeable, unlike films, etc., so it is gripped on a net conveyor and blows hot air from the resin-treated surface. Is desirable. Further, in order to obtain an ironing effect for improving the surface uniformity and smoothness, it is desirable to wind by passing a hot roll having a hot press function, a Yankee drum, a calendar roll, or the like.
  • 16 to 21 are schematic views showing an example of a system flow including a method for producing a water-resistant and highly breathable composite sheet according to the present invention.
  • FIG. 16 is a flowchart showing an example in which the system flow 1: impregnation treatment of the refined cellulose fiber / nonwoven fabric composite with an organic solvent-based dissolved resin is performed.
  • MFC basis weight 12 g / m 2 spunbond meltblown composites having a basis weight of 13g / m 2 (SMS) consisting fine cellulose fibers, nonwoven complex (MFC-nonwoven composite), a polyurethane resin in toluene
  • the resin treatment is performed by impregnating the liquid containing 20% polyurethane / toluene resin. Thereafter, pressing and desolution are performed, and then drying is performed to remove the solvent contained in the composite, and the composite thus treated is wound up. Thereafter, the resin is cured by an arbitrary method to obtain a water-resistant and highly breathable composite sheet having a basis weight of 6 g / m 2 .
  • FIG. 17 is a flowchart showing an example in which system flow 2: twice-treatment with an SBR aqueous emulsion of a refined cellulose fiber / nonwoven fabric composite is performed.
  • MFC basis weight 8 g / m 2 spunbond meltblown composites having a basis weight of 15g / m 2 (SMS) consisting fine cellulose fibers, nonwoven complex (MFC-nonwoven composite), 8 with SBR resin latex
  • SMS spunbond meltblown composites having a basis weight of 15g / m 2
  • MFC-nonwoven composite nonwoven complex
  • the first coating is performed by microgravure roll coating using a% water diluted emulsion. Thereafter, the obtained composite is dried with hot air (about 90 ° C.) on a net conveyor.
  • the surface of the composite thus dried is subjected to a second coating by gravure roll coating using a 15% water diluted emulsion having SBR latex as a resin.
  • the composite thus obtained is dried with hot air (about 90 ° C.) on a net conveyor in the same manner as described above.
  • a press treatment is performed using a roll heated to a surface temperature of 130 ° C. to obtain a water-resistant and highly breathable composite sheet containing a basis weight of 6 g / m 2 .
  • FIG. 18 is a flowchart showing an example of a combination of system flow 3: treatment with an SBR aqueous emulsion in which zeolite of a fine cellulose fiber / nonwoven fabric complex is co-dispersed and treatment with a single SBR aqueous emulsion.
  • MFC basis weight 6 g / m 2 spunbond meltblown composites having a basis weight of 14g / m 2 (SMS) consisting fine cellulose fibers, nonwoven complex (MFC-nonwoven composite), having SBR latex as a resin
  • SMS spunbond meltblown composites having a basis weight of 14g / m 2
  • MFC-nonwoven composite nonwoven complex
  • the first coating by microgravure roll coating using 8% water diluted emulsion is performed. Thereafter, the obtained composite is dried with hot air (about 90 ° C.) on a net conveyor.
  • FIG. 19 is a flowchart showing an example in which the system flow 4: the refined cellulose fiber / nonwoven fabric composite supporting zeolite is treated twice with the SBR aqueous emulsion.
  • the refined cellulose fiber / nonwoven fabric composite supporting zeolite is treated twice with the SBR aqueous emulsion.
  • SMS spunbond / meltblown composite
  • the cellulose fiber / nonwoven fabric composite (MFC / nonwoven fabric composite) is first coated by flexo roll coating using 8% water-diluted emulsion having SBR latex as a resin.
  • the obtained composite is dried with hot air (about 90 ° C.) on a net conveyor with suction (suction mechanism).
  • the thus dried composite has a SBR latex as a resin and a water repellent material (trade name: Petrox P300 (manufactured by Meisei Chemical Co., Ltd.)) as a water repellent material.
  • a second coating is performed by flexo roll coating using a mixed solution containing 10% and 10% SBR.
  • the composite thus obtained is preliminarily dried (70 to 80 ° C.) on a net conveyor with suction in the same manner as described above.
  • finish drying is further performed using a Yankee dryer (surface temperature 130 ° C.). In this way, a water-resistant and highly air-permeable composite sheet having a water repellency with a resin amount of 6 g / m 2 and a water repellent material amount of 2 g / m 2 is obtained.
  • FIG. 20 is a flowchart showing an example in which the system flow 5: the production of the refined cellulose fiber / nonwoven fabric composite and the SBR latex treatment are continuously performed.
  • a refined cellulose fiber / nonwoven fabric composite is produced and prepared. That is, from PE / PET composite fiber (15d ⁇ 45mm), which is a raw material for the nonwoven fabric of fine cellulose fiber / nonwoven fabric composite, an easily heat-meltable card web (20 g / m 2 per unit area) is obtained using a defibrator and a card machine. To manufacture.
  • water is added to the resulting web in a saturator to saturate the entire web with water.
  • the web is coated with MFC at a wet coating station using an MFC 1% aqueous dispersion of MFC and water.
  • vacuum dehydration is performed by suction (suction mechanism) to remove free water, and then the web and MFC are heat-sealed using a Yankee drum dryer having a surface temperature of 130 to 140 ° C.
  • a refined cellulose fiber / nonwoven fabric composite is obtained.
  • a 20% water-diluted emulsion having SBR latex as a resin is coated on the MFC surface of the fine cellulose fiber / nonwoven fabric composite by flexo roll coating.
  • the obtained composite is dried with hot air (about 90 ° C.) on a net conveyor. In this way, a water-resistant and highly breathable composite sheet containing a basis weight of 6 g / m 2 is obtained.
  • FIG. 21 is a flowchart showing an example in which the system flow 6: production of a refined cellulose fiber / nonwoven fabric composite and treatment with an acrylic acid emulsion and a water repellent material are continuously performed.
  • a refined cellulose fiber / nonwoven fabric composite is produced and prepared. That is, in a saturator, water containing a polyether nonionic active agent 200PPM as an activator is added to a spunbond melt blown (SMS nonwoven fabric) having a basis weight of 15 g / m 2 to saturate the SMS nonwoven fabric.
  • SMS nonwoven fabric spunbond melt blown
  • the SMS nonwoven fabric is coated with a mixed slurry containing MFC 0.8% and zeolite 0.5% composed of MFC, zeolite and water. Thereafter, vacuum dehydration is performed by suction (suction mechanism).
  • an acrylic acid emulsion (20% aqueous dispersion) containing an ammonium zirconium carbonate-based crosslinking agent (trade name: Baycoat 20 (manufactured by Nippon Light Metal Co., Ltd.)) is used as the crosslinking agent.
  • Perform spray coating is performed.
  • the obtained nonwoven fabric is dried with hot air (about 90 ° C.) on a net conveyor to obtain a composite.
  • the obtained composite is further subjected to a water repellent treatment by microgravure roll coating using an aqueous dispersion (15%) having a paraffinic water repellent (trade name: Petrox P300 (manufactured by Meisei Chemical Co., Ltd.)). Apply. Thereafter, the treated composite is dried with hot air (about 90 ° C.) on a net conveyor, and the water-resistant and highly breathable composite containing a resin amount of 6 g / m 2 and a water repellent amount of 3 g / m 2. Get a sheet.
  • a water repellent treatment by microgravure roll coating using an aqueous dispersion (15%) having a paraffinic water repellent (trade name: Petrox P300 (manufactured by Meisei Chemical Co., Ltd.)). Apply. Thereafter, the treated composite is dried with hot air (about 90 ° C.) on a net conveyor, and the water-resistant and highly breathable composite containing a resin amount of 6 g / m 2
  • Example 1 Example of producing a refined cellulose fiber / nonwoven fabric composite using a refined cellulose fiber and a nonwoven fabric
  • This example shows a refined cellulose fiber and a nonwoven fabric used for producing a water-resistant and highly breathable composite sheet according to the present invention.
  • miniaturized cellulose fiber and nonwoven fabric composite (MFC / nonwoven fabric composite) which consists of these is shown.
  • DDR model AW14 (manufactured by Aikawa Tekko)
  • Disc plate Blade width 2.0mm, groove width 3.0mm
  • Pulp flow rate to DDR 1 m 3 / min Average number of passes of DDR: 100 times Blade clearance: 0.13 to 0.23 mm
  • the characteristics of the prepared finely divided cellulose fiber were as follows.
  • the water retention was measured as follows.
  • the degree of water retention is for the purpose of comparing dispersion stability, and a simple and stable method is preferable as the measurement method. Therefore, in the present invention, the degree of water retention is determined by directly reading the capacity of the sedimentation MFC of the centrifugal treatment and evaluating this as the degree of water retention. The measurement method is shown below.
  • SMS non-woven fabric made of polypropylene (manufactured by AVGOL) having the following characteristics was used.
  • the refined cellulose fiber / nonwoven fabric composite of Sample 3 was used for the production of the following water-resistant and highly breathable composite sheet.
  • Example 2 Production example of water-resistant and highly breathable composite sheet according to the present invention (pre-coating and coating using resin) Using the refined cellulose fiber / nonwoven fabric composite (MFC / SMS composite) of Sample 3 obtained in Example 1, the water-resistant and highly air-permeable composite sheet of Samples 6 to 9 according to the present invention according to the flowchart shown in FIG. Manufactured. Table 8 below summarizes the solid content concentrations of the precoat and resin emulsion described in FIG.
  • MFC / SMS composite refined cellulose fiber / nonwoven fabric composite
  • the diameter of the wire used for coating and the drying and curing conditions are as follows.
  • the resin emulsion used for coating was obtained by dispersing SBR latex as a resin (manufactured by A & L, catalog number: PA0339) in ion-exchanged water.
  • the pre-coating may be performed using a solvent of 100% water.
  • MFC on the surface hydrates and swells with time, and bulges are generated on the surface.
  • ethanol / water that does not easily swell the MFC was adopted.
  • the ethanol / water ratio may be appropriately selected according to the characteristics of the material used and the conditions such as coating conditions.
  • “visual observation of coating state” is an evaluation by visually observing and evaluating the surface state of the surface of the water-resistant and highly breathable composite sheet coated with the obtained resin.
  • “Air permeability” refers to the air permeability obtained according to ⁇ Air permeability> described in the following evaluation method.
  • the “surface strength” is an evaluation of the state of the constituent components of the sheet according to ⁇ Evaluation of Bond Strength of Coated Surface> described in the following evaluation method. Here, the surface strength is measured by a 90 ° pilling test. The results obtained are shown.
  • “nonwoven fabric destruction” indicated by * 1 means that the MFC layer and the nonwoven fabric layer are stably bonded by a resin.
  • the “5-spot test” indicates the time when the physiological saline was spotted on the MFC surface and infiltrated according to ⁇ Evaluation of diffusibility and permeability from the surface> described in the following evaluation method. is there.
  • the “ring test” refers to leakage of stained physiological saline 2 hours, 6 hours and 24 hours after the start of the test according to ⁇ Evaluation of occurrence of swelling and water penetration state> described in the following evaluation method. The presence or absence of occurrence was evaluated.
  • sample 7 had a more uniform coating state, and the amount of coated resin and air permeability were similar. There was little variation. Further, comparing sample 7 with sample 9 having a larger amount of resin than sample 7, the level of water resistance (5-spot test, ring test) was high while maintaining low air permeability. From these things, like the conditions of sample 9, as coating conditions, pre-coating was performed as a pretreatment, and the basis weight was 4.0 g / m 2 or more.
  • Example 3 Production example of water-resistant and highly breathable composite sheet according to the present invention (multistage treatment using resin)
  • a predetermined surface MFC surface or SMS surface
  • SBR latex made by A & L, catalog number: PA3807
  • the solid content was 5%, 10%, and 15%.
  • a resin emulsion was used.
  • the coating with the resin emulsion was performed by coating using a hand coat as in Example 2 above.
  • the diameters of the hand coat wires used for the hand coat were 0.1 mm ⁇ , 0.15 mm ⁇ and 0.20 mm ⁇ . It was. Of each sample obtained using these wires, three samples having a uniform resin amount were selected per sample and subjected to the following evaluations.
  • the impregnation treatment using the resin emulsion is performed by preparing a sufficient amount of a resin emulsion having a predetermined solid content in a stainless steel bat and immersing the MFC / SMS composite having a hand coat size for 1 minute. went. Moreover, about the amount of impregnation, after the immersion, the filter paper was put in an assistance, passed through a nip roll, and then the amount of impregnation was defined.
  • the conditions of air drying, drying and curing are as follows.
  • Example 4 Production example of water-resistant and highly breathable composite sheet according to the present invention (coating using resin and zeolite)
  • resin emulsion used in this example solid content obtained by dispersing SBR latex (manufactured by A & L, catalog number: PA3807) as resin used in Example 2 described in Example 2 above in ion-exchanged water, 5% and 10% resin emulsions were used.
  • zeolite-containing resin emulsion used in this example a zeolite-containing resin emulsion obtained by adding zeolite to the resin emulsion having a solid content of 5% or 10% to a final concentration of 5% by weight was used. .
  • the zeolite-containing resin emulsion was used by stirring immediately before coating because the zeolite easily precipitates in the emulsion.
  • the water-resistant and highly breathable composite sheet having the resin and zeolite of Samples 15 to 18 thus obtained was evaluated according to the following evaluation method.
  • a filter paper for detection (trade name: GRADE2 (manufactured by Advantec), basis weight: 125 g / m 2 , thickness: 0.26 mm) for detecting leakage of moisture from the sample on a transparent glass plate. And put the sample to be evaluated on it. Predetermined amounts (0.1, 0.2, 0.4, 0.8, and 1.0.1) on predetermined surfaces (surfaces directly coated and uncoated) of the sample thus arranged. 5 mL) of stained saline was spotted. After a lapse of a certain time, the detection filter paper and the sample were observed, and the infiltration start time, the presence / absence of occurrence of leak and the time thereof, and the test end time were evaluated.
  • GRADE2 manufactured by Advantec
  • a filter paper for detection (trade name: GRADE2 (manufactured by Advantec), basis weight: 125 g / m 2 , thickness: 0.26 mm) for detecting leakage of moisture from the sample on a transparent glass plate. And put the sample to be evaluated on it.
  • a ring (made of stainless steel, weight 500 g, thickness 5 mm, inner area 50 cm 2 ) is placed thereon.
  • a resin adhesive (trade name: New Polygrip S (Earth Pharmaceutical Co., Ltd.) is placed between the sample and the ring to prevent leakage of water from between the sample and the ring. To do. Further, a push plate (made of stainless steel, weight 3 kg) is placed on the ring. Further, an observation mirror capable of observing the state of the detection filter paper is placed below the transparent glass plate.
  • the detection filter paper and the sample are observed, and the leak occurrence time (time) and location
  • the test end time (time), the state of the detection filter paper at that time, and the expanded state of the sample at the end of the test were evaluated.
  • the predetermined time was recorded 2 hours and / or 6 hours after the start of the test, and 24 hours after being left overnight.
  • a protective sheet (trade name: TCF (manufactured by Nimura Chemical Co., Ltd.)) for protecting the sample was placed, and a liquid absorption mat (trade name: TCF (manufactured by Nimura Chemical Co., Ltd., weight per mat: 20 mats each having 30 g / m 2 laid on top of each other) was placed, and weight (2.25 kg (as combined with the push plate)) was placed through the push plate.
  • an observation mirror capable of observing the state of the detection filter paper was placed below the transparent glass plate. The weight of 2.25 kg corresponds to a weight of 10 g / cm 2 .
  • the time when the physiological saline solution first leaks from the sample (leak generation), the time when the leak grows and expands (leak expansion), the time required from the occurrence of the leak to the growth expansion, detection
  • the time when the physiological saline leaked to the filter paper exceeded the limit, the weight of the physiological saline absorbed by the detection filter paper, and the like were evaluated. The test was terminated after 8 hours from the start of the test.
  • a 15 mm wide Nichiban cellophane tape is applied to the coated surface of the target sheet so that the adhesive surface is 15 mm ⁇ 10 mm. After lightly pressing with flannel from above, a load of 1 kg / cm 2 is applied for 10 minutes. It was. Thereafter, the cellophane tape was peeled off from the target sheet at an angle of 90 ° or 180 °, and the state of the components of the sheet adhering to the cellotape was visually evaluated.
  • a test performed at an angle of 180 ° is referred to as a 180 ° pilling test, and a test performed at an angle of 90 ° is referred to as a 90 ° pilling test.

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Abstract

This invention provides a water-resistant and high air permeability composite sheet, which can exhibit desired properties while maintaining high water resistance and high air permeability and can be produced by treating a sheet-like composite of a refined cellulose fiber and a nonwoven fabric with a resin, and a process for producing the water-resistant and high-air permeability composite sheet. The water-resistant and high-air permeability composite sheet is characterized in that it has a four-layer structure comprising a resin layer (A), a resin/MFC coexisting layer (B), an MFC/nonwoven fabric coexisting layer (C), and a nonwoven fabric layer (D) as viewed from the top surface toward the back surface, wherein the MFC surface and the nonwoven fabric surface constitute the upper surface and the back surface, respectively, and is produced by treating, with a resin, a refined cellulose fiber/nonwoven fabric composite having a three-layer structure of a refined cellulose fiber (MFC) and a nonwoven fabric, that is, an MFC layer, an MFC/nonwoven fabric coexisting layer, and a nonwoven fabric layer.

Description

耐水性高通気性複合シート及びその製造方法Water resistant and highly breathable composite sheet and method for producing the same

　本発明は、耐水性高通気性複合シート及びその製造方法に関する。 The present invention relates to a water-resistant and highly breathable composite sheet and a method for producing the same.

　衛生用又は医療用製品に用いられるシート状又はフィルム状材料には、液体を漏らさない一方で、ある程度の通気性が必要とされる。プラスチックフィルムは、液体を浸透させることは困難であることから液体を漏らさない機能を有するものの、組織が緻密であるために通気性を有していない。すなわち、耐水性と通気性の両立が要求されているおむつのバックシート（人体との非接触側）等のシート素材としてポリエチレン等の疎水性フィルムに炭酸カルシウム等のフィラーと異種ポリマーとの混合による相分離層を形成するなどの手段による微多孔質フィルムが使用されているが、透気度（ＪＩＳ　Ｐ　８１１７）３００～８００秒／１００ｍＬ程度で実用上十分な通気性能を発揮するものとはいえないのが現状である。一方、不織布や紙などは、通気性を有するものの、液体の漏出を完全に防止することはできない。これらのシート材料の欠点を解決するため、特許文献１は、微細繊維状セルロース（Ｍｉｃｒｏｆｉｂｒｉｌｌａｔｅｄ　Ｃｅｌｌｕｌｏｓｅ）と不織布とからなるシート材料の発明を提案する。この発明では、微細繊維状セルロースとして、平均繊維長が０．３ｍｍ以下であり、且つ１５ｍＬ／ｇ以上の抱水度を有する極めて細い繊維状セルロースが用いられている。このような繊維状セルロースとしては、パルプ又はコットン繊維のスラリーを機械的処理により微細繊維化することによって得られるものや、バクテリアがつくりだすバクテリアセルロースとよばれるものが挙げられる。機械的処理方法としては高圧ホモジナイザー、グラインダー、リファイナー等による方法が挙げられる。この微細繊維状セルロースを溶媒に分散した分散液を不織布上に塗工して薄層を形成しておき、この薄層から脱溶媒することによって上記シート材が作製される。 A sheet-like or film-like material used for hygiene or medical products requires a certain degree of breathability while not leaking liquid. The plastic film has a function not to leak the liquid because it is difficult to permeate the liquid, but does not have air permeability because the tissue is dense. That is, by mixing a hydrophobic film such as polyethylene with a filler such as calcium carbonate and a heterogeneous polymer as a sheet material such as a back sheet (non-contact side with a human body) of a diaper that requires both water resistance and air permeability. Although a microporous film by means such as forming a phase separation layer is used, it can be said that air permeability (JIS P 8117) is about 300 to 800 seconds / 100 mL and exhibits practically sufficient ventilation performance. There is no current situation. On the other hand, although non-woven fabrics and paper have air permeability, it is impossible to completely prevent liquid leakage. In order to solve the drawbacks of these sheet materials, Patent Document 1 proposes an invention of a sheet material composed of microfibrous cellulose and a nonwoven fabric. In the present invention, as the fine fibrous cellulose, an extremely thin fibrous cellulose having an average fiber length of 0.3 mm or less and a water retention of 15 mL / g or more is used. Examples of such fibrous cellulose include those obtained by making a pulp or cotton fiber slurry into fine fibers by mechanical treatment, and those called bacterial cellulose produced by bacteria. Examples of the mechanical treatment method include a method using a high-pressure homogenizer, a grinder, a refiner, and the like. A thin layer is formed by applying a dispersion obtained by dispersing the fine fibrous cellulose in a solvent on a nonwoven fabric, and the sheet material is prepared by removing the solvent from the thin layer.

　上記シート材料は、薄いため、通風性もよく、防塵性やバクテリアバリアー性を有しているので、衛生用又は医療用材料としては優れた材料である。しかしながら、女性用品、子ども用及び大人用おむつ等の吸収体製品の用途としては、尿などの液体の漏出防止性が不十分であるため、実用に供されていない。また、このようなシート材に、撥水性や脱臭性などの所望の機能を付与する場合、合成ポリマーからなる種々の樹脂成分を含有させる方法が挙げられるが、上記のような高い耐水性や通気性を維持しつつ、このような所望の機能を発揮させることは、困難であって、未だ実用上利用し得るレベルに達していないのが実状である（特許文献２）。
特開平１０－２４８８７２号公報 特開２００８－０８０７４７号公報 国際公開第２００４／００９９０２号パンフレット Ｓ．Ｙａｍａｎａｋａら著、Ｊ．Ｍａｔｅｒｉａｌ　Ｓｃｉｅｎｃｅ、１９８９年、２４巻、ｐ．３１４１ Since the sheet material is thin, it has good ventilation, and has dust resistance and bacteria barrier properties. Therefore, it is an excellent material for sanitary or medical use. However, it has not been put to practical use as absorbent products such as women's products, diapers for children and adults, because the prevention of leakage of liquids such as urine is insufficient. In addition, when a desired function such as water repellency and deodorizing property is imparted to such a sheet material, a method of incorporating various resin components made of a synthetic polymer can be mentioned. It is difficult to exhibit such a desired function while maintaining the properties, and the actual situation is that it has not yet reached a practically usable level (Patent Document 2).
Japanese Patent Laid-Open No. 10-248872 JP 2008-080747 A International Publication No. 2004/009902 Pamphlet S. Yamanaka et al. Material Science, 1989, 24, p. 3141

　本発明は、上記の従来の問題に鑑みてなされたものであり、高い耐水性と、高い通気性を維持しつつ、所望の特性を発揮し得る、微細化セルロース繊維と不織布とのシート状複合体に樹脂加工して得られる、耐水性高通気性複合シート及びこの耐水性高通気性複合シートの製造方法を提供することを目的とする。 The present invention has been made in view of the above-described conventional problems, and is a sheet-like composite of fine cellulose fibers and a nonwoven fabric that can exhibit desired characteristics while maintaining high water resistance and high air permeability. An object of the present invention is to provide a water-resistant and highly breathable composite sheet obtained by processing a resin on a body and a method for producing this water-resistant and highly breathable composite sheet.

　本発明による耐水性高通気性複合シートは、微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面から裏面に向かって樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、ＭＦＣ・不織布共存層（Ｃ）及び不織布層（Ｄ）の４層構造からなることを特徴とする。これにより、耐水性と通気性のバランスのとれた耐水性高通気性複合シートを得ることができる。 The water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of an MFC layer composed of a finely divided cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer. The resin layer (A), resin / MFC coexistence layer (B), MFC · It consists of 4 layer structure of a nonwoven fabric coexistence layer (C) and a nonwoven fabric layer (D), It is characterized by the above-mentioned. Thereby, a water-resistant and highly breathable composite sheet in which water resistance and breathability are balanced can be obtained.

　本発明による耐水性高通気性複合シートは、微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面から裏面に向かって樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、樹脂・ＭＦＣ・不織布共存層（Ｅ）及び不織布層（Ｄ）の４層構造からなることを特徴とする。これにより、耐水性と通気性のさらにバランスのとれた耐水性高通気性複合シートを得ることができる。 The water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of an MFC layer composed of a finely divided cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer. When the MFC surface is the upper surface and the nonwoven fabric surface is the lower back surface, the resin layer (A), resin / MFC coexistence layer (B), resin It has a four-layer structure of an MFC / nonwoven fabric coexisting layer (E) and a nonwoven fabric layer (D). Thereby, a water-resistant and highly breathable composite sheet in which water resistance and breathability are further balanced can be obtained.

　本発明による耐水性高通気性複合シートは、微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面から裏面に向かって樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、樹脂・ＭＦＣ・不織布共存層（Ｅ）及び樹脂・不織布共存層（Ｆ）の４層構造からなることを特徴とする。これにより、耐水性と通気性のさらにバランスのとれた耐水性高通気性複合シートを得ることができる。 The water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of an MFC layer composed of a finely divided cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer. When the MFC surface is the upper surface and the nonwoven fabric surface is the lower back surface, the resin layer (A), resin / MFC coexistence layer (B), resin It has a four-layer structure of an MFC / nonwoven fabric coexisting layer (E) and a resin / nonwoven fabric coexisting layer (F). Thereby, a water-resistant and highly breathable composite sheet in which water resistance and breathability are further balanced can be obtained.

　本発明による耐水性高通気性複合シートは、微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面から裏面に向かって樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、樹脂・ＭＦＣ・不織布共存層（Ｅ）、ＭＦＣ・不織布共存層（Ｃ）及び不織布層（Ｄ）の５層構造からなることを特徴とする。これにより、耐水性と通気性のさらにバランスのとれた耐水性高通気性複合シートを得ることができる。 The water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of an MFC layer composed of a finely divided cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer. When the MFC surface is the upper surface and the nonwoven fabric surface is the lower back surface, the resin layer (A), resin / MFC coexistence layer (B), resin It has a five-layer structure of an MFC / nonwoven fabric coexisting layer (E), an MFC / nonwoven fabric coexisting layer (C), and a non-woven fabric layer (D). Thereby, a water-resistant and highly breathable composite sheet in which water resistance and breathability are further balanced can be obtained.

　本発明による耐水性高通気性複合シートは、微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面から裏面に向かって樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、樹脂・ＭＦＣ・不織布共存層（Ｅ）、樹脂・不織布共存層（Ｆ）及び不織布層（Ｄ）の５層構造からなることを特徴とする。これにより、耐水性と通気性のさらにバランスのとれた耐水性高通気性複合シートを得ることができる。 The water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of an MFC layer composed of a finely divided cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer. When the MFC surface is the upper surface and the nonwoven fabric surface is the lower back surface, the resin layer (A), resin / MFC coexistence layer (B), resin It has a five-layer structure of an MFC / nonwoven fabric coexisting layer (E), a resin / nonwoven fabric coexisting layer (F), and a non-woven fabric layer (D). Thereby, a water-resistant and highly breathable composite sheet in which water resistance and breathability are further balanced can be obtained.

　本発明による耐水性高通気性複合シートにおいて、微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面のＭＦＣ面上に存在する樹脂層（Ａ）と、さらに裏面の不織布面下に存在する樹脂層（Ａ）と上下に２つの樹脂層（Ａ）を備えたことを特徴とする。これにより、耐水性をさらに高めた耐水性高通気性複合シートを得ることができる。 In the water-resistant and highly breathable composite sheet according to the present invention, a refined cellulose fiber / nonwoven fabric composite having a three-layer structure consisting of an MFC layer composed of a refined cellulose fiber (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer When the MFC surface is the upper surface and the nonwoven fabric surface is the lower back surface, which is obtained by applying resin processing to the body, the resin layer (A) that exists on the MFC surface on the front surface, and further under the nonwoven fabric surface on the back surface And a resin layer (A) and two resin layers (A) above and below. Thereby, the water-resistant highly breathable composite sheet which further improved water resistance can be obtained.

　本発明による耐水性高通気性複合シートにおいて、前記Ａ層の上表面に撥水材層（Ｒ）を更に形成させたことを特徴とする。これにより、耐水性及び通気性にさらに撥水性を付与した耐水性高通気性複合シートを得ることができる。 The water-resistant and highly breathable composite sheet according to the present invention is characterized in that a water repellent material layer (R) is further formed on the upper surface of the A layer. Thereby, the water-resistant highly breathable composite sheet which gave water repellency to water resistance and breathability can be obtained.

　本発明による耐水性高通気性複合シートにおいて、前記Ａ層は、樹脂と撥水材とを含有する樹脂・撥水材共存層（Ｓ）であることを特徴とする。これにより、耐水性と通気性に加え、撥水性を有する耐水性高通気性複合シートを得ることができる。 In the water-resistant and highly breathable composite sheet according to the present invention, the layer A is a resin / water repellent material coexisting layer (S) containing a resin and a water repellent material. Thereby, in addition to water resistance and breathability, a water-resistant highly breathable composite sheet having water repellency can be obtained.

　本発明による耐水性高通気性複合シートにおいて、撥水材層（Ｒ）と樹脂・撥水材共存層（Ｓ）とを併せ持つことを特徴とする。これにより、耐水性と通気性に加え、撥水性を有する耐水性高通気性複合シートを得ることができる。 The water-resistant and highly breathable composite sheet according to the present invention is characterized by having both a water-repellent material layer (R) and a resin / water-repellent material coexisting layer (S). Thereby, in addition to water resistance and breathability, a water-resistant highly breathable composite sheet having water repellency can be obtained.

　本発明による耐水性高通気性複合シートにおいて、前記Ｂ、Ｃ、Ｄ、Ｅ及びＦ層のいずれかの層には、固形粉体成分が担持されていることを特徴とする。これにより、耐水性及び通気性に加え、固形粉体成分に由来する所望の特性を有する耐水性高通気性複合シートを得ることができる。 The water-resistant and highly breathable composite sheet according to the present invention is characterized in that a solid powder component is supported on any one of the B, C, D, E, and F layers. Thereby, in addition to water resistance and air permeability, a water resistant and highly air permeable composite sheet having desired characteristics derived from the solid powder component can be obtained.

　本発明による耐水性高通気性複合シートにおいて、前記固形粉体成分は、脱臭剤（臭気吸着剤）であることを特徴とする。これにより、耐水性及び通気性に加え、脱臭性を有する耐水性高通気性複合シートを得ることができる。 In the water-resistant and highly breathable composite sheet according to the present invention, the solid powder component is a deodorizer (odor adsorbent). Thereby, in addition to water resistance and breathability, the water-resistant highly breathable composite sheet which has deodorizing property can be obtained.

　本発明による耐水性高通気性複合シートにおいて、前記微細化セルロース繊維は、脱臭剤と結合されていることを特徴とする。これにより、脱臭性がさらに向上された耐水性高通気性複合シートを得ることができる。 In the water-resistant and highly breathable composite sheet according to the present invention, the refined cellulose fiber is combined with a deodorizer. As a result, a water-resistant and highly breathable composite sheet with further improved deodorization can be obtained.

　本発明による耐水性高通気性複合シートにおいて、ガーレー法による透気度測定で１０秒／１００ｍＬ～１５０秒／１００ｍＬの通気性と、水深１０ｍｍでのリング式テストで６時間以上漏れが生じない耐久耐水性をもったことを特徴とする。これにより、さらに耐水性が安定化される。 In the water-resistant and highly air-permeable composite sheet according to the present invention, the air permeability measured by the Gurley method is 10 seconds / 100 mL to 150 seconds / 100 mL, and the durability is such that leakage does not occur for 6 hours or more in a ring test at a water depth of 10 mm. It is characterized by having water resistance. Thereby, water resistance is further stabilized.

　本発明による吸収体製品は、上記の耐水性高通気性複合シートを防漏体として用いてなることを特徴とする。これにより、高い耐水性と通気性とを両立した吸収体製品を得ることができる。 The absorbent product according to the present invention is characterized by using the above water-resistant and highly breathable composite sheet as a leak preventer. Thereby, an absorbent product having both high water resistance and air permeability can be obtained.

　本発明による耐水性高通気性複合シートの製造方法は：
　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ複合体に樹脂加工を施すことによって得られる、耐水性高通気性複合シートの製造方法であって、
　樹脂成分が少なくとも前記複合体のＭＦＣ層に行き渡るような樹脂処理（全層樹脂処理）と、
　樹脂成分を前記複合体の上表面層のみにとどめる樹脂処理（表層樹脂処理）と、
　を組合わせて複合体に樹脂加工を施すことを特徴とする。これにより、耐水性と通気性のバランスのとれた耐水性高通気性複合シートを得ることができる。 The method for producing a water-resistant and highly breathable composite sheet according to the present invention is:
A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of
Resin treatment (all-layer resin treatment) such that the resin component reaches at least the MFC layer of the composite;
Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite;
The composite is subjected to resin processing in combination. Thereby, a water-resistant and highly breathable composite sheet in which water resistance and breathability are balanced can be obtained.

　また、本発明による耐水性高通気性複合シートの製造方法は：
　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ複合体に樹脂加工を施すことによって得られる、耐水性高通気性複合シートの製造方法であって、
　樹脂成分が少なくとも前記複合体のＭＦＣ層及びＭＦＣ・不織布共存層に行き渡るような樹脂処理（全層樹脂処理）と、
　樹脂成分を前記複合体の上表面層のみにとどめる樹脂処理（表層樹脂処理）と、
　を組合わせて複合体に樹脂加工を施すことを特徴とする。これにより、耐水性と通気性のバランスのとれた耐水性高通気性複合シートを得ることができる。 Also, the method for producing a water-resistant and highly breathable composite sheet according to the present invention is:
A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of
Resin treatment (all-layer resin treatment) in which the resin component reaches at least the MFC layer and the MFC / nonwoven fabric coexisting layer of the composite,
Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite;
The composite is subjected to resin processing in combination. Thereby, a water-resistant and highly breathable composite sheet in which water resistance and breathability are balanced can be obtained.

また、本発明による耐水性高通気性複合シートの製造方法は：
　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ複合体に樹脂加工を施すことによって得られる、耐水性高通気性複合シートの製造方法であって、
　樹脂成分が少なくとも前記複合体の３層全層に行き渡るような樹脂処理（全層樹脂処理）と、
　樹脂成分を前記複合体の上表面層のみにとどめる樹脂処理（表層樹脂処理）と、
　を組合わせて複合体に樹脂加工を施すことを特徴とする。これにより、耐水性と通気性のバランスのとれた耐水性高通気性複合シートを得ることができる。 Also, the method for producing a water-resistant and highly breathable composite sheet according to the present invention is:
A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of
Resin treatment in which the resin component spreads over at least the three layers of the composite (all layer resin treatment);
Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite;
The composite is subjected to resin processing in combination. As a result, a water-resistant and highly breathable composite sheet having a good balance between water resistance and breathability can be obtained.

　本発明による耐水性高通気性複合シートの製造方法において、前記全層樹脂処理を最初に行い、その後、前記表層樹脂処理を行うことを特徴とする。これにより、安定した耐水性を賦与することができる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the all-layer resin treatment is performed first, and then the surface layer resin treatment is performed. Thereby, stable water resistance can be imparted.

　本発明による耐水性高通気性複合シートの製造方法において、前記表層樹脂処理を最初に行い、その後、前記全層樹脂処理を行うことを特徴とする。これにより、安定した耐水性を賦与することができる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the surface resin treatment is performed first, and then the all-layer resin treatment is performed. Thereby, stable water resistance can be imparted.

　本発明による耐水性高通気性複合シートの製造方法において、撥水材を用いた加工処理をさらに行うことを特徴とする。これにより、さらに安定した耐水性を賦与することができる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the processing using a water repellent material is further performed. Thereby, more stable water resistance can be imparted.

　本発明による耐水性高通気性複合シートの製造方法において、前記表層樹脂処理は、前記樹脂に撥水材を混在させて行うことを特徴とする。これにより、プロセスを簡略化して、安定した耐水性を賦与することができる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the surface resin treatment is performed by mixing a water repellent material with the resin. This simplifies the process and provides stable water resistance.

　本発明による耐水性高通気性複合シートの製造方法において、前記複合体は、該複合体中にあらかじめ脱臭剤層を形成したものであることを特徴とする。これにより、安定に脱臭剤層を内部に担持させることができる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the composite is characterized in that a deodorant layer is previously formed in the composite. Thereby, a deodorizer layer can be stably carried inside.

　本発明による耐水性高通気性複合シートの製造方法において、前記全層樹脂処理は、前記樹脂に脱臭剤を混在させて行うことを特徴とする。これにより、プロセスを簡略化して脱臭効果を賦与することができる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the all-layer resin treatment is performed by mixing a deodorizer with the resin. Thereby, a process can be simplified and a deodorizing effect can be provided.

　本発明による耐水性高通気性複合シートの製造方法において、前記全層樹脂処理は、固形分８％以下の熱可塑性合成樹脂の水系エマルジョンを用いて行われることを特徴とする。これにより、通気性と耐水性のバランスのとれた性能を賦与できる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the all-layer resin treatment is performed using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 8% or less. Thereby, the performance with which air permeability and water resistance were balanced can be provided.

　本発明による耐水性高通気性複合シートの製造方法において、前記表層樹脂処理は、固形分１０％以上の熱可塑性合成樹脂の水系エマルジョンを用いて行われることを特徴とする。これにより、安定した表層樹脂層を形成させることができる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the surface resin treatment is performed using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 10% or more. Thereby, a stable surface resin layer can be formed.

　本発明による耐水性高通気性複合シートの製造方法において、前記全層樹脂処理は、固形分８％以下の熱可塑性合成樹脂の水系エマルジョンを用いて、前記複合体の裏面上に対して行われることを特徴とする。これにより、耐水性の安定性ををより高めることができる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the all-layer resin treatment is performed on the back surface of the composite using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 8% or less. It is characterized by that. Thereby, the stability of water resistance can be further improved.

　本発明による耐水性高通気性複合シートの製造方法において、前記全層樹脂処理は、固形分１％～５％の熱可塑性合成樹脂の水系エマルジョンを用いて行う工程と、固形分３％～８％の熱可塑性合成樹脂の水系エマルジョンを用いて行う工程と、を有することを特徴とする。これにより、ムラのない均一な樹脂加工を行うことができる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the all-layer resin treatment is performed using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 1% to 5%, and a solid content of 3% to 8%. % Using a water-based emulsion of thermoplastic synthetic resin. Thereby, uniform resin processing without unevenness can be performed.

　本発明による耐水性高通気性複合シートの製造方法において、前記の撥水材を用いた加工処理は、撥水材の水系エマルジョンを用いて行われることを特徴とする。これにより、撥水材を安定に表面に固着できる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the processing using the water-repellent material is performed using an aqueous emulsion of the water-repellent material. Thereby, the water repellent material can be stably fixed to the surface.

　本発明による耐水性高通気性複合シートの製造方法において、前記表層樹脂処理は、固形分１０％以上の熱可塑性合成樹脂の水系エマルジョンに撥水材の水系エマルジョンを混和した混合エマルジョンを用いて行われることを特徴とする。これにより、プロセスを簡略化して撥水材層を表面層部位に形成することができる。 In the method for producing a water-resistant and highly breathable composite sheet according to the present invention, the surface resin treatment is performed using a mixed emulsion in which an aqueous emulsion of a water-repellent material is mixed with an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 10% or more. It is characterized by being. Thereby, a process can be simplified and a water repellent material layer can be formed in a surface layer site | part.

　本発明によれば、高い耐水性と、高い通気性とを維持しつつ、樹脂による所望の特性を発揮し得る耐水性高通気性複合シートを得ることが可能となる。 According to the present invention, it is possible to obtain a water-resistant and highly breathable composite sheet capable of exhibiting desired properties with a resin while maintaining high water resistance and high breathability.

本発明における微細化セルロース繊維・不織布複合体を示す概略図である。It is the schematic which shows the micronized cellulose fiber and nonwoven fabric complex in this invention. ＭＦＣと、微細化セルロース繊維・不織布複合体の諸特性とその応用である。Various characteristics of MFC and refined cellulose fiber / nonwoven fabric composites and their applications. 本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、ＭＦＣ・不織布共存層（Ｃ）と、不織布層（Ｄ）とからなる４層構造を有する耐水性高通気性複合シートを示す。It is an example of the water-resistant highly breathable composite sheet by this invention, Comprising: From resin layer (A), resin and MFC coexistence layer (B), MFC and nonwoven fabric coexistence layer (C), and nonwoven fabric layer (D) A water-resistant and highly breathable composite sheet having a four-layer structure is shown. 本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布層（Ｄ）とからなる４層構造を有する耐水性高通気性複合シートを示す。It is an example of the water-resistant highly breathable composite sheet by this invention, Comprising: Resin layer (A), Resin / MFC coexistence layer (B), Resin / MFC / nonwoven fabric coexistence layer (E), Nonwoven fabric layer (D) The water-resistant highly breathable composite sheet which has the 4 layer structure which consists of these is shown. 本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、樹脂・不織布共存層（Ｆ）とからなる４層構造を有する耐水性高通気性複合シートを示す。It is an example of the water-resistant highly breathable composite sheet by this invention, Comprising: Resin layer (A), Resin / MFC coexistence layer (B), Resin / MFC / nonwoven fabric coexistence layer (E), Resin / nonwoven fabric coexistence layer The water-resistant highly breathable composite sheet which has a four-layer structure consisting of (F) is shown. 本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、ＭＦＣ・不織布共存層（Ｃ）と、不織布層（Ｄ）とからなる５層構造を有する耐水性高通気性複合シートを示す。It is an example of the water-resistant highly breathable composite sheet by this invention, Comprising: Resin layer (A), Resin / MFC coexistence layer (B), Resin / MFC / nonwoven fabric coexistence layer (E), MFC / nonwoven fabric coexistence layer The water-resistant highly breathable composite sheet which has 5 layer structure which consists of (C) and a nonwoven fabric layer (D) is shown. 本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、樹脂・不織布共存層（Ｆ）と、不織布層（Ｄ）とからなる５層構造を有する耐水性高通気性複合シートを示す。It is an example of the water-resistant highly breathable composite sheet by this invention, Comprising: Resin layer (A), Resin / MFC coexistence layer (B), Resin / MFC / nonwoven fabric coexistence layer (E), Resin / nonwoven fabric coexistence layer The water-resistant highly breathable composite sheet which has 5 layer structure which consists of (F) and a nonwoven fabric layer (D) is shown. 本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布層（Ｄ）と、樹脂層（Ａ）とからなる５層構造を有する耐水性高通気性複合シートを示す。It is an example of the water-resistant highly breathable composite sheet by this invention, Comprising: Resin layer (A), Resin / MFC coexistence layer (B), Resin / MFC / nonwoven fabric coexistence layer (E), Nonwoven fabric layer (D) And a water-resistant and highly breathable composite sheet having a five-layer structure comprising a resin layer (A). 本発明による耐水性高通気性複合シートの例であって、（１）は、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布層（Ｄ）とからなる４層構造に、さらに撥水材層（Ｒ）を有する耐水性高通気性複合シートを、（２）は、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、樹脂・不織布共存層（Ｆ）と、不織布層（Ｄ）とからなる５層構造に、さらに撥水材層（Ｒ）を有する耐水性高通気性複合シートを、それぞれ示す。Examples of the water-resistant and highly breathable composite sheet according to the present invention, wherein (1) is a resin layer (A), a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), A water-resistant and highly breathable composite sheet having a water repellent material layer (R) in a four-layer structure comprising a nonwoven fabric layer (D), (2) is a resin layer (A) and a resin / MFC coexisting layer ( B), a resin / MFC / nonwoven fabric coexisting layer (E), a resin / nonwoven fabric coexisting layer (F), and a non-woven fabric layer (D) having a water-repellent material layer (R) The highly breathable composite sheet is shown respectively. 本発明による耐水性高通気性複合シートの例であって、（１）は、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布層（Ｄ）とからなる４層構造を有する耐水性高通気性複合シートであって、樹脂層（Ａ）に撥水材Ｒが担持された樹脂・撥水材共存層（Ｓ）を有する態様を、（２）は、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、樹脂・不織布共存層（Ｆ）と、不織布層（Ｄ）とからなる５層構造を有する耐水性高通気性複合シートであって、樹脂層（Ａ）に撥水材Ｒが担持された樹脂・撥水材共存層（Ｓ）を有する態様を、それぞれ示す。Examples of the water-resistant and highly breathable composite sheet according to the present invention, wherein (1) is a resin layer (A), a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), A water-resistant and highly breathable composite sheet having a four-layer structure composed of a nonwoven fabric layer (D), and having a resin / water-repellent material coexisting layer (S) in which a water-repellent material R is supported on the resin layer (A) Aspect (2) includes a resin layer (A), a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), a resin / nonwoven fabric coexistence layer (F), and a nonwoven fabric layer ( D) is a water-resistant and highly breathable composite sheet having a five-layer structure, and has a resin / water-repellent material coexisting layer (S) in which a water-repellent material R is supported on the resin layer (A), Each is shown. 本発明による耐水性高通気性複合シートの例であって、（１）は、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布層（Ｄ）とからなる４層構造に、さらに撥水材層（Ｒ）を有する耐水性高通気性複合シートであって、樹脂層（Ａ）に撥水材Ｒが担持された樹脂・撥水材共存層（Ｓ）を有する態様、（２）は、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、樹脂・不織布共存層（Ｆ）と、不織布層（Ｄ）とからなる５層構造に、さらに撥水材層（Ｒ）を有する耐水性高通気性複合シートであって、樹脂層（Ａ）に撥水材Ｒが担持された樹脂・撥水材共存層（Ｓ）を有する態様を、それぞれ示す。Examples of the water-resistant and highly breathable composite sheet according to the present invention, wherein (1) is a resin layer (A), a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), A water-resistant and highly breathable composite sheet having a four-layer structure comprising a nonwoven fabric layer (D) and a water-repellent material layer (R), wherein the resin layer (A) carries the water-repellent material R. A mode having a water repellent coexisting layer (S), (2) is a resin layer (A), a resin / MFC coexisting layer (B), a resin / MFC / nonwoven coexisting layer (E), and a resin / nonwoven coexisting layer A water-resistant and highly breathable composite sheet having a water repellent material layer (R) in a five-layer structure comprising a layer (F) and a nonwoven fabric layer (D), wherein the water repellent material R is applied to the resin layer (A). A mode having a resin / water-repellent material coexisting layer (S) on which is supported is shown. 本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、ＭＦＣ・不織布共存層（Ｃ）と、不織布層（Ｄ）とからなる４層構造に、撥水材層（Ｒ）を有する耐水性高通気性複合シートであって、（１）は、樹脂・ＭＦＣ共存層（Ｂ）及びＭＦＣ・不織布共存層（Ｃ）に脱臭剤が担持されている態様を、（２）は、ＭＦＣ・不織布共存層（Ｃ）及び不織布層（Ｄ）に脱臭剤が担持されている態様を、それぞれ示す。It is an example of the water-resistant highly breathable composite sheet by this invention, Comprising: From resin layer (A), resin and MFC coexistence layer (B), MFC and nonwoven fabric coexistence layer (C), and nonwoven fabric layer (D) A water-resistant and highly breathable composite sheet having a water repellent material layer (R) in a four-layer structure, wherein (1) is deodorized in the resin / MFC coexistence layer (B) and the MFC / nonwoven fabric coexistence layer (C) (2) shows an embodiment in which a deodorizing agent is carried on the MFC / nonwoven fabric coexisting layer (C) and the nonwoven fabric layer (D), respectively. 本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布層（Ｄ）とからなる４層構造を有する耐水性高通気性複合シートであって、（１）は、樹脂・ＭＦＣ・不織布共存層（Ｅ）に脱臭剤が担持されている態様を、（２）は、樹脂・ＭＦＣ・不織布共存層（Ｅ）及び樹脂・不織布共存層（Ｆ）に脱臭剤が担持されている態様を、それぞれ示す。It is an example of the water-resistant highly breathable composite sheet by this invention, Comprising: Resin layer (A), Resin / MFC coexistence layer (B), Resin / MFC / nonwoven fabric coexistence layer (E), Nonwoven fabric layer (D) (1) is an embodiment in which a deodorant is supported on the resin / MFC / nonwoven fabric coexisting layer (E), (2) A mode in which a deodorizing agent is supported on the resin / MFC / nonwoven fabric coexisting layer (E) and the resin / nonwoven fabric coexisting layer (F) is shown. 微細化セルロース繊維に脱臭剤が結合された微細化セルロース繊維・不織布複合体を用いて得た、本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布層（Ｄ）とからなる４層構造に、さらに撥水材層（Ｒ）を有する耐水性高通気性複合シートを示す。An example of a water-resistant and highly breathable composite sheet according to the present invention obtained by using a finely divided cellulose fiber / nonwoven fabric composite in which a deodorizer is bonded to finely divided cellulose fibers, the resin layer (A), A water-resistant and highly breathable composite sheet having a four-layer structure comprising an MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), and a nonwoven fabric layer (D), and a water repellent material layer (R). Indicates. ５スポットによる無荷重下浸透性評価における液体の浸透挙動の違いを示す断面図及び平面図であって、（１）は、樹脂処理品を用いた場合、（２）は、撥水処理のみを行った場合、（３）は、樹脂処理及び撥水処理を行った場合をそれぞれ示す。It is sectional drawing and a top view which show the difference of the penetration behavior of the liquid in the no-load permeability evaluation by 5 spots, Comprising: (1) is the case where a resin-treated product is used, (2) is only water-repellent treatment When performed, (3) shows a case where a resin treatment and a water repellent treatment are performed, respectively. システムフロー１：微細化セルロース繊維・不織布複合体の有機溶媒系溶解樹脂による含浸処理を行う例を示すフローチャートである。System flow 1: It is a flowchart which shows the example which performs the impregnation process by the organic solvent type melted resin of a refined cellulose fiber and a nonwoven fabric composite. システムフロー２：微細化セルロース繊維・不織布複合体のＳＢＲ水系エマルジョンによる２回処理を行う例を示すフローチャートである。System flow 2: It is a flowchart which shows the example which performs the process twice by SBR aqueous emulsion of a refined cellulose fiber and a nonwoven fabric composite. システムフロー３：微細化セルロース繊維・不織布複合体のゼオライトを共分散させたＳＢＲ水系エマルジョンによる処理と単独ＳＢＲ水系エマルジョンによる処理とを組合せた例を示すフローチャートである。System flow 3: It is a flowchart showing an example in which a treatment with an SBR aqueous emulsion in which zeolite of a fine cellulose fiber / nonwoven fabric complex is co-dispersed and a treatment with a single SBR aqueous emulsion are combined. システムフロー４：ゼオライトを担持した微細化セルロース繊維・不織布複合体にＳＢＲ水系エマルジョンによる処理を２回行う例を示すフローチャートである。System flow 4: It is a flowchart which shows the example which performs the process by SBR aqueous emulsion twice to the refined cellulose fiber and nonwoven fabric composite which carry | supported the zeolite. システムフロー５：微細化セルロース繊維・不織布複合体の製造とＳＢＲラテックス処理とを連続して行う例を示すフローチャートである。System flow 5: It is a flowchart which shows the example which manufactures refined cellulose fiber and a nonwoven fabric composite, and SBR latex process continuously. システムフロー６：微細化セルロース繊維・不織布複合体の製造とアクリル酸エマルジョン及び撥水材による処理とを連続して行う例を示すフローチャートである。System flow 6: It is a flowchart which shows the example which performs manufacture of a refined cellulose fiber and nonwoven fabric composite, and the process by an acrylic acid emulsion and a water repellent material continuously. 表面の濡れ性、拡散性及び浸透性の評価に用いた装置の概略断面図を示す。The schematic sectional drawing of the apparatus used for evaluation of the wettability of a surface, a diffusivity, and the permeability is shown. フクレの発生と水の浸透移動状態の評価に用いた装置の概略断面図を示す。The schematic sectional drawing of the apparatus used for generation | occurrence | production of a swelling and evaluation of the osmosis | permeation movement state of water is shown. 加圧下における漏れの発生状態の評価に用いる装置の概略断面図を示す。The schematic sectional drawing of the apparatus used for evaluation of the generation | occurrence | production state of the leak under pressure is shown. 例２において、本発明による耐水性高通気性複合シートの製造ステップを概略的に示すフローチャートである。In Example 2, it is a flowchart which shows schematically the manufacturing step of the water-resistant highly breathable composite sheet by this invention. 例３における、本発明による耐水性高通気性複合シートの製造ステップを概略的に示すフローチャートである。6 is a flowchart schematically showing steps for producing a water-resistant and highly breathable composite sheet according to the present invention in Example 3. 例３における、本発明による耐水性高通気性複合シートの製造ステップを概略的に示すフローチャートである。6 is a flowchart schematically showing steps for producing a water-resistant and highly breathable composite sheet according to the present invention in Example 3. 例４における、本発明による耐水性高通気性複合シートの製造ステップを概略的に示すフローチャートである。6 is a flowchart schematically showing steps for producing a water-resistant and highly breathable composite sheet according to the present invention in Example 4. 例４における、本発明による耐水性高通気性複合シートの製造ステップを概略的に示すフローチャートである。6 is a flowchart schematically showing steps for producing a water-resistant and highly breathable composite sheet according to the present invention in Example 4.

　なお、図３、図４、図５、図６、図７、図８、図９、図１０、図１１、図１２、図１３、及び図１４において、各図の右端部に各層の成分が突出した部分があるが、これは、図の説明上、構成をより明確にするためにこのように記載したもので、本発明により得られる製品がこのような構成を有することを意図したものではない。 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, and 14, the components of each layer are present at the right end of each figure. Although there is a protruding portion, this is described in this figure for the sake of clarity in the description of the drawings, and the product obtained by the present invention is not intended to have such a configuration. Absent.

符号の説明Explanation of symbols

　１　　ＭＦＣ単独層
　２　　ＭＦＣ・不織布共存層
　３　　不織布単独層
　Ａ　　樹脂層
　Ｂ　　樹脂・ＭＦＣ共存層
　Ｃ　　ＭＦＣ・不織布共存層
　Ｄ　　不織布層
　Ｅ　　樹脂・ＭＦＣ・不織布共存層
　Ｆ　　樹脂・不織布共存層
　Ｒ　　撥水材層
　Ｓ　　樹脂・撥水材共存層 1 MFC single layer 2 MFC / nonwoven fabric coexisting layer 3 Nonwoven fabric single layer A Resin layer B Resin / MFC coexisting layer C MFC / nonwoven fabric coexisting layer D Nonwoven fabric layer E Resin / MFC / nonwoven fabric coexisting layer F Resin / nonwoven fabric coexisting layer R Water repellent material Layer S Resin / water repellent layer

　以下、本発明の好適な実施形態につき説明する。 Hereinafter, preferred embodiments of the present invention will be described.

　＜本発明による耐水性高通気性複合シート＞
　本発明による耐水性高通気性複合シートは、微細化セルロース繊維（ＭＦＣ）と不織布とからなる微細化セルロース繊維・不織布複合体（ＭＦＣ・不織布複合体とも称する。）に、更に樹脂を適正に結合・共存させたものである。なお、樹脂加工の具体的な方法については、本発明による耐水性高通気性複合シートの製造方法に従って詳細に後述する。 <Waterproof and highly breathable composite sheet according to the present invention>
The water-resistant and highly breathable composite sheet according to the present invention further appropriately binds a resin to a refined cellulose fiber / nonwoven fabric composite (also referred to as an MFC / nonwoven fabric composite) composed of a refined cellulose fiber (MFC) and a nonwoven fabric.・ It was made to coexist. The specific method of resin processing will be described later in detail according to the method for producing a water-resistant and highly breathable composite sheet according to the present invention.

　まず、本発明において、耐水性高通気性複合シートの製造に用いられる微細化セルロース繊維・不織布複合体について、説明する。 First, the refined cellulose fiber / nonwoven fabric composite used in the production of the water-resistant and highly breathable composite sheet in the present invention will be described.

　（微細化セルロース繊維と不織布との微細化セルロース繊維・不織布複合体の調製）
　図１は、本発明における微細化セルロース繊維・不織布複合体を示す概略図である。本発明における微細化セルロース繊維・不織布複合体（ＭＦＣ・不織布複合体）は、微細化セルロース繊維からなるＭＦＣ単独層（以下、ＭＦＣ層とも称する。）１と、不織布からなる不織布単独層（以下、不織布層とも称する。）３と、ＭＦＣ層と不織布層とが複合されたＭＦＣ・不織布共存層２とを有する。 (Preparation of refined cellulose fiber / nonwoven fabric composite of refined cellulose fiber and nonwoven fabric)
FIG. 1 is a schematic view showing a refined cellulose fiber / nonwoven fabric composite in the present invention. The refined cellulose fiber / nonwoven fabric composite (MFC / nonwoven fabric composite) in the present invention includes an MFC single layer (hereinafter also referred to as MFC layer) 1 made of fine cellulose fiber, and a single layer of nonwoven fabric (hereinafter referred to as MFC layer). 3) and an MFC / nonwoven fabric coexisting layer 2 in which the MFC layer and the nonwoven fabric layer are combined.

　微細化セルロース繊維とは、詳しくは後述するがいわゆるミクロフィブリル単位まで超微細化した繊維状セルローズであり、一般呼称としてＭＦＣ（Ｍｉｃｒｏ　Ｆｉｂｒｉｌｌａｔｅｄ　Ｃｅｌｌｕｌｏｓｅ）と称されるものである。この微細化セルロース繊維は、図２に示したように、その繊維の微小サイズと強い水和性とに起因する、水素結合性能と固形粉体の吸着性能のような特異性能をもち、ＭＦＣを水に分散すると、その分散液は大きな非ニュートン粘性を示す。 As will be described in detail later, the micronized cellulose fiber is a fibrous cellulose that has been micronized to a so-called microfibril unit, and is generally referred to as MFC (Microfibrillated Cellulose). As shown in FIG. 2, this refined cellulose fiber has specific performance such as hydrogen bonding performance and solid powder adsorption performance due to the fine size and strong hydration property of the fiber. When dispersed in water, the dispersion exhibits a large non-Newtonian viscosity.

　このような性状をもつ微細化セルロース繊維（以下ＭＦＣと略称する）を、多孔性の不織布を支持体にして、その多孔部位をＭＦＣで充填、被覆することにより複合シート化したＭＦＣ・不織布複合体が得られる。この複合体は、いろいろな特異的性能をもつが、その性能の１つが均一で安定したミクロポーラス構造をもつことである。このＭＦＣに起因する複合シートのもつミクロポーラス構造は、その強い親水性の故に大量の水分と接するとＭＦＣが水和・膨潤して複合構造が破壊されてしまうが、乾燥状態で疎水性の樹脂成分で処理することによりＭＦＣ相互、ＭＦＣと不織布と間を充填樹脂により結合させ、ミクロポーラス構造の固定を行うことによって、液状の水は通過させないが水蒸気や空気は容易に透過するという「高通気性」で「耐水性」を併せもった、通気性をもった耐水バリヤーとして極めて効果的に機能する複合シートが得られることを本発明者らは発見した。 An MFC / nonwoven fabric composite made of a finely divided cellulose fiber (hereinafter abbreviated as MFC) having such properties by using a porous nonwoven fabric as a support and filling and coating the porous portion with MFC. Is obtained. This composite has various specific performances, one of which is a uniform and stable microporous structure. The microporous structure of the composite sheet resulting from this MFC is due to its strong hydrophilicity, when it comes into contact with a large amount of water, the MFC hydrates and swells and the composite structure is destroyed. By treating with the components, the MFCs are bonded to each other, the MFC and the nonwoven fabric are bonded with a filling resin, and the microporous structure is fixed, so that liquid water does not pass but water vapor and air easily pass through. The inventors of the present invention have found that a composite sheet that functions extremely effectively as a water-resistant barrier having air permeability, combined with “water resistance” can be obtained.

　原料となるＭＦＣ・不織布複合体の性能は、下記の諸条件で多様に変化する。 The performance of the raw material MFC / nonwoven fabric composite varies depending on the following conditions.

　１）用いられるＭＦＣ及び不織布のそれぞれの素材性状
　２）ＭＦＣ及び不織布の存在量比
　３）ＭＦＣ及び不織布の層状の分布状態
　４）ＭＦＣと不織布との複合化の方式 1) Material properties of MFC and non-woven fabric used 2) Abundance ratio of MFC and non-woven fabric 3) Layered distribution state of MFC and non-woven fabric 4) Method of combining MFC and non-woven fabric

　このＭＦＣ・不織布複合体の調製方法として代表的な方法を列挙すると、例えば下記の１）～４）の複合方式が考えられる。 As typical methods for preparing this MFC / nonwoven fabric composite, for example, the following composite methods 1) to 4) can be considered.

　１）積層方式
　ＭＦＣ層と不織布層とを別々に成形し、両層を重ね合わせて一体化する方式である。ＭＦＣ層と不織布層とが大部分で、ＭＦＣ・不織布共存層の部分は殆どない 1) Lamination method In this method, the MFC layer and the nonwoven fabric layer are separately formed, and both layers are overlapped and integrated. Most of the MFC layer and non-woven fabric layer, and almost no MFC / non-woven fabric coexisting layer

　２）積層・熱融着方式
　ＭＦＣ層と、易熱融着繊維を含む繊維ウェブから構成される不織布層とを別々に成形し、両層を重ね合わせて熱圧着処理により一体化する方式である。ＭＦＣ層と不織布層とがやはり大部分を占めるが、熱融着繊維がＭＦＣ層の中に浸透するので、ＭＦＣ・不織布共存層の割合は増加する。 2) Lamination and heat-sealing method This is a method in which an MFC layer and a non-woven fabric layer composed of a fiber web containing heat-fusible fibers are separately molded, and both layers are overlapped and integrated by thermocompression bonding. . The MFC layer and the non-woven fabric layer still occupy the majority, but since the heat-sealing fibers penetrate into the MFC layer, the ratio of the MFC / non-woven fabric coexisting layer increases.

　３）ＭＦＣスラリーのコーティング方式
　不織布を基材として、その上表面にＭＦＣの水分散スラリーをコーティングして圧着一体化した後、残存水分を乾燥して構造固定する方式である。この時のＭＦＣスラリー濃度は、０．８％～３％程度であり、不織布組成の中にＭＦＣ層がかみ込んだ状態になるため、上記の１）の積層方式と比較して、ＭＦＣ・不織布共存層の割合は大きく増加する。 3) MFC slurry coating method In this method, a nonwoven fabric is used as a base material, and an MFC water dispersion slurry is coated on the upper surface of the non-woven fabric and integrated by pressure bonding. At this time, the MFC slurry concentration is about 0.8% to 3%, and the MFC layer is in the nonwoven fabric composition. The proportion of coexistence layers is greatly increased.

　４）抄紙方式
　不織布を基材として、その上表層に希釈水分散したＭＦＣスラリーを流延し、基材上にＭＦＣ層を形成しつつ真空脱水しＭＦＣ層と不織布層とを一体化した後、残留水分を乾燥してＭＦＣ層を不織布層に固定したものである。この時のＭＦＣスラリー濃度は０．１％～０．８％程度であり、不織布層の内部までＭＦＣが入り込み混合一体化しているので、ＭＦＣ・不織布共存層の割合が大きくなってくる。 4) Papermaking method After using a non-woven fabric as a base material, casting an MFC slurry in which diluted water is dispersed on the upper surface, and forming an MFC layer on the base material, vacuum dehydrating and integrating the MFC layer and the non-woven fabric layer, The residual moisture is dried and the MFC layer is fixed to the nonwoven fabric layer. The concentration of the MFC slurry at this time is about 0.1% to 0.8%, and MFC enters the inside of the nonwoven fabric layer and is integrated and integrated, so the ratio of the MFC / nonwoven fabric coexistence layer increases.

　下記の表１は、ＭＦＣ層１５ｇ／ｍ２、不織布層１５ｇ／ｍ２で複合させた状態での、ＭＦＣ層、ＭＦＣ・不織布共存層、不織布層の占める割合を比較したものである。 Table 1 below compares the proportions of the MFC layer, the MFC / nonwoven fabric coexisting layer, and the non-woven fabric layer in a state of being combined with the MFC layer 15 g / m 2 and the non-woven fabric layer 15 g / m 2 .

　なお、表１において、積層方式、コーティング方式及び抄紙方式では、基材となる不織布は、Ａｖｇｏｌ社製のＳＭＳ不織布を用いた。積層・熱融着方式では、基材となる不織布は、クラレ製のＰＥ／ＰＥＴ繊維からなる乾式エアスルー不織布を用いた。この例では、乾燥後熱処理してＰＥ成分を溶融させたものである。また、コーティング方式や抄紙方式においても基材として熱融着性の不織布を組み合わせることも可能である。また、表１において表示されている数値は、微細化セルロース繊維・不織布複合体の全体重量を１００％としたときの各層の重量比（％）で表記した。例えば、ＭＦＣ層と不織布とを単に組み合わせて、共存層のない系では、ＭＦＣ層５０％、共存層０％、不織布層５０％となる。また、４）の抄紙方式の例で、ＭＦＣ層３０％、共存層３５％、不織布層３５％となっているが、この複合体において、ＭＦＣ層及び不織布層は、それぞれ重量比で５０％であるから、共存層３５％は、ＭＦＣ２０％と、不織布１５％とから構成されているという意味である。 In Table 1, in the lamination method, the coating method, and the papermaking method, the nonwoven fabric used as the base material was an SMS nonwoven fabric manufactured by Avgor. In the lamination / heat fusion method, a dry air-through nonwoven fabric made of Kuraray PE / PET fibers was used as the nonwoven fabric. In this example, the PE component is melted by heat treatment after drying. Moreover, it is also possible to combine a heat-fusible non-woven fabric as a base material in the coating method and the paper making method. Moreover, the numerical value displayed in Table 1 was described by the weight ratio (%) of each layer when the total weight of the refined cellulose fiber / nonwoven fabric composite was 100%. For example, in a system in which an MFC layer and a nonwoven fabric are simply combined and there is no coexistence layer, the MFC layer is 50%, the coexistence layer is 0%, and the nonwoven fabric layer is 50%. In the example of the papermaking method of 4), the MFC layer is 30%, the coexistence layer is 35%, and the nonwoven fabric layer is 35%. In this composite, the MFC layer and the nonwoven fabric layer are 50% by weight, respectively. Therefore, the coexisting layer 35% means that it is composed of 20% MFC and 15% nonwoven fabric.

Figure JPOXMLDOC01-appb-T000001
Figure JPOXMLDOC01-appb-T000001

　上述した複合方式については、積層方式をとると、ＭＦＣ層は、しっかり形成されるが、ＭＦＣ層と不織布層の界面での層間剥離は生じ易くなる。一方、抄紙方式の場合は、層間剥離は起こりにくくなるがＭＦＣ層の形成状態は不均一になりやすい。これらの特徴も複合時に使用される原料のＭＦＣの量や性状によって、また後述する樹脂加工との組合せによって変わってくるので、求める製品の機能に応じてそれにあう複合方式を適宜選択する。 For the composite method described above, when the lamination method is adopted, the MFC layer is firmly formed, but delamination is likely to occur at the interface between the MFC layer and the nonwoven fabric layer. On the other hand, in the papermaking method, delamination hardly occurs, but the formation state of the MFC layer tends to be nonuniform. These characteristics also vary depending on the amount and properties of the raw material MFC used at the time of compounding and in combination with the resin processing described later. Therefore, a suitable compounding system is selected according to the desired product function.

　（微細化セルロース繊維・不織布複合体の構成素材の要件）
　微細化セルロース繊維
　１）微細化セルロース繊維の性状
　微細化セルロース繊維とは、木材パルプ、コットン、砂糖キビ、砂糖ダイコン等の植物由来のセルローズ繊維を機械的に超微細化したものが一般的であり、ミクロフィブリル化セルローズＭＦＣ（Ｍｉｃｒｏ　Ｆｉｂｒｉｌｌａｔｅｄ　Ｃｅｌｌｕｌｏｓｅ）と呼称されている。酢酸菌などのバクテリアが産出するものはバクテリアセルローズあるいはバイオセルローズと呼称されている。 (Requirements for constituent materials of fine cellulose fiber / nonwoven fabric composite)
Refined cellulose fiber 1) Properties of refined cellulose fiber The refined cellulose fiber is generally a mechanically refined cellulose fiber such as wood pulp, cotton, sugar millet, sugar beet, etc. It is called microfibrillated cellulose MFC (Microfibrillated Cellulose). Those produced by bacteria such as acetic acid bacteria are called bacterial cellulose or biocellulose.

　ＭＦＣについては特許文献３に開示され、バイオセルローズについては非特許文献１に開示されている。いずれも繊維長が短く、１００ｎｍ前後のナノ単位の超微細な直径を持ち、しかも水和性に富んでいる。本発明に用いられる微細化セルロース繊維は、平均繊維長は０．３ｍｍ以下好ましくは０．２ｍｍ以下のものである。０．３ｍｍ以上になると繊維同士がからまり、不均一な固まりを形成し易くなる。水和性の目安となる抱水度は１５ｍＬ／ｇ以上であることが好ましい。１５ｍＬ／ｇ未満であると安定な分散状態をつくるスラリーが得られなくなるし水素結合力も低下する。微細化セルロース繊維は、以後ＭＦＣに代表させて表現する。 MFC is disclosed in Patent Document 3, and Biocellulose is disclosed in Non-Patent Document 1. All of them have a short fiber length, an ultrafine diameter of nano units of around 100 nm, and are rich in hydration. The refined cellulose fiber used in the present invention has an average fiber length of 0.3 mm or less, preferably 0.2 mm or less. If the thickness is 0.3 mm or more, the fibers are entangled and it becomes easy to form a non-uniform mass. It is preferable that the water retention that is a measure of hydration is 15 mL / g or more. If it is less than 15 mL / g, a slurry that produces a stable dispersion state cannot be obtained, and the hydrogen bonding force also decreases. The micronized cellulose fiber is hereinafter represented by MFC.

　２）ＭＦＣの必要量
　本発明による耐水性高通気性複合シートの高通気性構造は、不織布の多孔質部を充填したＭＦＣの微細繊維間のミクロポーラス構造に依存している。従って、耐水性高通気性複合シートの製造に用いられるＭＦＣ・不織布複合体において、複合化に必要なＭＦＣ量は適切に選ばれる必要がある。 2) Required amount of MFC The highly breathable structure of the water-resistant and highly breathable composite sheet according to the present invention depends on the microporous structure between the fine fibers of MFC filled with the porous portion of the nonwoven fabric. Therefore, in the MFC / nonwoven fabric composite used for the production of the water-resistant and highly breathable composite sheet, the amount of MFC necessary for the composite needs to be appropriately selected.

　ＭＦＣは、水素結合性が強く、乾燥により硬化し乾燥収縮が大きいため、ＭＦＣ層の表面にはひび割れが生じ易い。従って、不織布の多孔組織を充填し被覆するのに必要な量が確保されれば、それ以上量を多くする必要はない。ＭＦＣの量としては、不織布の稠密度・目付にも影響されるが、１ｇ／ｍ２～３０ｇ／ｍ２の範囲が望ましく、更に望ましくは２ｇ／ｍ２～２０ｇ／ｍ２である。１ｇ／ｍ２未満では不織布の組織を充填する量としては不充分であり、また均一な層形成も難しい。３０ｇ／ｍ２を超えるとＭＦＣ層の紙化が起こり易く、硬化し柔軟性がなくなると同時に表面ひび割れが多く発生するようになる。 MFC has strong hydrogen bonding properties, is hardened by drying, and has a large shrinkage due to drying. Therefore, cracks are likely to occur on the surface of the MFC layer. Therefore, if the amount necessary for filling and covering the porous structure of the nonwoven fabric is secured, it is not necessary to increase the amount further. The amount of MFC is influenced by the density and basis weight of the nonwoven fabric, but is preferably in the range of 1 g / m 2 to 30 g / m 2 , more preferably 2 g / m 2 to 20 g / m 2 . If it is less than 1 g / m 2 , it is insufficient as an amount for filling the nonwoven fabric structure, and it is difficult to form a uniform layer. If it exceeds 30 g / m 2 , the MFC layer is likely to be made into paper, is hardened and loses flexibility, and at the same time, many surface cracks occur.

　基材となる不織布
　１）不織布の性状
　本発明における不織布としては、柔軟で、組織が均一で、目付８ｇ／ｍ２～４０ｇ／ｍ２で厚さ０．５ｍｍ以下の比較的目付が低く薄い不織布が用いられるが、代表的なものを例示すると次のような性状を持つものである。 Non-woven fabric used as substrate 1) Properties of non-woven fabric The nonwoven fabric of the present invention is flexible, has a uniform structure, has a basis weight of 8 g / m 2 to 40 g / m 2 and a thickness of 0.5 mm or less, and has a relatively low basis weight and is a thin nonwoven fabric. Are used, but typical ones have the following properties.

　２）不織布の構成繊維
　０．５～８．０デニールの比較的細繊度のポリエチレン、ポリプロピレン、ポリエステル、アクリル、Ｐ．Ｖ．Ａ．等の合成繊維、ＰＥ／ＰＥＴ、ＰＥ／ＰＰ、ＥＶＡ／ＰＥ等の易溶融性複合繊維、木材パルプ、コットン、レーヨン、リヨセル、アセテート等のセルローズ系繊維、およびこれらの混合体が使用可能であるが、化合繊系の疎水性の繊維が樹脂加工処理によって耐水性を賦与することが比較的容易なため望ましい。 2) Nonwoven fabric constituent fibers Polyethylene, polypropylene, polyester, acrylic, P.I. V. A. Synthetic fibers such as PE / PET, PE / PP, EVA / PE and other fusible composite fibers, wood pulp, cotton, rayon, lyocell, acetate and other cellulose fibers, and mixtures thereof can be used. However, it is desirable because the synthetic fiber-based hydrophobic fibers are relatively easy to impart water resistance by resin processing.

　３）不織布の形状、製法
　短繊維を原料としたカード法によるスポットボンド不織布、エアスルー法不織布、エアレイド法によるパルプ不織布、フィラメント不織布であるスパンボンド不織布、メルトブローン不織布、この複合体であるスパンボンド・メルトブローン複合体等が使用可能であるが、大量生産可能で、コストが安価でしかも耐水性もあるスパンボンド・メルトブローン複合体（ＳＭＳと略称される）が特に望ましい。 3) Shape and manufacturing method of non-woven fabric Spot bond non-woven fabric by card method using short fiber as raw material, air through method non-woven fabric, pulp non-woven fabric by airlaid method, spunbond non-woven fabric, melt-blown non-woven fabric, and spunbond / melt-blown composite A composite or the like can be used, but a spunbond / meltblown composite (abbreviated as SMS) that can be mass-produced, is inexpensive, and has water resistance is particularly desirable.

　（本発明による耐水性高通気性複合シートの構成）
　次に、本発明による耐水性高通気性複合シートの構成について説明する。本発明による耐水性高通気性複合シートは、冒頭の説明のように、上記の微細化セルロース繊維・不織布複合体に、さらに樹脂を適正に結合、共存させたものであって、図３～１４は、本発明による耐水性高通気性複合シートの例を示す。 (Configuration of water-resistant and highly breathable composite sheet according to the present invention)
Next, the structure of the water resistant highly breathable composite sheet according to the present invention will be described. The water-resistant and highly breathable composite sheet according to the present invention is obtained by appropriately combining and coexisting a resin with the above-mentioned refined cellulose fiber / nonwoven fabric composite as described at the beginning. These show the example of the water-resistant highly breathable composite sheet by this invention.

　本発明による耐水性高通気性複合シートの一態様によると、耐水性高通気性複合シートは、微細化セルロース繊維・不織布複合体のＭＦＣ層の上表面に樹脂加工して得られるものであって、樹脂加工の深度に応じて、様々な態様をとり得る。 According to one aspect of the water-resistant and highly breathable composite sheet according to the present invention, the water-resistant and highly breathable composite sheet is obtained by resin processing on the upper surface of the MFC layer of the fine cellulose fiber / nonwoven fabric composite. Depending on the depth of the resin processing, various modes can be taken.

　本発明による耐水性高通気性複合シートは、例えば、図３に示すように、樹脂のみからなる樹脂層（Ａ）と、樹脂とＭＦＣ層とからなる樹脂・ＭＦＣ共存層（Ｂ）と、ＭＦＣと不織布とからなるＭＦＣ・不織布共存層（Ｃ）と、不織布からなる不織布層（Ｄ）とを有してもよい。また、図４に示すように、樹脂のみからなる樹脂層（Ａ）と、樹脂とＭＦＣ層とからなる樹脂・ＭＦＣ共存層（Ｂ）と、樹脂とＭＦＣ層と不織布とからなる樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布からなる不織布層（Ｄ）とを有してもよい。さらに、図５に示すように、樹脂のみからなる樹脂層（Ａ）と、樹脂とＭＦＣ層とからなる樹脂・ＭＦＣ共存層（Ｂ）と、樹脂とＭＦＣ層と不織布とからなる樹脂・ＭＦＣ・不織布共存層（Ｅ）と、樹脂と不織布とからなる樹脂・不織布共存層（Ｆ）とかを有してもよい。 The water-resistant and highly breathable composite sheet according to the present invention includes, for example, as shown in FIG. 3, a resin layer (A) composed only of a resin, a resin / MFC coexisting layer (B) composed of a resin and an MFC layer, and an MFC. And a non-woven fabric coexisting layer (C) and a non-woven fabric layer (D). In addition, as shown in FIG. 4, a resin layer (A) made only of a resin, a resin / MFC coexistence layer (B) made of a resin and an MFC layer, a resin made of a resin, an MFC layer, and a nonwoven fabric, MFC, You may have a nonwoven fabric coexistence layer (E) and the nonwoven fabric layer (D) which consists of a nonwoven fabric. Further, as shown in FIG. 5, a resin layer (A) made of only resin, a resin / MFC coexistence layer (B) made of resin and MFC layer, and a resin / MFC made of resin, MFC layer and nonwoven fabric. You may have a nonwoven fabric coexistence layer (E) and the resin and nonwoven fabric coexistence layer (F) which consist of resin and a nonwoven fabric.

　このように、耐水性高通気性複合シートの製造に用いる微細化セルロース繊維・不織布複合体を構成するＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層に樹脂加工を施して、その加工の深度に応じて、ＭＦＣ層が、樹脂とＭＦＣ層とからなる樹脂・ＭＦＣ共存層（Ｂ）に処理され、ＭＦＣ・不織布共存層が、樹脂とＭＦＣと不織布とからなる樹脂・ＭＦＣ・不織布共存層（Ｅ）に処理され、及び／又は不織布層が、樹脂と不織布とからなる樹脂・不織布共存層（Ｆ）に処理されることとなる。このように樹脂の程度に応じて得られた層を適宜組み合わされたものが耐水性高通気性複合シートの各層を構成することとなる。従って、樹脂加工の程度に応じて得られた全ての構成（つまり、樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、ＭＦＣ・不織布共存層（Ｃ）、不織布層（Ｄ）、樹脂・ＭＦＣ・不織布共存層（Ｅ）、樹脂・不織布共存層（Ｆ））を組み合わせたいずれのものも、本発明の範囲に包含される。 In this way, resin processing is applied to the MFC layer, MFC / nonwoven fabric coexisting layer and nonwoven fabric layer constituting the finely divided cellulose fiber / nonwoven fabric composite used for the production of the water-resistant and highly breathable composite sheet, and depending on the processing depth The MFC layer is processed into a resin / MFC coexisting layer (B) composed of a resin and an MFC layer, and the MFC / nonwoven fabric coexisting layer is a resin / MFC / nonwoven fabric coexisting layer (E) composed of a resin, MFC and a non-woven fabric. And / or the nonwoven fabric layer is processed into a resin / nonwoven fabric coexisting layer (F) comprising a resin and a nonwoven fabric. Thus, what combined suitably the layer obtained according to the grade of resin will comprise each layer of a water-resistant highly air permeable composite sheet. Therefore, all the structures obtained according to the degree of resin processing (that is, resin layer (A), resin / MFC coexistence layer (B), MFC / nonwoven fabric coexistence layer (C), nonwoven fabric layer (D), resin / Any combination of the MFC / nonwoven fabric coexisting layer (E) and the resin / nonwoven fabric coexisting layer (F)) is also included in the scope of the present invention.

　また、本発明において、樹脂加工を施す微細化セルロース繊維・不織布複合体の面は、ＭＦＣ層の存在する側から行ってもよく、また、不織布層が存在する側から行ってもよい。図１～図７は、樹脂加工をＭＦＣ層の存在する側から行って得た例であり、樹脂加工を不織布層側から行って得た例を図８に示す。図８は、本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布層（Ｄ）と、樹脂層（Ａ）とからなる５層構造を有する耐水性高通気性複合シートを示す。 In the present invention, the surface of the refined cellulose fiber / nonwoven fabric composite subjected to resin processing may be performed from the side where the MFC layer exists, or from the side where the nonwoven fabric layer exists. FIGS. 1 to 7 show examples obtained by performing resin processing from the side where the MFC layer is present, and FIG. 8 shows an example obtained by performing resin processing from the nonwoven fabric layer side. FIG. 8 is an example of a water-resistant and highly breathable composite sheet according to the present invention, which is a resin layer (A), a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), and a non-woven fabric. The water-resistant highly breathable composite sheet which has a 5 layer structure which consists of a layer (D) and a resin layer (A) is shown.

　［撥水材］
　本発明において、上記のように、微細化セルロース繊維・不織布複合体に樹脂を共存させて得た耐水性高通気性複合シートに、さらに撥水材からなる撥水材層（Ｒ）を設けてもよい。この態様を示したのが、図９の（１）及び（２）である。図９は、本発明による耐水性高通気性複合シートの例であって、（１）は、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布層（Ｄ）とからなる４層構造に、さらに撥水材層（Ｒ）を有する耐水性高通気性複合シートを、（２）は、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、樹脂・不織布共存層（Ｆ）と、不織布層（Ｄ）とからなる５層構造に、さらに撥水材層（Ｒ）を有する耐水性高通気性複合シートを、それぞれ示す。 [Water repellent]
In the present invention, as described above, a water-repellent material layer (R) made of a water-repellent material is further provided on a water-resistant and highly breathable composite sheet obtained by coexisting a resin with a fine cellulose fiber / nonwoven fabric composite. Also good. This mode is shown in (1) and (2) of FIG. FIG. 9 is an example of a water-resistant and highly breathable composite sheet according to the present invention. (1) is a resin layer (A), a resin / MFC coexistence layer (B), and a resin / MFC / nonwoven fabric coexistence layer ( E) and a non-woven fabric layer (D) having a four-layer structure and a water-resistant and highly breathable composite sheet having a water-repellent material layer (R). (2) is a resin layer (A), The water-repellent material layer (R) has a five-layer structure comprising an MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), a resin / nonwoven fabric coexistence layer (F), and a nonwoven fabric layer (D). The water-resistant and highly breathable composite sheet having) is shown respectively.

　撥水材を耐水性高通気性複合シートに含有させる態様としては、上記の通り撥水材からなる撥水材層（Ｒ）として設けてもよく、また、耐水性高通気性複合シートの所望する層位置に含有させてもよく、さらに、これら撥水材層（Ｒ）として設ける態様及び所望する層位置に含有させる態様を適宜組み合わせてもよい。図１０の（１）及び（２）は、樹脂からなる樹脂層（Ａ）に撥水材を共存させた樹脂・撥水材共存層（Ｓ）を設ける形式で撥水材を耐水性高通気性複合シートに含有させる態様を示すものであり、図１１の（１）及び（２）は、樹脂からなる樹脂層（Ａ）に撥水材を共存させた樹脂・撥水材共存層（Ｓ）の上にさらに撥水材からなる撥水材層（Ｒ）を設けた態様を示すものである。 As an aspect in which the water-repellent material is contained in the water-resistant and highly breathable composite sheet, it may be provided as the water-repellent material layer (R) made of the water-repellent material as described above. The layer provided as the water repellent material layer (R) and the mode contained in the desired layer position may be appropriately combined. (1) and (2) in FIG. 10 show that the water-repellent material is water-resistant and highly ventilated by providing a resin / water-repellent material coexisting layer (S) in which a water-repellent material coexists with a resin layer (A) made of resin. FIG. 11 (1) and (2) show a resin / water repellent material coexisting layer (S) in which a water repellent material coexists with a resin layer (A) made of resin. ) Is further provided with a water repellent layer (R) made of a water repellent material.

　［脱臭剤］
　本発明において、上記のように、微細化セルロース繊維・不織布複合体に樹脂を共存させて得た耐水性高通気性複合シートに、さらに脱臭剤などの固形粉体成分を含有させてもよい。この態様を示したのが、図１２～１３である。脱臭剤は、耐水性高通気性複合シートを構成するいずれの層に含有させてもよいが、親水性の強い組成が多く、そのような親水性固形物が表面に存在すると、液が浸潤しやすくなり、耐水性能を低下させるので、樹脂層（Ａ）以外の各層、つまり、樹脂・ＭＦＣ共存層（Ｂ）、ＭＦＣ・不織布共存層（Ｃ）、不織布層（Ｄ）、樹脂・ＭＦＣ・不織布共存層（Ｅ）及び樹脂・不織布共存層（Ｆ）からなる群から選択された少なくとも一つの層に含有されることが好ましい。例えば、図１２の（１）に示すように、樹脂・ＭＦＣ共存層（Ｂ）及びＭＦＣ・不織布共存層（Ｃ）に脱臭剤を含有させてもよく、図１２の（２）に示すように、ＭＦＣ・不織布共存層（Ｃ）及び不織布層（Ｄ）に含有させてもよい。また、図１３の（１）に示すように、樹脂・ＭＦＣ・不織布共存層（Ｅ）にのみ脱臭剤を含有させてもよい。さらに、樹脂・ＭＦＣ・不織布共存層（Ｅ）及び樹脂・不織布共存層（Ｆ）に脱臭剤を含有させてもよい。 [Deodorizer]
In the present invention, as described above, the water-resistant and highly breathable composite sheet obtained by allowing the resin to coexist with the fine cellulose fiber / nonwoven fabric composite may further contain a solid powder component such as a deodorant. This embodiment is shown in FIGS. The deodorizer may be contained in any layer constituting the water-resistant and highly breathable composite sheet, but has a strong hydrophilic composition, and when such a hydrophilic solid is present on the surface, the liquid infiltrates. Each layer other than the resin layer (A), that is, a resin / MFC coexisting layer (B), an MFC / nonwoven fabric coexisting layer (C), a non-woven fabric layer (D), a resin / MFC / nonwoven fabric, because the water resistance is reduced. It is preferably contained in at least one layer selected from the group consisting of the coexistence layer (E) and the resin / nonwoven fabric coexistence layer (F). For example, as shown in (1) of FIG. 12, a resin / MFC coexistence layer (B) and an MFC / nonwoven fabric coexistence layer (C) may contain a deodorizer, as shown in (2) of FIG. And may be contained in the MFC / nonwoven fabric coexisting layer (C) and the nonwoven fabric layer (D). Moreover, as shown to (1) of FIG. 13, you may make a deodorizing agent contain only in resin, MFC, and a nonwoven fabric coexistence layer (E). Further, a deodorant may be contained in the resin / MFC / nonwoven fabric coexisting layer (E) and the resin / nonwoven fabric coexisting layer (F).

　また、本発明において、脱臭剤を設ける態様としては、上記に加え、耐水性高通気性複合シートの原料となる微細化セルロース繊維・不織布複合体のうち、微細化セルロース繊維に脱臭剤を結合させてもよい。この態様を示したのが、図１４である。図１４は、微細化セルロース繊維に脱臭剤が結合された微細化セルロース繊維・不織布複合体を用いて得た、本発明による耐水性高通気性複合シートの例であって、樹脂層（Ａ）と、樹脂・ＭＦＣ共存層（Ｂ）と、樹脂・ＭＦＣ・不織布共存層（Ｅ）と、不織布層（Ｄ）とからなる４層構造に、さらに撥水材層（Ｒ）を有する耐水性高通気性複合シートを示す。 Further, in the present invention, as a mode of providing the deodorizer, in addition to the above, among the fine cellulose fiber / nonwoven fabric composite used as a raw material of the water-resistant and highly breathable composite sheet, the deodorizer is bonded to the fine cellulose fiber. May be. This mode is shown in FIG. FIG. 14 is an example of a water-resistant and highly breathable composite sheet according to the present invention obtained by using a finely divided cellulose fiber / nonwoven fabric composite in which a deodorizing agent is bonded to finely divided cellulose fibers, and a resin layer (A) And a water / repellent material layer (R) in a four-layer structure comprising a resin / MFC coexistence layer (B), a resin / MFC / nonwoven fabric coexistence layer (E), and a nonwoven fabric layer (D). A breathable composite sheet is shown.

　（本発明による耐水性高通気性複合シートに求められる耐水性能とその評価方法）
　本発明の耐水性を賦与した高通気性の樹脂、ＭＦＣ，不織布から構成された耐水性高通気性複合シートは、滅菌ラップ、食品包材及び紙おむつや女性生理用品の防漏バックシート等に使用されるものであり、使用時にモレが発生しないことが必須であり、加圧下での耐水性も要求される。 (Water resistance required for water-resistant and highly breathable composite sheet according to the present invention and its evaluation method)
The water-resistant and highly breathable composite sheet composed of the highly breathable resin, MFC, and nonwoven fabric imparted with the water resistance of the present invention is used for sterilization wrap, food wrapping materials, paper diapers, and leak-proof back sheets for feminine sanitary products, etc. Therefore, it is essential that no leakage occurs during use, and water resistance under pressure is also required.

　１）複合シート使用時の液モレ発生のステップ
　例えば本発明の複合シートを紙おむつのバックシートとして用いた場合を例に説明すると、例えば尿（水性液）は次のような過程を経て「モレ」となる。 1) Step of generating liquid leakage when using a composite sheet For example, the case where the composite sheet of the present invention is used as a back sheet of a disposable diaper will be described as an example. For example, urine (aqueous liquid) is subjected to the following process. It becomes.

　ステップ１：水性液の最表面層の液濡れと表面層への液の拡散・浸透
 　　　　　　　　↓
　ステップ２：ＭＦＣ層の水膨潤によるフクレの発生
 　　　　　　　　↓
　ステップ３：ＭＦＣ層からＭＦＣ／不織布層への浸透移動
 　　　　　　　　↓
　ステップ４：最下層の不織布層からの液の滲出透過（モレの発生） Step 1: Wetting of the outermost surface layer of aqueous liquid and diffusion / penetration of liquid into the surface layer ↓
Step 2: Generation of swelling due to water swelling of MFC layer ↓
Step 3: Permeation transfer from MFC layer to MFC / nonwoven fabric layer ↓
Step 4: Permeation of liquid from the lowermost nonwoven fabric layer (generation of leakage)

　２）表面の濡れ性、拡散及び浸透性の評価
　―５スポット法による無荷重下浸透性の評価参照―
　図１５の（１）～（３）は、５スポット法による無荷重下の浸透性を観察したものである。 2) Evaluation of surface wettability, diffusion and permeability-See Evaluation of permeability under no load by the 5-spot method-
(1) to (3) in FIG. 15 are observations of the permeability under no load by the 5-spot method.

　例えば紙おむつのバックシートとして本発明品を用いた場合、まず尿等の体液は、バックシートの最上表面に接触すると、バックシート表面の撥水性が大であれば、図１５の（２）及び（３）のように水玉状に、撥水性が弱ければ、図１５の（１）のように半月状になって表面に留まる。 For example, when the product of the present invention is used as a back sheet of a paper diaper, first, when body fluid such as urine comes into contact with the uppermost surface of the back sheet, if the water repellency of the back sheet surface is large, (2) and ( If the water repellency is weak as shown in 3), it becomes a half moon as shown in (1) of FIG. 15 and stays on the surface.

　図１５の（１）のように樹脂処理がきちんと行われていると、経時的にみても０．１ｍＬ～１ｍＬの小さなスポットも大きなスポットも若干周囲に少し拡大するがそれ以上は進まず、表面で蒸発するまで表面のみに留まる。ところが撥水性があっても樹脂処理がきちんと行われていないと、図１５の（２）のように時間経過とともに拡大浸透し液が表面から消えてなくなる。浸透した液は、下面から滲み出して最終的にはモレ状態に至る。樹脂処理を適性に行いこれに撥水剤処理を組み合わせると、図１５の（３）のように長時間安定な撥水性を保つようになる。 When the resin treatment is performed properly as shown in (1) of FIG. 15, both the small spot and the large spot of 0.1 mL to 1 mL slightly expand to the surroundings over time, but the surface does not progress further. Stays on the surface only until it evaporates. However, even if there is water repellency, if the resin treatment is not performed properly, as shown in (2) of FIG. 15, it spreads and penetrates over time, and the liquid does not disappear from the surface. The infiltrated liquid oozes out from the lower surface and finally reaches a mole state. When resin treatment is appropriately performed and this is combined with a water repellent treatment, stable water repellency can be maintained for a long time as shown in FIG.

　このように（１）液の濡れ状態；（２）液の拡散状態；及び（３）液の浸透状態；を評価、解析することは、複合体の耐水性評価の重要なポイントの１つである。 Thus, evaluation and analysis of (1) the wet state of the liquid; (2) the diffusion state of the liquid; and (3) the penetration state of the liquid are one of the important points in the water resistance evaluation of the composite. is there.

　本発明による耐水性高通気性複合シートにおいては、このような５スポット法によるテストによって、少なくとも３０分以上、好ましくは２時間以上経過しても、いずれのスポットからも下面への滲み出しが生じないことを前提としている。 In the water-resistant and highly breathable composite sheet according to the present invention, bleed to the lower surface occurs from any spot even after elapse of at least 30 minutes, preferably 2 hours or more, by the test by the 5-spot method. It is assumed that there is no.

　３）ＭＦＣ層の水膨潤によるフクレの発生と下層への浸透移動状態の評価
　―リング式シールテストによる複合体表面の浸透安定性の評価参照―
　紙おむつの中に尿が多量に排出されると、バックシートの表面は殆ど水溶液で浸漬されたような状態に至り時間を経過することになる。 3) Generation of swelling due to water swelling in the MFC layer and evaluation of the state of permeation migration to the lower layer-See the evaluation of the permeation stability of the composite surface by the ring seal test-
When a large amount of urine is discharged into the paper diaper, the surface of the back sheet is almost immersed in an aqueous solution, and time elapses.

　このような浸漬状態における複合体表面の安定性を評価する方法として、リング式のシールテストを行う。即ち、内径８０ｍｍφのステンレスリングの中に染色した生理食塩水を満たし、水深１０ｍｍのＷａｔｅｒ　Ｐｏｏｌを複合シート上に設置して、経時的にその間の表面状態の変化、モレの発生の有無及び状態を解析する方法である。 As a method for evaluating the stability of the composite surface in such an immersion state, a ring type seal test is performed. In other words, a stainless steel ring with an inner diameter of 80 mmφ is filled with a dyed physiological saline, and a water pool with a water depth of 10 mm is placed on the composite sheet. It is a method of analysis.

　樹脂加工がきちんと行われていると６時間後、更に２４時間経過しても複合シートの表面状態に大きな変化も生じずモレの発生もないが、樹脂加工が不充分であると、経時的に表層のＭＦＣが膨潤し、ぶつぶつ状の“フクレ”が発生して部分的な層間剥離が発生し、ＭＦＣ層、ＭＦＣ・不織布共存層を通過して不織布層に達して下部へ滲出してモレとなる。 If the resin processing is performed properly, the surface state of the composite sheet does not change greatly and the generation of moisture does not occur even after 24 hours after 6 hours. However, if the resin processing is insufficient, MFC on the surface layer swells, a crumpled "fluff" occurs, and partial delamination occurs, passes through the MFC layer and MFC / nonwoven fabric coexisting layer, reaches the nonwoven fabric layer, and exudes to the lower part. Become.

　このように（１）表面層の“フクレ”の発生状態と頻度；（２）表面層の着色状態（色素の吸着状態）；（３）モレの発生の有無とその状態；を評価、解析することは、複合体の耐水性評価にとって重要なポイントの１つである。 As described above, (1) the occurrence state and frequency of “swelling” on the surface layer; (2) the coloring state (pigment adsorption state) of the surface layer; This is one of the important points for the water resistance evaluation of the composite.

　本発明による耐水性高通気性複合シートにおいては、このようなリング式シールテストにおいて、２時間以上は、モレの検知がなく、６時間経過しても全面的なモレがなく、中・小のスポット状にとどまっていることを製品基準としている。 In the water-resistant and highly breathable composite sheet according to the present invention, in such a ring-type seal test, there is no detection of leakage for 2 hours or more, and there is no overall leakage even after 6 hours. The product standard is that it stays in a spot shape.

　４）加圧下における複合体下層からのモレの発生状態の評価
　―複合体シートの加圧下における耐水性の評価測定法参照―
　紙おむつの場合は、体位によって荷重のかかる部位は異なるが、必ず体重という荷重がかかった状態で使用される。耐水性という点で一番厳しい条件は、吸収体が水分の飽和状態で、荷重下で使用される場合である。例えば就寝時等はこのような荷重下で数時間放置されることもあり得るので、荷重下で経時的にモレの発生の有無とその状態を解析することは極めて重要である。 4) Evaluation of the state of mole formation from the lower layer of the composite under pressure-Refer to the evaluation and measurement method of water resistance under pressure of the composite sheet-
In the case of a disposable diaper, the portion to which the load is applied varies depending on the posture, but the diaper is always used in a state of being loaded with a weight. The most severe condition in terms of water resistance is when the absorber is used under load in a saturated state of moisture. For example, at bedtime, it may be left for several hours under such a load. Therefore, it is extremely important to analyze whether or not a leak has occurred over time under the load and its state.

　加圧下リークテストは、極めて苛酷なテストであり、通常の用途であれば、このような負荷テストは必要ないが、本発明による耐水性高通気性複合シートとしては、好ましくは、３０分以上、リークの発生を検知しないことを目標としている。 The leak test under pressure is an extremely severe test, and such a load test is not necessary for normal use, but the water-resistant and highly breathable composite sheet according to the present invention is preferably 30 minutes or more, The goal is not to detect the occurrence of leaks.

　消費者テスト等の検討結果から、加圧下リークテストで４時間以上に亘ってリークの発生がなければ、まずモレトラブルの発生はないという結果を得ている。 From the examination results of the consumer test and the like, it has been obtained that if no leak occurs for 4 hours or more in the leak test under pressure, there will be no more trouble.

　テスト法では、飽和液として青色に着色した生理食塩水を用い、検知紙として白色濾紙を用いて、鋭敏に微妙なモレも検知できるようになっている。 In the test method, a saline solution colored in blue is used as a saturated solution, and white filter paper is used as detection paper, so that sensitive and delicate moisture can be detected.

　樹脂加工が適切に行われていると荷重下でも４時間以上に亘って安定でリークの発生はないが、樹脂加工が不充分であると数十分でリークが発生する。 If the resin processing is performed properly, it will be stable for 4 hours or more even under load and no leakage will occur, but if the resin processing is insufficient, leakage will occur in several tens of minutes.

　このように複合体の最終状態として、（１）荷重下におけるモレ発生の時間；（２）荷重下におけるモレの発生状態；を評価、解析することは、複合体の耐水性評価として最重点事項である。 Thus, as the final state of the composite, the evaluation and analysis of (1) the time of generation of moisture under load; (2) the state of generation of leakage under load; It is.

　（本発明による耐水性高通気性複合シートに求められる通気性能）
　本発明による耐水性高通気性複合シートは、耐水性とともに高通気性をもつものである。ここでいう通気性は、液状の水は透過しないが空気や水蒸気は透過する性質をもつものである。 (Breathability required for water-resistant and highly breathable composite sheet according to the present invention)
The water-resistant and highly breathable composite sheet according to the present invention has water permeability and high breathability. The air permeability mentioned here has a property that liquid water does not permeate but air and water vapor permeate.

　本発明の複合体に求められる通気度は、ガーレー法の透気度で表現すると、３００秒／１００ｍＬ未満、好ましくは、２００秒／１００ｍＬ以下、より好ましくは、２０秒／１００ｍＬ～１５０秒／１００ｍＬ、よりさらに好ましくは１０～１００秒／１００ｍＬという非常に高いものであり、従来のいわゆるＰＥフィルム系の高通気性、耐水性シートとは、透気度の数値の点で、非常にレベルの異なるものである。 The air permeability required for the composite of the present invention is less than 300 seconds / 100 mL, preferably 200 seconds / 100 mL or less, more preferably 20 seconds / 100 mL to 150 seconds / 100 mL, when expressed by the air permeability of the Gurley method. More preferably, it is very high of 10 to 100 seconds / 100 mL, and the level of air permeability is very different from that of a conventional so-called PE film-based highly breathable and water-resistant sheet. Is.

　下記の表２は、本発明による耐水性高通気性複合シートの製造方法に従って製造した耐水性高通気性複合シート（本発明品）と、従来から使用されてきたＰＥ製のいわゆるＭｉｃｒｏ　Ｐｏｒｏｕｓ　Ｆｉｌｍとの通気性能を比較したものである。 Table 2 below shows a water-resistant and highly breathable composite sheet manufactured according to the method of manufacturing a water-resistant and highly breathable composite sheet according to the present invention (a product of the present invention), and a so-called Micro Porous Film made of PE that has been conventionally used. This is a comparison of the ventilation performance.

　表２において、Ｍｉｃｒｏ　Ｐｏｒｏｕｓ　Ｆｉｌｍとしては代表的なＴｏｋｕｙａｍａ製の“Ｐｏｌｕｍ（登録商標）”とＭｉｔｓｕｉ　Ｃｈｅｍｉｃａｌｓ製の“Ｅｓｐｏｉｒ（登録商標）”を従来例として示した。 In Table 2, as a typical example of Micro Porous Film, “Polum (registered trademark)” manufactured by Tokuyama and “Espoir (registered trademark)” manufactured by Mitsui Chemicals are shown as conventional examples.

　ＰＥ製のＭｉｃｒｏ　Ｐｏｒｏｕｓ　Ｆｉｌｍの場合、通気性が非常に低い（３００秒／１００ｍＬ以上）ため、透湿性を目安としている。本発明品の場合、通気性が高いのでガーレー法による透気度を主要な目安としている。 In the case of PE made by Micro Porous Film, the air permeability is very low (300 seconds / 100 mL or more), so the moisture permeability is a standard. In the case of the product of the present invention, since air permeability is high, the air permeability by the Gurley method is used as a main measure.

Figure JPOXMLDOC01-appb-T000002
Figure JPOXMLDOC01-appb-T000002

　フィルム状のＰｏｌｕｍやＥｓｐｏｉｒと比較して本発明品の厚みが５倍～１０倍と非常に厚いのは、本発明品が不織布複合体のためである。 The reason why the thickness of the product of the present invention is very thick, 5 to 10 times, compared with film-like Polum and Espoir is because the product of the present invention is a nonwoven fabric composite.

　＜本発明による耐水性高通気性複合シートの製造方法＞
　本発明による耐水性高通気性複合シートの製造方法は：
　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ複合体に樹脂加工を施すことによって得られる、耐水性高通気性複合シートの製造方法であって、
　樹脂成分が少なくとも前記複合体のＭＦＣ層及びＭＦＣ・不織布共存層に行き渡るような樹脂処理（全層樹脂処理）と、
　樹脂成分を前記複合体の上表面層のみにとどめる樹脂処理（表層樹脂処理）と、
　を組合わせて複合体に樹脂加工を施すことを特徴とする。 <Method for Producing Water-Resistant, Highly Breathable Composite Sheet According to the Present Invention>
The method for producing a water-resistant and highly breathable composite sheet according to the present invention is:
A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of
Resin treatment (all-layer resin treatment) in which the resin component reaches at least the MFC layer and the MFC / nonwoven fabric coexisting layer of the composite,
Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite;
The composite is subjected to resin processing in combination.

　（本発明による耐水性高通気性複合シートの製造方法における樹脂処理の考え方）
　本発明による耐水性高通気性複合シートの製造方法は、図１に示すような、ＭＦＣ単独層（１）、ＭＦＣ・不織布共存層（２）及び不織布単独層（３）の３層構造をもつ微細化セルロース繊維・不織布複合体（ＭＦＣ・不織布複合体）を熱可塑性樹脂などの樹脂を用いて加工するものであって、この３層構造を有する微細化セルロース繊維・不織布複合体が本来的に持っている高通気性を維持しながら耐水性をも賦与することが目的である。 (Concept of resin treatment in the method for producing a water-resistant and highly breathable composite sheet according to the present invention)
The method for producing a water-resistant and highly breathable composite sheet according to the present invention has a three-layer structure of an MFC single layer (1), an MFC / nonwoven fabric coexisting layer (2) and a non-woven fabric single layer (3) as shown in FIG. A refined cellulose fiber / nonwoven fabric composite (MFC / nonwoven fabric composite) is processed using a resin such as a thermoplastic resin. The purpose is to impart water resistance while maintaining the high air permeability.

　高い通気性を維持し且つ安定な耐水性を賦与し、その状態を長時間に渡って保つためには、ＭＦＣ層の最上表面から不織布層の下層に至る部位それぞれに対して適切な樹脂加工による疎水化処理を施す必要がある。 In order to maintain high breathability and provide stable water resistance, and maintain the state for a long time, appropriate resin processing is applied to each part from the uppermost surface of the MFC layer to the lower layer of the nonwoven fabric layer. It is necessary to apply a hydrophobic treatment.

　即ち、ＭＦＣ層の最上表面に対しては、ＭＦＣ層の上表面に存在する大小の割れ目や欠陥部分を充填、補修するとともに、ＭＦＣ層上表面全体を被覆するような樹脂単独層（Ａ）（以下、単に樹脂層とも称する。）を形成する。 In other words, the uppermost surface of the MFC layer is filled and repaired with large and small cracks and defects existing on the upper surface of the MFC layer, and the resin alone layer (A) ( Hereinafter, it is also simply referred to as a resin layer).

　ＭＦＣ層内に対しては、ＭＦＣ層内に浸透して、微細なＭＦＣ各繊維表面を被覆して疎水化するとともに、ＭＦＣ繊維間の隙間を充填、結合して、樹脂・ＭＦＣ共存層（Ｂ）を形成する。 For the inside of the MFC layer, it penetrates into the MFC layer, coats the surface of each fine MFC fiber to make it hydrophobic, fills and bonds the gaps between the MFC fibers, and combines the resin / MFC coexisting layer (B ).

　ＭＦＣ・不織布共存層に対しては、ＭＦＣ表面とともに不織布構成繊維表面も被覆して、樹脂も加わった、樹脂・ＭＦＣ・不織布共存層（Ｅ）を形成する。 For the MFC / nonwoven fabric coexisting layer, a resin / MFC / nonwoven fabric coexisting layer (E) is formed by coating the surface of the non-woven fabric as well as the MFC surface and adding resin.

　不織布層に対しては、最下面の不織布層とも結合、被覆して、樹脂・不織布共存層（Ｆ）も形成することが望ましい。 For the nonwoven fabric layer, it is desirable to form a resin / nonwoven fabric coexistence layer (F) by bonding and covering the lowermost nonwoven fabric layer.

　但し、この最下層については、不織布がＰＥやＰＰのスパンメルト不織布の場合は、不織布自体が強い疎水性や撥水性をもつので、必ずしも樹脂・不織布共存層を設ける必要性は余り重要ではない。 However, regarding the lowermost layer, when the nonwoven fabric is a spun melt nonwoven fabric of PE or PP, the nonwoven fabric itself has strong hydrophobicity and water repellency, and therefore it is not always necessary to provide a resin / nonwoven fabric coexistence layer.

　（樹脂の濃度分布あるいは濃度勾配）
　高通気性と耐水性のバランスを保つためには、樹脂量と樹脂の存在状態をコントロールする必要がある。 (Concentration distribution or gradient of resin)
In order to maintain a balance between high air permeability and water resistance, it is necessary to control the amount of resin and the presence state of the resin.

　全層を多量な樹脂で固めたような構造をとると、コストがアップすることは勿論であるが、耐水性は充分あっても通気性が殆どないフィルムのような状態になってしまう。また樹脂量が少なすぎると、短時間は耐水性をもつが、時間の経過につれＭＦＣの親水性の故にＭＦＣへの吸水、膨潤により液の浸出が起こるようになる。 If a structure in which all the layers are hardened with a large amount of resin is taken, the cost will rise, but it will be in the state of a film that has almost no breathability even though it has sufficient water resistance. On the other hand, if the amount of resin is too small, it has water resistance for a short time, but as time passes, liquid leaching occurs due to water absorption and swelling into the MFC due to the hydrophilicity of the MFC.

　従って、最上表面には薄くて大部分が樹脂層によって形成するバリヤーを形成するとともに、ＭＦＣ層及びＭＦＣ・不織布共存層に対しては、出来るだけ少ない樹脂量で均一に多孔質構造を維持しながらＭＦＣの表面を疎水化して、水分の浸透を防止する必要がある。 Therefore, while forming a thin barrier on the uppermost surface, most of which is formed by a resin layer, the MFC layer and the MFC / nonwoven fabric coexisting layer maintain a uniform porous structure with as little resin as possible. It is necessary to hydrophobize the surface of the MFC to prevent moisture penetration.

　このように上表面には濃く、下部にそして内部に移行するにつれて濃度が薄くなるような樹脂成分の濃度分布あるいは濃度勾配を形成せしむるためには、いろいろな工夫が必要になる。 In order to form a concentration distribution or concentration gradient of the resin component that is dark on the upper surface and decreases in concentration toward the bottom and inside as described above, various measures are required.

　例えば１回の樹脂処理で上述したような濃度勾配を実現するために、乾燥時の水分移動を利用して、樹脂のｍｉｇｒａｔｉｏｎ（移行）を促進して濃度勾配を形成する方法もあるが、確実性や再現性が低下してしまう場合がある。 For example, in order to realize the concentration gradient as described above in one resin treatment, there is a method of forming a concentration gradient by promoting the migration of the resin by using moisture movement during drying. And reproducibility may be reduced.

　確実性や再現性よく樹脂の濃度勾配を形成する方法としては、下記に述べる（１）及び（２）の処理を組み合わせて行う、いわゆる多段処理法が望ましい。 As a method for forming a resin concentration gradient with high certainty and reproducibility, a so-called multi-stage treatment method, which is a combination of the treatments (1) and (2) described below, is desirable.

　即ち、（１）樹脂成分が少なくともＭＦＣ層全体、好ましくは、ＭＦＣ層及びＭＦＣ・不織布共存層、さらに好ましくはＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層全層に行き渡るような樹脂処理（これを全層樹脂処理と称することにする）；及び（２）樹脂成分をＭＦＣの上表面層のみに留め、樹脂成分がＭＦＣ層の上表面に主として配置されるようにする処理（これを表層樹脂処理と称することにする）の組合せからなるものである。 That is, (1) Resin treatment in which the resin component reaches at least the entire MFC layer, preferably the MFC layer and the MFC / nonwoven fabric coexisting layer, more preferably the MFC layer, the MFC / nonwoven fabric coexisting layer, and the nonwoven fabric layer. (This will be referred to as a full-layer resin treatment); and (2) A treatment in which the resin component is kept only on the upper surface layer of the MFC and the resin component is mainly disposed on the upper surface of the MFC layer (this is called It is called a surface layer resin treatment).

　この多段処理法の考えについてより詳しく説明する。全層樹脂処理においては、出来るだけ表面層から裏面に至るまで全層に均一に樹脂を行き渡らせる必要があり、相対的に薄い樹脂濃度で加工するのが望ましく、一方表層樹脂処理については、相対的に濃い濃度で薄い皮膜状の組織を上表面に形成するのが望ましい。 The concept of this multistage processing method will be explained in more detail. In the all-layer resin treatment, it is necessary to spread the resin uniformly in all layers from the surface layer to the back surface as much as possible, and it is desirable to process with a relatively thin resin concentration, while for the surface resin treatment, It is desirable to form a thin film-like structure on the upper surface with an extremely high concentration.

　（全層樹脂処理と表層樹脂処理の実施態様）
　具体的な全層樹脂処理と表層樹脂処理を組み合わせる方法としては、下記の（１）及び（２）のいずれかに大別できるが、どちらであってもよい。 (Embodiments of full-layer resin treatment and surface resin treatment)
Specific methods for combining all-layer resin treatment and surface resin treatment can be broadly classified into either (1) and (2) below, but either method may be used.

　（１）全層樹脂処理を行った後に表層樹脂処理を行う方法
　（２）表層樹脂処理をまず行った後に全層樹脂処理を行う方法
のどちらかに大別できるが、どちらであってもよい。 (1) Method of performing surface layer resin treatment after performing all layer resin treatment (2) The method can be broadly classified into either method of performing full layer resin treatment after first performing surface layer resin treatment. .

　（全層樹脂処理を行う方法）
　まず全層樹脂処理についてより詳しく説明する。 (Method to perform all-layer resin treatment)
First, the full-layer resin treatment will be described in more detail.

　樹脂を全体に均一に存在させることによって、上記の「本発明による耐水性高通気性複合シートの製造方法における樹脂処理の考え方」に記述したように、ＭＦＣの疎水化、ＭＦＣ相互を結合して樹脂・ＭＦＣ共存層を形成し、ＭＦＣと不織布とを結合して樹脂・ＭＦＣ・不織布共存層を形成し、そして更には不織布構成繊維の表面の疎水化を図り樹脂・不織布共存層を形成するものであり、ＭＦＣ間、不織布間に存在する空隙全てを充填するものではない。従って、例えばＳＢＲの水系ラテックス、アクリル酸樹脂系の水系サスペンション、ポリウレタン樹脂の溶媒溶液等の樹脂原料を用いる場合には、水や溶媒で更に希釈した状態で用いる必要がある。 By making the resin uniformly present on the whole, as described in the above-mentioned “Concept of resin treatment in the method for producing a water-resistant and highly breathable composite sheet according to the present invention”, the hydrophobization of MFC and the MFC are combined with each other. Resin / MFC coexistence layer is formed, MFC and non-woven fabric are combined to form resin / MFC / non-woven fabric coexistence layer, and further, the surface of non-woven fabric constituent fiber is made hydrophobic to form resin / non-woven fabric coexistence layer It does not fill all the voids existing between MFCs and non-woven fabrics. Therefore, for example, when using a resin raw material such as an SBR aqueous latex, an acrylic resin aqueous suspension, or a solvent solution of a polyurethane resin, it is necessary to use it in a state further diluted with water or a solvent.

　全層樹脂処理は、上記のような態様でＭＦＣ・不織布複合体に樹脂を分布させる方法であれば特に制約はないが、例えば、下記（１）～（４）の方法によって行われてもよい。 The all-layer resin treatment is not particularly limited as long as it is a method for distributing the resin to the MFC / nonwoven fabric composite in the above-described manner, but may be performed by the following methods (1) to (4), for example. .

　（１）上表面のＭＦＣ面から５％～８％の濃度の樹脂希釈液を、まず真空サクション下で１回目のコーティングを行って、コーティング時に樹脂液を全層に行き渡らせるようにする方法 (1) A method in which a resin dilution solution having a concentration of 5% to 8% from the MFC surface on the upper surface is first coated under vacuum suction so that the resin solution is spread over the entire layer during coating.

　（２）上表面のＭＦＣ面から更に薄い樹脂液を２回コーティングすることにより、液量を多くして全層に行き渡らせるようにする方法
　例えば、第１回目は３％～４％の濃度の樹脂希釈液で処理し、更に第２回目は５％～６％の濃度の樹脂希釈液でやはりＭＦＣ面から処理することにより、全層均一に樹脂液を行き渡らせるように行ってもよい。 (2) A method of increasing the amount of the liquid by spreading a thinner resin liquid twice from the MFC surface on the upper surface and spreading it over the entire layer. For example, in the first time, the concentration is 3% to 4%. The treatment may be performed with the resin diluent, and the second treatment may be performed from the MFC surface with the resin diluent having a concentration of 5% to 6% so that the resin solution can be distributed uniformly throughout the entire layer.

　（３）まず上表面のＭＦＣ面から第１回目の樹脂処理を３％～４％の濃度の樹脂希釈液で行い、次いで下裏面側の不織布面から第２回目の樹脂処理を５％～６％の濃度の樹脂希釈液で行うことによって、上、下から処理することにより全層に樹脂を行き渡らせる方法 (3) First, the first resin treatment is carried out from the MFC surface of the upper surface with a resin diluent having a concentration of 3% to 4%, and then the second resin treatment is carried out from the nonwoven fabric surface on the lower back surface to 5% to 6%. A method that spreads the resin to all layers by processing from above and below by performing the resin dilution with a concentration of%.

　（４）まず下裏面の不織布面から第１回目の樹脂処理を３％～４％の濃度の樹脂希釈液で行い、次いで上表面のＭＦＣ面から第２回目の樹脂処理を５％～６％の濃度の樹脂希釈液で行うことによって、下、上から処理することにより全層に樹脂を行き渡らせる方法 (4) First, the first resin treatment is performed from the nonwoven fabric surface of the lower back surface with a resin diluent having a concentration of 3% to 4%, and then the second resin treatment is performed from the MFC surface of the upper surface to 5% to 6%. To spread the resin to all layers by treating from below and above by performing with a diluted resin solution

　全層樹脂処理に必要な樹脂の塗工量は、１０ｇ／ｍ２以下、好ましくは８ｇ／ｍ２～１ｇ／ｍ２、更に好ましくは５ｇ／ｍ２～２ｇ／ｍ２である。１０ｇ／ｍ２を超えると充填状態になりシート全体が硬くなると同時に通気性が低下するし、また勿論コストも増加する。１ｇ／ｍ２未満となると塗工効果が発揮されない。 The coating amount of the resin necessary for the all-layer resin treatment is 10 g / m 2 or less, preferably 8 g / m 2 to 1 g / m 2 , more preferably 5 g / m 2 to 2 g / m 2 . If it exceeds 10 g / m 2 , it will be in a filled state and the entire sheet will become hard and at the same time the air permeability will be reduced, and of course the cost will also increase. When it is less than 1 g / m 2 , the coating effect is not exhibited.

　（表層樹脂処理を行う方法）
　表層樹脂処理は、ＭＦＣの最上表面に対して処理を施す手段であり、一部ＭＦＣと共存するが大部分は樹脂単独層（Ａ）を形成するためであり、そのため比較的濃厚な濃度の樹脂液を用いて、出来るだけ薄い皮膜を形成する必要がある。 (Method of surface resin treatment)
Surface resin treatment is a means for treating the uppermost surface of the MFC, and partly coexists with the MFC, but most of it is for forming the resin single layer (A), and therefore a relatively dense resin. It is necessary to form a thin film as much as possible using the liquid.

　樹脂層（Ａ）の厚さは、少なくとも１０μｍ以下、好ましくは５μｍ～１μｍ、更に好ましくは４μｍ～２μｍが望ましい。目付で表現すれば、１０ｇ／ｍ２以下、好ましくは５ｇ／ｍ２～１ｇ／ｍ２、更に好ましくは４ｇ／ｍ２～２ｇ／ｍ２である。１０ｇ／ｍ２を超えると通気性が大幅に低下するし、またシート自体も硬化しコストも増大する。１ｇ／ｍ２未満となると皮膜形成が難しくなる。 The thickness of the resin layer (A) is at least 10 μm or less, preferably 5 μm to 1 μm, more preferably 4 μm to 2 μm. Expressed in terms of basis weight, it is 10 g / m 2 or less, preferably 5 g / m 2 to 1 g / m 2 , more preferably 4 g / m 2 to 2 g / m 2 . If it exceeds 10 g / m 2 , the air permeability is greatly lowered, and the sheet itself is cured and the cost is increased. When it is less than 1 g / m 2 , film formation becomes difficult.

　表層樹脂処理の方法としては、例えばＳＢＲの水系ラテックス、アクリル酸樹脂系の水系サスペンション、ポリウレタン樹脂の溶媒溶液等の樹脂原料を用いる場合には、１０％～３０％の比較的濃厚な水希釈樹脂あるいは溶媒希釈樹脂を用いて、表面にグラビア、フレキソ、マイクログラビア等のコーティングロールを用いて表面コーティングを行ってもよい。 As a method for surface layer resin treatment, for example, when using a resin raw material such as SBR aqueous latex, acrylic resin aqueous suspension, polyurethane resin solvent solution, etc., a relatively thick water diluted resin of 10% to 30% is used. Alternatively, surface coating may be performed using a coating roll such as gravure, flexo, or micro gravure on the surface using a solvent diluted resin.

　（表層樹脂処理と更なる撥水加工処理）
　本発明において、耐水性を賦与するためには、樹脂処理による疎水化は必須条件であるが、それ以上の撥水性の賦与は必ずしも必要ではない。しかし、上記の樹脂を用いた処理の他に、撥水材を用いた処理をさらにつけ加えてもよい。この撥水材を用いた処理の目的としては、次のようなものが挙げられる。 (Surface resin treatment and further water repellent treatment)
In the present invention, hydrophobization by resin treatment is an essential condition for imparting water resistance, but further imparting water repellency is not necessarily required. However, in addition to the treatment using the above resin, a treatment using a water repellent material may be further added. The purpose of the treatment using this water repellent material is as follows.

　（１）耐水性が特に重要な用途に応用する場合等、耐水性を更に強化する必要が生じた場合
　（２）樹脂量を出来るだけ少なくして、表面の撥水性を賦与することを目的とする場合
　（３）通気性と耐水性のバランスを改良する場合 (1) When water resistance needs to be further strengthened, such as when it is applied to applications where water resistance is particularly important. (2) To reduce the amount of resin as much as possible, and to impart surface water repellency. (3) When improving the balance between breathability and water resistance

　上記のような目的で撥水材を用いた処理を行う方法としては、下記の（１）～（３）の方法が挙げられる。 The following methods (1) to (3) may be mentioned as a method for performing the treatment using a water repellent material for the above purpose.

　（１）表層樹脂処理を行った後、更にその上表面に撥水材の層をコーティングする方法　（２）表層樹脂処理を行う樹脂剤に撥水材を混和させて、樹脂と撥水材の共存層を形成する方法
　（３）全層樹脂処理を行った後に、更にその上表面に撥水材の層をコーティングする方法 (1) A method of coating a surface of the water-repellent material on the upper surface after the surface resin treatment, and (2) mixing the water-repellent material with the resin agent for the surface resin treatment, Method of forming coexistence layer (3) Method of coating water repellent layer on the upper surface after all-layer resin treatment

　本発明において、上記の目的で使用される撥水材としては、特に制約はないが、例えばオレフィン系撥水剤、パラフィン系撥水剤、シリコーン系撥水剤、テフロン系撥水剤等が適宜用いられる。 In the present invention, the water repellent material used for the above purpose is not particularly limited, and for example, olefin water repellents, paraffin water repellents, silicone water repellents, Teflon water repellents and the like are appropriately used. Used.

　上記（１）及び（３）のように表層に存在する樹脂層の上に撥水材の層を形成する場合には、表層樹脂との接合性を持つことを前提として考えれば、溶液状、スプレー状、エマルジョン状、サスペンション状等いろいろな形状の撥水材の形態で処理が可能である。 In the case of forming a water repellent layer on the resin layer present in the surface layer as in (1) and (3) above, assuming that it has bonding properties with the surface layer resin, It can be processed in the form of water repellent materials of various shapes such as spray, emulsion and suspension.

　一方、上記（２）のように、樹脂と混和して撥水材を用いる場合には、樹脂剤との混和性が重要であるので、制約される条件が必然的に多くなる。例えば、樹脂エマルジョンやサスペンションに撥水材のエマルジョンを一定の割合で混合して、混合エマルジョン、混合サスペンションの形で利用すれば、比較的条件選択が容易である。特に、用いる樹脂と適度な親和性を有する撥水材を用いることが好ましい。 On the other hand, as described in (2) above, when a water repellent material is used by mixing with a resin, the miscibility with the resin agent is important, and thus the conditions that are restricted are inevitably increased. For example, if a water-repellent material emulsion is mixed with a resin emulsion or a suspension at a certain ratio and used in the form of a mixed emulsion or a mixed suspension, it is relatively easy to select conditions. In particular, it is preferable to use a water repellent material having an appropriate affinity with the resin to be used.

　反面、撥水材の添加により樹脂皮膜の形成が阻害されることがあるので、添加率や撥水材の選択には充分注意する必要がある。例えば、ＳＢＲラテックスにワックス系の撥水材の水系エマルジョンをほぼ１：１の割合で混合して表層樹脂処理液として使用した場合、表面から液の浸潤が、樹脂を単独で用いた処理よりも大幅に低下する。それは、撥水材によって樹脂相互の層形成が阻害されるためである。なお、樹脂が主成分である場合のような、混合比を樹脂／撥水材＝３／１程度とすると、このような現象は起こらなくなる。 On the other hand, since the formation of the resin film may be hindered by the addition of the water repellent material, it is necessary to pay close attention to the addition rate and the selection of the water repellent material. For example, when an aqueous emulsion of a wax-based water repellent material is mixed with SBR latex at a ratio of approximately 1: 1 and used as a surface layer resin treatment liquid, the infiltration of the liquid from the surface is more than the treatment using the resin alone. Decrease significantly. This is because the layer formation between the resins is hindered by the water repellent material. Note that this phenomenon does not occur when the mixing ratio is about resin / water repellent material = 3/1, as in the case where the resin is the main component.

　（本発明に使用される樹脂成分とその形態）
　本発明に使用される樹脂成分とその形態について説明する。本発明において、複合体の処理に用いられる樹脂としては、上記の目的で用いられるものであれば、特に制約はないが、下記（１）～（４）のものが挙げられる。 (Resin component used in the present invention and its form)
The resin component used for this invention and its form are demonstrated. In the present invention, the resin used for the treatment of the composite is not particularly limited as long as it is used for the above purpose, and includes the following (1) to (4).

　（１）水や有機溶媒等の媒体中に熱可塑性樹脂成分を分散剤や乳化剤を用いて分散あるいは乳化した状態の材料、例えばアクリル酸及びその誘導体のエマルジョン、ＥＶＡエマルジョン、ＳＢＲ等の合成ゴムのラテックス類、ＰＥやＰＰの微粒子サスペンション等である。これらは比較的取り扱いが容易で、表層樹脂処理、全層樹脂処理のいずれにも用いられる。 (1) A material in which a thermoplastic resin component is dispersed or emulsified in a medium such as water or an organic solvent using a dispersant or an emulsifier, such as an acrylic acid and its derivative emulsion, an EVA emulsion, a synthetic rubber such as SBR Latex, PE and PP fine particle suspension. These are relatively easy to handle and can be used for both surface resin treatment and all layer resin treatment.

　（２）樹脂やそのプレポリマーの水あるいは有機溶媒溶液、例えばＰＶＡや反応性アクリル酸プレポリマーの水溶液、ポリウレタンあるいは反応性ポリウレタンプレポリマーの有機溶媒溶液等である。これらは皮膜形成性が強いので、表層樹脂処理に好んで用いられる。 (2) Water or an organic solvent solution of the resin or its prepolymer, such as an aqueous solution of PVA or reactive acrylic acid prepolymer, an organic solvent solution of polyurethane or reactive polyurethane prepolymer, or the like. Since these have strong film-forming properties, they are preferably used for surface layer resin treatment.

　（３）粉体状、粒状の熱可塑性ポリマー、例えばＰＥ、ＰＰ、ＥＶＡ等の粉体あるいは粒状体である。これらは、取り扱いは難しいが、表層樹脂処理、全層樹脂処理のいずれにも用いられる。 (3) Powdery or granular thermoplastic polymer, such as PE, PP, EVA powder or granular material. Although these are difficult to handle, they are used for both surface layer resin treatment and full layer resin treatment.

　（４）ＭＦＣとの複合化に用いる不織布として易熱溶融性成分を含むケース、例えばＰＥ／ＰＥＴ、ＰＥ／ＰＰ、易溶融性ＰＥＴ／難溶融性ＰＥＴとの複合成分を組み合わせたいわゆるＢｉ－ｃｏｍｐｏｎｅｎｔ　Ｆｉｂｅｒから構成された不織布、或いはポリオレフィン系合成パルプ（商品名：ＳＷＰ（登録商標）（三井化学社製））を結合材とした不織布等を用いるケースである。この場合には全層樹脂処理を行う手段としては極めて有効であるが、表層樹脂処理の手段としてはフィルム化すると硬化するので難しい。 (4) Cases containing easily heat-meltable components as non-woven fabrics used for composite with MFC, for example, so-called Bi-component that combines PE / PET, PE / PP, and easily meltable PET / hardly meltable PET composite components This is a case of using a non-woven fabric made of Fiber or a non-woven fabric using a polyolefin synthetic pulp (trade name: SWP (registered trademark) (manufactured by Mitsui Chemicals)) as a binder. In this case, it is extremely effective as a means for carrying out all-layer resin treatment, but it is difficult as a means for surface resin treatment since it is cured when formed into a film.

　これらの樹脂成分の中で特に表層樹脂処理にも全層樹脂処理にも使用可能な水系サスペンション、エマルジョン、特にＳＢＲ系のゴムラテックスを用いた樹脂処理を例として、より詳細に説明する。 Among these resin components, a resin suspension using an aqueous suspension and emulsion, particularly an SBR rubber latex that can be used for both surface layer resin treatment and all layer resin treatment will be described in detail.

　（ＳＢＲ系ラテックスを用いた表層樹脂処理及び全層樹脂処理について）
　ＳＢＲ系ラテックスを樹脂処理剤として使用する場合、通常の紙加工等の耐水化処理に用いられる水分散系ＳＢＲ系ラテックスは、例えば次のような組成をもっている。 (About surface layer resin treatment and all layer resin treatment using SBR latex)
When SBR latex is used as a resin treatment agent, water-dispersed SBR latex used for water resistance treatment such as normal paper processing has the following composition, for example.

Figure JPOXMLDOC01-appb-T000003
　＊尚、上記の系での架橋剤添加はＳＢＲと共存するアクリル酸、ＭＭＡ等の親水性のモノマー成分を架橋して疎水化するためであり、５０～６０℃の温度で６時間程度保持して硬化する必要がある。
Figure JPOXMLDOC01-appb-T000003
 * Addition of a cross-linking agent in the above system is to make hydrophilic monomer components such as acrylic acid and MMA coexisting with SBR to be hydrophobized and kept at a temperature of 50 to 60 ° C. for about 6 hours. Need to be cured.

　このような組成のラテックスは、主成分の疎水性樹脂に加えて乳化剤、親水性モノマー、消泡剤中の浸透剤等の親水化成分を含有している。上記のような組成のラテックスでも、条件を適切に選択すれば耐水性を賦与することは可能であるが、逆に条件が振れると安定な耐水性が確保されない場合がある。例えば硬化が不充分であったり消泡剤を多用したりすると、親水化成分がシート中に残存し、水が浸透し易くなって耐水性を大幅に阻害することになる。 The latex having such a composition contains a hydrophilic component such as an emulsifier, a hydrophilic monomer, and a penetrating agent in an antifoaming agent in addition to the hydrophobic resin as a main component. Even with a latex having the composition as described above, it is possible to impart water resistance if the conditions are appropriately selected, but on the contrary, if the conditions change, stable water resistance may not be ensured. For example, if the curing is insufficient or a large amount of antifoaming agent is used, the hydrophilic component remains in the sheet, and water easily penetrates and water resistance is greatly inhibited.

　上記のような耐水性の阻害を回避するためには、乳化剤の添加量、アクリル酸モノマーの添加量を少なくして、架橋処理をしなくても耐水性を発揮できる条件、更にはノニオン活性剤を含有しない消泡剤等の条件選択が必要である。例えば、乳化剤としては、使用後に反応して界面活性剤効果を消滅させる反応性界面活性剤を用いることも望ましい。 In order to avoid the inhibition of water resistance as described above, the addition amount of the emulsifier and the addition amount of the acrylic acid monomer are reduced so that the water resistance can be exhibited without performing the crosslinking treatment. It is necessary to select conditions such as an antifoaming agent that does not contain. For example, as the emulsifier, it is also desirable to use a reactive surfactant that reacts after use to extinguish the surfactant effect.

　下記の表３は、親水化成分を比較的多く含む場合と親水化成分を少なくした場合とを比較したものである。 Table 3 below compares the case where a relatively large amount of hydrophilic component is included with the case where the amount of hydrophilic component is decreased.

　表３は、ラテックス組成中の親水化成分をできるだけ除いた樹脂で処理した場合（Ｎｏ．１）と、アクリル酸や乳化剤、消泡剤に親水化成分を混在している上記に示したＳＢＲ系ラテックスを樹脂材として用いて処理した場合の、硬化前（Ｎｏ．２）及び硬化後（Ｎｏ．３）の耐水性能の比較を示したものである。 Table 3 shows the SBR system shown above in which the hydrophilic component in the latex composition is removed as much as possible (No. 1), and the hydrophilic component is mixed in acrylic acid, an emulsifier, and an antifoaming agent. The comparison of the water resistance before hardening (No. 2) and after hardening (No. 3) at the time of processing using latex as a resin material is shown.

Figure JPOXMLDOC01-appb-T000004
Figure JPOXMLDOC01-appb-T000004

　（耐水加工に必要な樹脂量の影響）
　ＭＦＣ層とＭＦＣ・不織布共存層と不織布層とからなる微細化セルロース繊維・不織布複合体に耐水性を賦与する目的で、全層樹脂処理と表層樹脂処理の樹脂加工を行うわけであるが、それに必要な樹脂量の好適範囲は、ＭＦＣの存在量、全層樹脂処理と表層樹脂処理のバランス等によって変化する。樹脂処理に用いる樹脂の量の好適な範囲は、必要な樹脂量の全量で表現すれば、既述したように２０ｇ／ｍ２を超えない範囲、好ましくは１５ｇ／ｍ２～２ｇ／ｍ２、更に好ましくは１０ｇ／ｍ２～３ｇ／ｍ２の範囲が望ましい。２０ｇ／ｍ２を超えると複合体の全層が樹脂で充填され、耐水性は向上するが透気度が２００秒／１００ｍＬを超えるようになる。相対的にいえば、ＭＦＣ量が多いと樹脂量が多くても透気度はあまり上昇しない。また、全層樹脂処理量に比較して表層樹脂処理量が相対的に多くなると、透気度は大幅に上昇する。耐水性と透気度のバランスを考慮すると、ＭＦＣ量が１０ｇ／ｍ２前後、全層樹脂処理量が３ｇ／ｍ２～６／ｍ２、表層樹脂処理量が２ｇ／ｍ２～４ｇ／ｍ２のであることが好ましい。このような範囲にあると、安定な耐水性と適切な透気度が得られる。 (Influence of the amount of resin required for water-resistant processing)
For the purpose of imparting water resistance to the refined cellulose fiber / nonwoven fabric composite consisting of the MFC layer, MFC / nonwoven fabric coexisting layer and nonwoven fabric layer, all-layer resin treatment and surface resin treatment are processed. The suitable range of the required resin amount varies depending on the abundance of MFC, the balance between all-layer resin treatment and surface resin treatment, and the like. A suitable range of the amount of resin used for the resin treatment is expressed in the range of not exceeding 20 g / m 2 as described above, preferably 15 g / m 2 to 2 g / m 2 , as described above. The range of 10 g / m 2 to 3 g / m 2 is more desirable. If it exceeds 20 g / m 2 , the entire layer of the composite is filled with resin, and the water resistance is improved, but the air permeability exceeds 200 seconds / 100 mL. Speaking relatively, if the amount of MFC is large, the air permeability does not increase so much even if the amount of resin is large. Moreover, if the surface resin treatment amount is relatively larger than the total layer resin treatment amount, the air permeability is significantly increased. Considering the balance between water resistance and air permeability, the MFC amount is around 10 g / m 2 , the total layer resin treatment amount is 3 g / m 2 to 6 / m 2 , and the surface layer resin treatment amount is 2 g / m 2 to 4 g / m. 2 is preferable. In such a range, stable water resistance and appropriate air permeability can be obtained.

　下記の表５は、ＭＦＣ量を５ｇ／ｍ２～１５ｇ／ｍ２まで変化させ、総樹脂量を５ｇ／ｍ２～１５ｇ／ｍ２まで変化させ、更に全層樹脂処理量と表層樹脂処理量の割合を変化させた場合の透気度に与える影響を示したものである。 Table 5 below shows that the MFC amount is changed from 5 g / m 2 to 15 g / m 2 , the total resin amount is changed from 5 g / m 2 to 15 g / m 2 , and the total resin treatment amount and the surface resin treatment amount are further changed. This shows the influence on the air permeability when the ratio is changed.

Figure JPOXMLDOC01-appb-T000005
Figure JPOXMLDOC01-appb-T000005

　なお、表５において、耐水性の評価は、下記の基準に基づいて行った。 In Table 5, the water resistance was evaluated based on the following criteria.

　◎：水浸透テスト、加圧下リークテストのいずれも合格
　○：加圧下リークテストでサンプルの一部に微小リーク発生あり
　△：加圧下リークテストにおいて、約１時間でリーク発生
　×：浸透テスト、加圧下リークテストのいずれも不合格 ◎: Passes both water penetration test and leak test under pressure ○: A small leak occurs in a part of the sample in the leak test under pressure △: Leak occurs in about 1 hour in the leak test under pressure ×: Penetration test, addition None of the reduction leak tests

　この表から耐水性と透気度のバランスを考えると、ＭＦＣ量が１０ｇ／ｍ２前後、全層樹脂処理量が３ｇ／ｍ２～５ｇ／ｍ２、表層樹脂処理量が２ｇ／ｍ２～３ｇ／ｍ２であることが好ましい。このような範囲にあると、適切な耐水性と透気度が得られる。 Considering the balance between water resistance and air permeability from this table, the MFC amount is around 10 g / m 2 , the total layer resin treatment amount is 3 g / m 2 to 5 g / m 2 , and the surface layer resin treatment amount is 2 g / m 2 to it is preferably 3 g / m 2. In such a range, appropriate water resistance and air permeability can be obtained.

　また、下記の表６は、樹脂を希釈した場合の透気度及び耐水性に及ぼす影響を検討したものである。ＭＦＣ量を１０ｇ／ｍ２に固定し、総樹脂量を８ｇ／ｍ２と６ｇ／ｍ２との２つのケースの場合に、全層樹脂処理及び表層樹脂処理を行う樹脂濃度を３％～２０％まで変化させた場合の、樹脂濃度の影響を示す。 Table 6 below examines the influence on the air permeability and water resistance when the resin is diluted. When the MFC amount is fixed at 10 g / m 2 and the total resin amount is two cases of 8 g / m 2 and 6 g / m 2 , the resin concentration for performing all layer resin treatment and surface layer resin treatment is 3% to 20%. The effect of resin concentration when changed to% is shown.

Figure JPOXMLDOC01-appb-T000006
Figure JPOXMLDOC01-appb-T000006

　この例でみるように、全層樹脂処理の樹脂濃度が高くしかも表層樹脂処理の樹脂量が多いと、通気性は阻害される傾向になる。 As seen in this example, when the resin concentration in the all-layer resin treatment is high and the amount of the resin in the surface resin treatment is large, the air permeability tends to be inhibited.

　一般的にいえば全層樹脂処理の樹脂濃度は少なくとも１０％以下、好ましくは８％以下が望ましい。表層樹脂処理の樹脂濃度は１０％以上でもよいが、樹脂量は、全層樹脂処理で用いる樹脂量の方が、表層樹脂処理で用いる樹脂量よりも多くすることが好ましい。このようにすることで、通気性も耐水性もバランスのとれた性能になる。 Generally speaking, the resin concentration in the all-layer resin treatment is at least 10% or less, preferably 8% or less. The resin concentration in the surface layer resin treatment may be 10% or more, but it is preferable that the resin amount used in the all layer resin treatment is larger than the resin amount used in the surface layer resin treatment. By doing in this way, it becomes the performance with which air permeability and water resistance were balanced.

　（固形粉体成分の添加複合）
　本発明による耐水性高通気性複合シートには、臭気、着色成分等の吸収・吸着剤、発熱剤、吸湿剤、乾燥剤、導電材料、あるいはシート状複合体のピンホールやクレーズ等の欠陥の補修、充填等の目的で、固形状粒子や粉体などの固形粉体成分を添加、複合させてもよい。 (Additional combination of solid powder components)
The water-resistant and highly breathable composite sheet according to the present invention has an odor, an absorbing / adsorbing agent such as a coloring component, a heat generating agent, a hygroscopic agent, a desiccant, a conductive material, or defects such as pinholes and crazes in a sheet-like composite. For the purpose of repair and filling, solid powder components such as solid particles and powder may be added and combined.

　これらの添加剤としては、無機物である場合と有機物である場合の両方のケースがある。 These additives include both cases of inorganic substances and organic substances.

　例えば無機物であれば炭酸カルシウム、カオリン、ゼオライト、活性炭、シリカゲル、鉄粉、銅粉等であり、有機物であれば木粉、セルローズ粉末、小麦粉、でんぷん、ＣＭＣ、ポリエチレン綿状ファイバー（商品名：ケミベスト（登録商標）（三井化学社製））、ＳＡＰあるいはＺｎ、Ｃｕ、銀イオン等の金属イオンを包接したシクロデキストリン、金属イオンを担持させたゼオライト等である。シクロデキストリンなどの包接体や金属イオンを担持させたゼオライトは、強い抗菌性をもち、これらは消臭効果と抗菌効果という二つの機能を併せもつようになる。 For example, calcium carbonate, kaolin, zeolite, activated carbon, silica gel, iron powder, copper powder, etc. are used for inorganic substances, and wood powder, cellulose powder, wheat flour, starch, CMC, polyethylene cotton fiber (trade name: Chemibest) for organic substances. (Registered trademark) (manufactured by Mitsui Chemicals, Inc.), cyclodextrin in which metal ions such as SAP or Zn, Cu, and silver ions are included, zeolite that supports metal ions, and the like. An inclusion body such as cyclodextrin and zeolite loaded with metal ions have strong antibacterial properties, and they have two functions of deodorizing effect and antibacterial effect.

　これらの固形粉体成分の添加複合方法としては、次のような２つの方法がある。 There are the following two methods for adding and combining these solid powder components.

　（１）基材となる微細化セルロース繊維・不織布複合体の製造時にあらかじめ固形粉体成分を添加、複合しておいて、樹脂処理により、より安定化する方法
　（２）微細化セルロース繊維・不織布複合体の樹脂処理時に樹脂に固形粉体成分を混合分散しておいて、樹脂処理と同時に添加、複合する方法 (1) A method in which a solid powder component is added and combined in advance during the production of a refined cellulose fiber / nonwoven fabric composite to be a base material, and is further stabilized by resin treatment. (2) Refined cellulose fiber / nonwoven fabric. A method in which a solid powder component is mixed and dispersed in a resin at the time of resin treatment of the composite, and added and compounded simultaneously with the resin treatment.

　表面に出ると感触を損なったり着色したりする材料や、耐水性に影響を与える強親水性の材料、例えばゼオライト、炭酸カルシウム、シリカゲル、活性炭、Ｆｅ粉、Ｃｕ粉等は、基材となる微細化セルロース繊維・不織布複合体にあらかじめ添加、複合させて、できるだけシートの内部特に下層部分に閉じ込めておくことが望ましい。 Materials that impair or color when exposed to the surface, or strongly hydrophilic materials that affect water resistance, such as zeolite, calcium carbonate, silica gel, activated carbon, Fe powder, Cu powder, etc. It is desirable to add and combine in advance with the cellulose oxide / nonwoven fabric composite so that it is confined as much as possible inside the sheet, particularly in the lower layer portion.

　カオリン、セルローズ粉末、木粉等の微粉体の場合は、樹脂処理の際、例えば前述のＳＢＲラテックスで処理するような場合には、希釈状態にしたラテックス樹脂液に分散させて全層樹脂処理を行うことによって、比較的容易に複合体全体に担持させることができる。 In the case of fine powders such as kaolin, cellulose powder, and wood powder, for example, in the case of treating with the above-mentioned SBR latex during the resin treatment, the whole layer resin treatment is performed by dispersing in a diluted latex resin solution. By carrying out, it can carry | support to the whole composite body comparatively easily.

　（耐水性高通気性複合シートの製造システム）
　本発明による耐水性高通気性複合シートの製造システムは、以下に述べるような基本的プロセスから構成されている。 (Production system for water-resistant and highly breathable composite sheet)
The manufacturing system of a water-resistant and highly breathable composite sheet according to the present invention comprises the basic processes as described below.

　１）出発原料である微細化セルロース繊維・不織布複合体の調製、供給
　本発明による耐水性高通気性複合シートの出発原料は、図１に記載の微細化セルロース繊維・不織布複合体（ＭＦＣ・不織布複合体）である。このシート状複合体があらかじめ準備されている場合と、シート状複合体を調製するプロセスをも製造システムの中に包含する場合との２つのケースに大別される。 1) Preparation and supply of fine cellulose fiber / nonwoven fabric composite as a starting material The starting raw material of the water-resistant and highly breathable composite sheet according to the present invention is a fine cellulose fiber / nonwoven fabric composite (MFC / nonwoven fabric) shown in FIG. Complex). The case is roughly divided into two cases: a case where the sheet-like composite is prepared in advance, and a case where a process for preparing the sheet-like composite is also included in the manufacturing system.

　製造システム例としては、図１６～図１９に示すように、システムフロー１～システムフロー４までの４例は、あらかじめ調製された微細化セルロース繊維・不織布複合体を用いた例である。また、図２０～図２１に示すように、システムフロー５及びシステムフロー６は、微細化セルロース繊維・不織布複合体の調製プロセスもそのシステムの中に包含された例である。なお、図１６～２１の各システムフローについては、後述する。 As examples of manufacturing systems, as shown in FIGS. 16 to 19, four examples from system flow 1 to system flow 4 are examples using a pre-prepared fine cellulose fiber / nonwoven fabric composite. Further, as shown in FIGS. 20 to 21, the system flow 5 and the system flow 6 are examples in which the preparation process of the fine cellulose fiber / nonwoven fabric composite is also included in the system. Each system flow in FIGS. 16 to 21 will be described later.

　２）微細化セルロース繊維・不織布複合体の予備処理
　樹脂処理工程に供給されるＭＦＣ・不織布複合体は、乾燥状態では空気層を含んでいるので、全層樹脂処理のように内部まで樹脂を浸透させるような場合には、その空気層が邪魔をして樹脂の不均一分布を起こしやすい。そのような場合は、有機溶媒系の樹脂液を用いる場合にはその有機溶媒で、水系のエマルジョンを用いる場合には水媒体で、あらかじめ複合体内の空気を置換しておくと、より均一なコーティングが可能になる。このような予備処理を「プリコート処理」あるいは「サチュレーション処理」と称する。ただし比較的濃厚な樹脂液で表面加工する表層樹脂処理の場合には、必ずしもこのような予備処理は必要としない。 2) Pretreatment of refined cellulose fiber / nonwoven fabric composite The MFC / nonwoven fabric composite supplied to the resin treatment process contains an air layer in the dry state, so that the resin penetrates into the interior as in all-layer resin treatment. In such a case, the air layer easily disturbs the resin to cause a non-uniform distribution. In such a case, if the organic solvent resin solution is used, the organic solvent is used, and if an aqueous emulsion is used, the aqueous medium is replaced with an aqueous medium. Is possible. Such a preliminary process is referred to as a “precoat process” or a “saturation process”. However, such a preliminary treatment is not necessarily required in the case of the surface resin treatment in which the surface is processed with a relatively thick resin liquid.

　３）樹脂処理加工の方法
　樹脂処理の方法は、樹脂の性状や濃度、粘度等の流動性によって様々な方法が採用可能である。例えば含浸方式、スプレー方式、塗工方式（グラビア、オフセットグラビア、マイクログラビア、フレキソ、リバースロール、ブレード、ダイ等）である。 3) Resin treatment method Various resin treatment methods can be employed depending on the properties, concentration, viscosity and other fluidity of the resin. For example, impregnation method, spray method, coating method (gravure, offset gravure, micro gravure, flexo, reverse roll, blade, die, etc.).

　これらの処理方式は同一の方式で済ますこともできるが、全層樹脂処理と表層樹脂処理とで使い分けることも行なわれる。例えば、全層樹脂処理に相当するプロセスには含浸方式やスプレー方式を採用し、表層樹脂処理には塗工方式を用いるシステムである。あるいは同じ塗工方式であっても、第一段の塗工では、薄い濃度の樹脂液をマイクログラビア方式で塗工し、第二段の塗工では、濃い濃度の樹脂液をフレキソ方式で塗工するように、求める仕様に合わせて最適なプロセスを選択し組み合わせることが望ましい。 These treatment methods can be the same method, but they can be used separately for all-layer resin treatment and surface resin treatment. For example, a system that employs an impregnation method or a spray method for a process corresponding to a full-layer resin treatment, and a coating method for a surface resin treatment. Alternatively, even in the same coating method, in the first stage coating, a thin concentration resin solution is applied by a micro gravure method, and in the second step coating, a high concentration resin solution is applied by a flexo method. It is desirable to select and combine optimal processes according to the required specifications.

　４）脱溶媒、乾燥の方法
　処理した樹脂の乾燥ロール表面への付着性、乾燥収縮の発生度、表面平滑度の必要性、ソフトな仕上がりの必要性等で多様な選択が考えられるが、本発明による耐水性高通気性複合シートは、高通気性であるので、フィルム等と違って比較的空気の透過性がよいので、ネットコンベア上に把持して樹脂処理面から熱風を吹き付けるような方式が望ましい。また、表面均一及び平滑度を向上させるためのアイロニング効果を出すため、熱プレス機能を備えた熱ロールやヤンキードラム、あるいはカレンダーロール等を通過させて巻取りを行うことが望ましい。 4) Solvent removal and drying methods Various choices can be considered depending on the adhesion of the treated resin to the surface of the drying roll, the degree of drying shrinkage, the need for surface smoothness, the need for a soft finish, etc. Since the water-resistant and highly breathable composite sheet according to the invention is highly breathable, it is relatively air permeable, unlike films, etc., so it is gripped on a net conveyor and blows hot air from the resin-treated surface. Is desirable. Further, in order to obtain an ironing effect for improving the surface uniformity and smoothness, it is desirable to wind by passing a hot roll having a hot press function, a Yankee drum, a calendar roll, or the like.

　５）後処理、後加工
　樹脂処理に際して、樹脂成分に加えて架橋剤等を添加して表面強度や耐水強度を上げるため、乾燥巻上げ後のロールに対して、いわゆるキュア加工や内部テンションの緩和のためのアニール処理を行うことも行なわれるが、これらの加工を完結させるためには大きなスペースと熱エネルギーが必要になる。従って、可能であれば、キュア処理やアニール処理を行うことなく、巻取りと同時に製品化できる条件を採用することが望ましい。 5) Post-treatment and post-processing In the resin treatment, in addition to the resin component, a crosslinking agent or the like is added to increase the surface strength and water-resistant strength. An annealing process is also performed, but a large space and heat energy are required to complete these processes. Therefore, if possible, it is desirable to employ conditions that allow commercialization at the same time as winding without performing a curing process or an annealing process.

　次に、上記の１）～５）で言及した各処理を組み合わせたフローシステムの例について、説明する。図１６～２１は、本発明による耐水性高通気性複合シートの製造方法を含むシステムフローの例を示す概略図である。 Next, an example of a flow system that combines the processes mentioned in 1) to 5) above will be described. 16 to 21 are schematic views showing an example of a system flow including a method for producing a water-resistant and highly breathable composite sheet according to the present invention.

　図１６は、システムフロー１：微細化セルロース繊維・不織布複合体の有機溶媒系溶解樹脂による含浸処理を行う例を示すフローチャートである。目付１２ｇ／ｍ２のＭＦＣと、目付１３ｇ／ｍ２のスパンボンド・メルトブローン複合体（ＳＭＳ）とからなる微細化セルロース繊維・不織布複合体（ＭＦＣ・不織布複合体）を、ポリウレタン樹脂をトルエン中に有する２０％のポリウレタン／トルエン樹脂含有液に含浸して樹脂処理を行う。その後、プレス及び脱溶液を行い、その後乾燥して複合体に含まれる溶媒を除去し、このように処理された複合体を巻き取る。その後、任意な方法で樹脂を硬化して、樹脂量として目付６ｇ／ｍ２を含む耐水性高通気性複合シートを得る。 FIG. 16 is a flowchart showing an example in which the system flow 1: impregnation treatment of the refined cellulose fiber / nonwoven fabric composite with an organic solvent-based dissolved resin is performed. And MFC basis weight 12 g / m 2, spunbond meltblown composites having a basis weight of 13g / m 2 (SMS) consisting fine cellulose fibers, nonwoven complex (MFC-nonwoven composite), a polyurethane resin in toluene The resin treatment is performed by impregnating the liquid containing 20% polyurethane / toluene resin. Thereafter, pressing and desolution are performed, and then drying is performed to remove the solvent contained in the composite, and the composite thus treated is wound up. Thereafter, the resin is cured by an arbitrary method to obtain a water-resistant and highly breathable composite sheet having a basis weight of 6 g / m 2 .

　図１７は、システムフロー２：微細化セルロース繊維・不織布複合体のＳＢＲ水系エマルジョンによる２回処理を行う例を示すフローチャートである。目付８ｇ／ｍ２のＭＦＣと、目付１５ｇ／ｍ２のスパンボンド・メルトブローン複合体（ＳＭＳ）とからなる微細化セルロース繊維・不織布複合体（ＭＦＣ・不織布複合体）を、ＳＢＲ樹脂ラテックスを有する８％の水希釈エマルジョンを用いたマイクログラビアロールコートによる第１回目のコーティングを行う。その後、得た複合体をネットコンベア上で熱風乾燥（約９０℃）する。さらに、このように乾燥した複合体の表面に、樹脂としてＳＢＲラテックスを有する１５％の水希釈エマルジョンを用いたグラビアロールコートによる第２回目のコーティングを行う。このようにして得た複合体を、上記と同様にネットコンベア上で熱風乾燥（約９０℃）する。その後、表面温度１３０℃に加熱されたロールを用いてプレス処理を行い、樹脂量として目付６ｇ／ｍ２を含む耐水性高通気性複合シートを得る。 FIG. 17 is a flowchart showing an example in which system flow 2: twice-treatment with an SBR aqueous emulsion of a refined cellulose fiber / nonwoven fabric composite is performed. And MFC basis weight 8 g / m 2, spunbond meltblown composites having a basis weight of 15g / m 2 (SMS) consisting fine cellulose fibers, nonwoven complex (MFC-nonwoven composite), 8 with SBR resin latex The first coating is performed by microgravure roll coating using a% water diluted emulsion. Thereafter, the obtained composite is dried with hot air (about 90 ° C.) on a net conveyor. Further, the surface of the composite thus dried is subjected to a second coating by gravure roll coating using a 15% water diluted emulsion having SBR latex as a resin. The composite thus obtained is dried with hot air (about 90 ° C.) on a net conveyor in the same manner as described above. Then, a press treatment is performed using a roll heated to a surface temperature of 130 ° C. to obtain a water-resistant and highly breathable composite sheet containing a basis weight of 6 g / m 2 .

　図１８は、システムフロー３：微細化セルロース繊維・不織布複合体のゼオライトを共分散させたＳＢＲ水系エマルジョンによる処理と単独ＳＢＲ水系エマルジョンによる処理とを組合せた例を示すフローチャートである。目付６ｇ／ｍ２のＭＦＣと、目付１４ｇ／ｍ２のスパンボンド・メルトブローン複合体（ＳＭＳ）とからなる微細化セルロース繊維・不織布複合体（ＭＦＣ・不織布複合体）を、樹脂としてＳＢＲラテックスを有する８％の水希釈エマルジョンを用いたマイクログラビアロールコートによる第１回目のコーティングを行う。その後、得た複合体をネットコンベア上で熱風乾燥（約９０℃）する。次に、このように乾燥した複合体の裏面に当たるＳＭＳ面に、樹脂としてＳＢＲラテックスを有し、且つ固形粉体成分としてゼオライトを有するＳＢＲ６％及びゼオライト５％を含有する共分散混合液を用いたグラビアロールコートによる第２回目のコーティングを行う。このようにして得た複合体を、上記と同様にネットコンベア上で熱風乾燥（約９０℃）する。その後、さらに、第１回目にコーティングを施したＭＦＣ面に、樹脂としてＳＢＲラテックスを有する１２％の水希釈エマルジョンを用いたマイクログラビアロールコートによる第３回目のコーティングを行う。このようにして得た複合体を、上記と同様にネットコンベア上で熱風乾燥（約９０℃）する。このようにして、樹脂量が目付８ｇ／ｍ２、ゼオライト量が目付２ｇ／ｍ２を含む脱臭機能を有する耐水性高通気性複合シートを得る。 FIG. 18 is a flowchart showing an example of a combination of system flow 3: treatment with an SBR aqueous emulsion in which zeolite of a fine cellulose fiber / nonwoven fabric complex is co-dispersed and treatment with a single SBR aqueous emulsion. And MFC basis weight 6 g / m 2, spunbond meltblown composites having a basis weight of 14g / m 2 (SMS) consisting fine cellulose fibers, nonwoven complex (MFC-nonwoven composite), having SBR latex as a resin The first coating by microgravure roll coating using 8% water diluted emulsion is performed. Thereafter, the obtained composite is dried with hot air (about 90 ° C.) on a net conveyor. Next, a co-dispersed liquid mixture containing 6% SBR and 5% zeolite having SBR latex as a resin and zeolite as a solid powder component was used on the SMS surface corresponding to the back surface of the composite thus dried. The second coating by gravure roll coating is performed. The composite thus obtained is dried with hot air (about 90 ° C.) on a net conveyor in the same manner as described above. Thereafter, the MFC surface coated in the first coating is further subjected to the third coating by microgravure roll coating using 12% water-diluted emulsion having SBR latex as a resin. The composite thus obtained is dried with hot air (about 90 ° C.) on a net conveyor in the same manner as described above. In this way, a water-resistant and highly breathable composite sheet having a deodorizing function including a resin amount of 8 g / m 2 and a zeolite amount of 2 g / m 2 is obtained.

　図１９は、システムフロー４：ゼオライトを担持した微細化セルロース繊維・不織布複合体にＳＢＲ水系エマルジョンによる処理を２回行う例を示すフローチャートである。目付８ｇ／ｍ２のＭＦＣと、固形粉体成分としてのゼオライト（目付４ｇ／ｍ２）と、目付１５ｇ／ｍ２のスパンボンド・メルトブローン複合体（ＳＭＳ）とからなるゼオライトを担持させた微細化セルロース繊維・不織布複合体（ＭＦＣ・不織布複合体）を、樹脂としてＳＢＲラテックスを有する８％の水希釈エマルジョンを用いたフレキソロールコートによる第１回目のコーティングを行う。その後、得た複合体をサクション（吸引機構）付きネットコンベア上で熱風乾燥（約９０℃）する。次に、このように乾燥した複合体を、樹脂としてＳＢＲラテックスを有し、且つ撥水材として撥水材（商品名：ペトロックスＰ３００（明成化学工業社製））を有する、パラフィン系撥水剤１０％及びＳＢＲ１０％を含有する混合液を用いたフレキソロールコートによる第２回目のコーティングを行う。このようにして得た複合体を、上記と同様にサクション付きネットコンベア上で予備的に乾燥（７０～８０℃）する。その後、さらに、ヤンキー式ドライヤー（表面温度１３０℃）を用いて仕上げの乾燥を行う。このようにして、樹脂量が目付６ｇ／ｍ２、撥水材量が目付２ｇ／ｍ２の撥水性を有する耐水性高通気性複合シートを得る。 FIG. 19 is a flowchart showing an example in which the system flow 4: the refined cellulose fiber / nonwoven fabric composite supporting zeolite is treated twice with the SBR aqueous emulsion. Refinement by supporting zeolite consisting of MFC with a basis weight of 8 g / m 2 , zeolite as a solid powder component (a basis weight of 4 g / m 2 ), and a spunbond / meltblown composite (SMS) with a basis weight of 15 g / m 2 The cellulose fiber / nonwoven fabric composite (MFC / nonwoven fabric composite) is first coated by flexo roll coating using 8% water-diluted emulsion having SBR latex as a resin. Thereafter, the obtained composite is dried with hot air (about 90 ° C.) on a net conveyor with suction (suction mechanism). Next, the thus dried composite has a SBR latex as a resin and a water repellent material (trade name: Petrox P300 (manufactured by Meisei Chemical Co., Ltd.)) as a water repellent material. A second coating is performed by flexo roll coating using a mixed solution containing 10% and 10% SBR. The composite thus obtained is preliminarily dried (70 to 80 ° C.) on a net conveyor with suction in the same manner as described above. Thereafter, finish drying is further performed using a Yankee dryer (surface temperature 130 ° C.). In this way, a water-resistant and highly air-permeable composite sheet having a water repellency with a resin amount of 6 g / m 2 and a water repellent material amount of 2 g / m 2 is obtained.

　図２０は、システムフロー５：微細化セルロース繊維・不織布複合体の製造とＳＢＲラテックス処理とを連続して行う例を示すフローチャートである。まず、微細化セルロース繊維・不織布複合体を製造・調製する。つまり、微細化セルロース繊維・不織布複合体の不織布の原料であるＰＥ／ＰＥＴ複合繊維（１５ｄ×４５ｍｍ）から、デファイブレータ及びカード機を用いて易熱溶融性カードウェブ（目付２０ｇ／ｍ２）を製造する。次に、得たウェブに、サチュレーター中で水を添加して、ウェブ全体を水によって飽和させる。その後、ウェットコーティングステーションにおいて、ＭＦＣと水とからなるＭＦＣ１％水分散液を用いてウェブにＭＦＣをコーティングする。その後、サクション（吸引機構）により真空脱水を行ってフリーな水を除去した後、これを、表面温度が１３０～１４０℃のヤンキードラムドライヤーを用いて、ウェブとＭＦＣとを熱融着する。このようにして、微細化セルロース繊維・不織布複合体が得られる。次に、この微細化セルロース繊維・不織布複合体のＭＦＣ面に、樹脂としてＳＢＲラテックスを有する２０％の水希釈エマルジョンを用いて、フレキソロールコートによるコーティングを行う。その後、得た複合体をネットコンベア上で熱風乾燥（約９０℃）する。このようにして、樹脂量として目付６ｇ／ｍ２を含む耐水性高通気性複合シートを得る。 FIG. 20 is a flowchart showing an example in which the system flow 5: the production of the refined cellulose fiber / nonwoven fabric composite and the SBR latex treatment are continuously performed. First, a refined cellulose fiber / nonwoven fabric composite is produced and prepared. That is, from PE / PET composite fiber (15d × 45mm), which is a raw material for the nonwoven fabric of fine cellulose fiber / nonwoven fabric composite, an easily heat-meltable card web (20 g / m 2 per unit area) is obtained using a defibrator and a card machine. To manufacture. Next, water is added to the resulting web in a saturator to saturate the entire web with water. Thereafter, the web is coated with MFC at a wet coating station using an MFC 1% aqueous dispersion of MFC and water. Thereafter, vacuum dehydration is performed by suction (suction mechanism) to remove free water, and then the web and MFC are heat-sealed using a Yankee drum dryer having a surface temperature of 130 to 140 ° C. In this way, a refined cellulose fiber / nonwoven fabric composite is obtained. Next, a 20% water-diluted emulsion having SBR latex as a resin is coated on the MFC surface of the fine cellulose fiber / nonwoven fabric composite by flexo roll coating. Thereafter, the obtained composite is dried with hot air (about 90 ° C.) on a net conveyor. In this way, a water-resistant and highly breathable composite sheet containing a basis weight of 6 g / m 2 is obtained.

　図２１は、システムフロー６：微細化セルロース繊維・不織布複合体の製造とアクリル酸エマルジョン及び撥水材による処理とを連続して行う例を示すフローチャートである。まず、微細化セルロース繊維・不織布複合体を製造・調製する。つまり、目付１５ｇ／ｍ２のスパンボンド・メルトブローン（ＳＭＳ不織布）に、サチュレーター中で、活性剤としてポリエーテル系ノニオン活性剤２００ＰＰＭを含有する水を添加して、ＳＭＳ不織布を飽和させる。その後、ウェットコーティングステーションにおいて、ＭＦＣとゼオライトと水とからなるＭＦＣ０．８％、ゼオライト０．５％を含有する混合スラリーを用いてＳＭＳ不織布にコーティングを行う。その後、サクション（吸引機構）により真空脱水を行う。次に、スプレーステーションにおいて、架橋剤として炭酸ジルコニウムアンモニウム系架橋剤（商品名：ベイコート２０（日本軽金属社製））を含有するアクリル酸エマルジョン（２０％水分散液）を用いて、上記の不織布にスプレーコーティングを行う。得た不織布を、ネットコンベア上で熱風乾燥（約９０℃）して、複合体を得る。得た複合体に、さらに、パラフィン系撥水材（商品名：ペトロックスＰ３００（明成化学工業社製））を有する水分散液（１５％）を用いて、マイクログラビアロールコートによる撥水材処理を施す。その後、処理された複合体を、ネットコンベア上で熱風乾燥（約９０℃）して、樹脂量が目付６ｇ／ｍ２、撥水材量が目付３ｇ／ｍ２を含む耐水性高通気性複合シートを得る。 FIG. 21 is a flowchart showing an example in which the system flow 6: production of a refined cellulose fiber / nonwoven fabric composite and treatment with an acrylic acid emulsion and a water repellent material are continuously performed. First, a refined cellulose fiber / nonwoven fabric composite is produced and prepared. That is, in a saturator, water containing a polyether nonionic active agent 200PPM as an activator is added to a spunbond melt blown (SMS nonwoven fabric) having a basis weight of 15 g / m 2 to saturate the SMS nonwoven fabric. Thereafter, in a wet coating station, the SMS nonwoven fabric is coated with a mixed slurry containing MFC 0.8% and zeolite 0.5% composed of MFC, zeolite and water. Thereafter, vacuum dehydration is performed by suction (suction mechanism). Next, in a spray station, an acrylic acid emulsion (20% aqueous dispersion) containing an ammonium zirconium carbonate-based crosslinking agent (trade name: Baycoat 20 (manufactured by Nippon Light Metal Co., Ltd.)) is used as the crosslinking agent. Perform spray coating. The obtained nonwoven fabric is dried with hot air (about 90 ° C.) on a net conveyor to obtain a composite. The obtained composite is further subjected to a water repellent treatment by microgravure roll coating using an aqueous dispersion (15%) having a paraffinic water repellent (trade name: Petrox P300 (manufactured by Meisei Chemical Co., Ltd.)). Apply. Thereafter, the treated composite is dried with hot air (about 90 ° C.) on a net conveyor, and the water-resistant and highly breathable composite containing a resin amount of 6 g / m 2 and a water repellent amount of 3 g / m 2. Get a sheet.

　以下、本発明について、具体例を挙げて、説明する。 Hereinafter, the present invention will be described with specific examples.

　例１：微細化セルロース繊維と不織布とを用いた微細化セルロース繊維・不織布複合体を製造する例
　本例は、本発明による耐水性高通気性複合シートの製造に用いる、微細化セルロース繊維と不織布とからなる微細化セルロース繊維・不織布複合体（ＭＦＣ・不織布複合体）の製造の例を示すものである。 Example 1: Example of producing a refined cellulose fiber / nonwoven fabric composite using a refined cellulose fiber and a nonwoven fabric This example shows a refined cellulose fiber and a nonwoven fabric used for producing a water-resistant and highly breathable composite sheet according to the present invention. The example of manufacture of the refined | miniaturized cellulose fiber and nonwoven fabric composite (MFC / nonwoven fabric composite) which consists of these is shown.

　［微細化セルロース繊維の調製］
　広葉樹製晒クラフトパルプ（商品名：ピースリバーＬＢＫＰ（大昭和・丸紅インターナショナル社製））を、パルパーに導入し、２０分間離解して、５重量％のスラリーを調製した。これを、循環タンクに移送した後、３．５重量％のスラリーに調製した。この３．５重量％のパルプスラリーを、下記の条件により、ダブル・ディスク・リファイナー（以下、ＤＤＲと称する。）を用いて、叩解して、微細化セルロース繊維を調製した。なお、叩解は、メタルタッチ（固定刃と回転刃の接触）を起こさないように行った。 [Preparation of refined cellulose fiber]
Hardwood bleached kraft pulp (trade name: Peace River LBKP (manufactured by Daishowa Marubeni International)) was introduced into a pulper and disaggregated for 20 minutes to prepare a 5 wt% slurry. This was transferred to a circulation tank and then prepared into a 3.5 wt% slurry. This 3.5 wt% pulp slurry was beaten using a double disc refiner (hereinafter referred to as DDR) under the following conditions to prepare fine cellulose fibers. The beating was performed so as not to cause metal touch (contact between the fixed blade and the rotary blade).

　ＤＤＲ機種：ＡＷ１４（相川鉄工社製）
　ディスクプレート：刃幅２．０ｍｍ、溝幅３．０ｍｍ
　ＤＤＲへのパルプ流量：１ｍ３／分
　ＤＤＲの平均パス回数：１００回
　刃のクリアランス：０．１３～０．２３ｍｍ DDR model: AW14 (manufactured by Aikawa Tekko)
Disc plate: Blade width 2.0mm, groove width 3.0mm
Pulp flow rate to DDR: 1 m 3 / min Average number of passes of DDR: 100 times Blade clearance: 0.13 to 0.23 mm

　調製した微細化セルロース繊維の特性は、以下の通りであった。 The characteristics of the prepared finely divided cellulose fiber were as follows.

　抱水度：２７ｍＬ／ｇ
　平均繊維長：０．１５ｍｍ
　０．５重量％スラリーの粘度：３２０ｍＰａ
　最終濃度：３．０重量％（シール水により希釈されたため） Water retention: 27 mL / g
Average fiber length: 0.15mm
Viscosity of 0.5 wt% slurry: 320 mPa
Final concentration: 3.0% by weight (because it was diluted with sealing water)

　なお、抱水度は、下記の通り、測定した。 The water retention was measured as follows.

　＜抱水度＞
　抱水度は、分散安定性を比較することを目的とするものであり、その測定法としては簡単で安定した方法がよい。従って、本発明において、抱水度とは、遠心処理の沈積ＭＦＣの容量を直接読み通り、これを抱水度として評価することにした。以下、その測定方法を示す。 <Degree of water retention>
The degree of water retention is for the purpose of comparing dispersion stability, and a simple and stable method is preferable as the measurement method. Therefore, in the present invention, the degree of water retention is determined by directly reading the capacity of the sedimentation MFC of the centrifugal treatment and evaluating this as the degree of water retention. The measurement method is shown below.

　対象となる微細化セルロース繊維（０．５ｇ）の水分散液５０ｍＬを遠心分離可能な試験管（内径３０ｍｍ×長さ１００ｍｍ、容積５０ｍＬ）中に計り取り、これを２０００×ｇ（３３００ｒｐｍ）で１０分間遠心分離して沈積量（ｍＬ）を読み取り、次の式に従って抱水量を算出した。 50 mL of the target finely divided cellulose fiber (0.5 g) aqueous dispersion was weighed into a centrifugeable test tube (inner diameter 30 mm × length 100 mm, volume 50 mL), and this was measured at 2000 × g (3300 rpm) at 10 The amount of sedimentation (mL) was read by centrifuging for minutes, and the amount of water retained was calculated according to the following formula.

　抱水量（ｍＬ／ｇ）＝沈積物の容量（ｍＬ）／セルロース繊維量（ｇ） Water content (mL / g) = volume of sediment (mL) / cellulose fiber content (g)

　［微細化セルロース繊維スラリーの調製］
　微細化セルロース繊維の濃度が０．７重量％となるように、上記の通り得た微細化セルロース繊維に、エタノール／水＝６５／３５（重量比率）を添加して、微細化セルロース繊維スラリーを調製した。 [Preparation of refined cellulose fiber slurry]
Ethanol / water = 65/35 (weight ratio) was added to the refined cellulose fiber obtained as described above so that the concentration of the refined cellulose fiber was 0.7% by weight. Prepared.

　［不織布の調製］
　下記の特性を有するポリプロピレン製のＳＭＳ（ＡＶＧＯＬ社製）不織布を用いた。 [Preparation of non-woven fabric]
An SMS non-woven fabric made of polypropylene (manufactured by AVGOL) having the following characteristics was used.

　目付量：１５ｇ／ｍ２
　ＳＭＳの構成：　スパンボンド（１）（５．０ｇ／ｍ２）
　　　　　　　　　メルトブローン（５．０ｇ／ｍ２）
　　　　　　　　　スパンボンド（２）（５．０ｇ／ｍ２）
　耐水性：１５０ｍｍＨ２Ｏ Weight per unit area: 15 g / m 2
Configuration of SMS: Spunbond (1) (5.0 g / m 2 )
Melt blown (5.0 g / m 2 )
Spunbond (2) (5.0 g / m 2 )
Water resistance: 150mmH 2 O

　［不織布への微細化セルロース繊維スラリーのコーティング］
　上記の不織布（ＳＭＳ）を、幅１，５００ｍｍ、４０ｍ／分で走行させ、この走行する不織布に、水を１７ｋｇ／分の割合で供給して、不織布を水で飽和させた。次に、同様に走行する不織布上に、上記の通り得た微細化セルロース繊維スラリー（ＭＦＣ）を、２０～８０ｋｇ／分の割合で供給した。これを、－３０ｋＰａの真空により脱液し、１００℃の温度で乾燥し、巻き取り、下記表７に示す特性を有するサンプル１～５の微細化セルロース繊維・不織布複合体を得た。 [Coating of non-woven cellulose fiber slurry on non-woven fabric]
The nonwoven fabric (SMS) was run at a width of 1,500 mm and 40 m / min, and water was supplied to the running nonwoven fabric at a rate of 17 kg / min to saturate the nonwoven fabric with water. Next, the finely divided cellulose fiber slurry (MFC) obtained as described above was fed at a rate of 20 to 80 kg / min onto the nonwoven fabric running in the same manner. This was drained by a vacuum of −30 kPa, dried at a temperature of 100 ° C., and wound up to obtain a refined cellulose fiber / nonwoven fabric composite of Samples 1 to 5 having the characteristics shown in Table 7 below.

Figure JPOXMLDOC01-appb-T000007
Figure JPOXMLDOC01-appb-T000007

　なお、表７において、「観察」とは、得た各サンプルの表面状態を目視で観察した結果を示し、表面強度は、下記の評価方法に記載の＜各層の結合強度の評価＞に従い、シートの構成成分の状態を評価したものであって、ここでは、１８０°ピリングテストにより行って得た結果を示した。 In Table 7, “Observation” indicates the result of visual observation of the surface state of each obtained sample, and the surface strength is a sheet according to <Evaluation of bonding strength of each layer> described in the following evaluation method. In this example, results obtained by a 180 ° pilling test are shown.

　上記の結果、本発明において、サンプル３の微細化セルロース繊維・不織布複合体を、下記の耐水性高通気性複合シートの製造に用いることとした。 As a result, in the present invention, the refined cellulose fiber / nonwoven fabric composite of Sample 3 was used for the production of the following water-resistant and highly breathable composite sheet.

　例２：本発明による耐水性高通気性複合シートの製造例（プリコート及び樹脂を用いたコーティング）
　例１で得たサンプル３の微細化セルロース繊維・不織布複合体（ＭＦＣ・ＳＭＳ複合体）を用いて、図２５に記載のフローチャートに従って、サンプル６から９の本発明による耐水性高通気性複合シートを製造した。なお、下記表８は、図２５に記載のプリコート及び樹脂エマルジョンの固形分の濃度をまとめたものである。 Example 2: Production example of water-resistant and highly breathable composite sheet according to the present invention (pre-coating and coating using resin)
Using the refined cellulose fiber / nonwoven fabric composite (MFC / SMS composite) of Sample 3 obtained in Example 1, the water-resistant and highly air-permeable composite sheet of Samples 6 to 9 according to the present invention according to the flowchart shown in FIG. Manufactured. Table 8 below summarizes the solid content concentrations of the precoat and resin emulsion described in FIG.

　本例において、コーティングに用いたワイヤの径、並びに乾燥及びキュアの条件は、下記の通りである。 In this example, the diameter of the wire used for coating and the drying and curing conditions are as follows.

　ワイヤの径：０．１５ｍｍφ
　乾燥の条件：５０℃１０分間
　キュアの条件：６０℃６時間 Wire diameter: 0.15mmφ
Drying conditions: 50 ° C for 10 minutes Cure conditions: 60 ° C for 6 hours

Figure JPOXMLDOC01-appb-T000008
Figure JPOXMLDOC01-appb-T000008

　なお、表８において、プリコートの条件は、エタノール／水＝５０／５０の混合溶媒１５ｍＬを用いて、微細化セルロース繊維・不織布複合体をこの混合溶媒で飽和するように行った。また、表８において、コーティングに用いた樹脂エマルジョンは、樹脂としてのＳＢＲラテックス（Ａ＆Ｌ社製、カタログ番号：ＰＡ０３３９）を、イオン交換水に分散して得たものである。なお、プリコートは、水１００％の溶媒を用いて行ってもよいが、ハンドコートによりプリコートを行う場合、経時的に表面のＭＦＣが水和膨潤して表面にフクレが生じるので、ハンドコート時の時間の影響等を少なくするため、ＭＦＣが膨潤しにくいエタノール／水を採用した。エタノール／水比は、５０／５０以上であれば、用いる材料の特性及びコーティングの条件等の状態に応じて適宜選択すればよい。 In Table 8, the precoat conditions were such that ethanol / water = 50/50 mixed solvent 15 mL was used to saturate the refined cellulose fiber / nonwoven fabric composite with this mixed solvent. In Table 8, the resin emulsion used for coating was obtained by dispersing SBR latex as a resin (manufactured by A & L, catalog number: PA0339) in ion-exchanged water. The pre-coating may be performed using a solvent of 100% water. However, when pre-coating is performed by hand coating, MFC on the surface hydrates and swells with time, and bulges are generated on the surface. In order to reduce the influence of time, etc., ethanol / water that does not easily swell the MFC was adopted. As long as the ethanol / water ratio is 50/50 or more, the ethanol / water ratio may be appropriately selected according to the characteristics of the material used and the conditions such as coating conditions.

　このようにして得たサンプル６～９の本発明による耐水性高通気性複合シート（それぞれ４枚ずつ）について、下記の評価方法に従って、評価した。その結果を表９に示す。 The water-resistant and highly breathable composite sheets according to the present invention of Samples 6 to 9 (four sheets each) thus obtained were evaluated according to the following evaluation method. The results are shown in Table 9.

Figure JPOXMLDOC01-appb-T000009
Figure JPOXMLDOC01-appb-T000009

　なお、表９において、「コーティング状態の目視観察」は、得た樹脂をコーティングした耐水性高通気性複合シートの樹脂をコーティングした面の表面状態を目視で観察して評価したものである。また、「透気度」は、下記の評価方法に記載の＜透気度＞に従って得た透気度をいう。また、「表面強度」は、下記の評価方法に記載の＜塗工面の結合強度の評価＞に従い、シートの構成成分の状態を評価したものであって、ここでは、９０°ピリングテストにより行って得た結果を示した。ここで、＊１印に示す「不織布破壊」とは、ＭＦＣ層と不織布層とが樹脂によって安定に結合されていることを意味する。また、「５スポットテスト」は、下記の評価方法に記載の＜表面からの拡散性及び浸透性の評価＞に従い、ＭＦＣ面に生理食塩水をスポットして浸透を開始した時間を示したものである。また、「リングテスト」は、下記の評価方法に記載の＜フクレの発生と水の浸透状態の評価＞に従って、テスト開始２時間後、６時間後及び２４時間後の染色した生理食塩水の漏れの発生の有無を評価した。 In Table 9, “visual observation of coating state” is an evaluation by visually observing and evaluating the surface state of the surface of the water-resistant and highly breathable composite sheet coated with the obtained resin. “Air permeability” refers to the air permeability obtained according to <Air permeability> described in the following evaluation method. The “surface strength” is an evaluation of the state of the constituent components of the sheet according to <Evaluation of Bond Strength of Coated Surface> described in the following evaluation method. Here, the surface strength is measured by a 90 ° pilling test. The results obtained are shown. Here, “nonwoven fabric destruction” indicated by * 1 means that the MFC layer and the nonwoven fabric layer are stably bonded by a resin. The “5-spot test” indicates the time when the physiological saline was spotted on the MFC surface and infiltrated according to <Evaluation of diffusibility and permeability from the surface> described in the following evaluation method. is there. In addition, the “ring test” refers to leakage of stained physiological saline 2 hours, 6 hours and 24 hours after the start of the test according to <Evaluation of occurrence of swelling and water penetration state> described in the following evaluation method. The presence or absence of occurrence was evaluated.

　表９から明らかなように、プレコートを行わなかったサンプル６とプレコートを行ったサンプル７とを比較すると、サンプル７の方が、コーティング状態が均一であり、コートされた樹脂量及び透気度にばらつきが少なかった。また、サンプル７と樹脂量がサンプル７よりも多いサンプル９とを比較すると、低い透気度を維持しつつ、耐水性（５スポットテスト、リングテスト）のレベルが高かった。これらのことから、サンプル９の条件のように、コーティングの条件としては、前処理としてプリコートを行うこと、及び樹脂量として目付４．０ｇ／ｍ２以上とすることとした。 As is clear from Table 9, when sample 6 that was not pre-coated and sample 7 that was pre-coated were compared, sample 7 had a more uniform coating state, and the amount of coated resin and air permeability were similar. There was little variation. Further, comparing sample 7 with sample 9 having a larger amount of resin than sample 7, the level of water resistance (5-spot test, ring test) was high while maintaining low air permeability. From these things, like the conditions of sample 9, as coating conditions, pre-coating was performed as a pretreatment, and the basis weight was 4.0 g / m 2 or more.

　例３：本発明による耐水性高通気性複合シートの製造例（樹脂を用いた多段処理）
　本例では、例１で得たサンプル３の微細化セルロース繊維・不織布複合体を用いて、図２６及び図２７に従って、サンプル１０～１４の本発明による耐水性高通気性複合シートを製造した。なお、プリコートは、エタノール／水＝６０／４０の混合溶媒１５ｍＬを用いて、所定の面（ＭＦＣ面又はＳＭＳ面）をコートすることにより行った。また、樹脂エマルジョンとしては、例２で用いた樹脂としてのＳＢＲラテックス（Ａ＆Ｌ社製、カタログ番号：ＰＡ３８０７）を、イオン交換水に分散して得た、固形分５％、１０％及び１５％の樹脂エマルジョンを用いた。また、樹脂エマルジョンによるコーティングは、上記例２と同様に、ハンドコートを用いたコーティングにより行い、ハンドコートに用いたハンドコート用ワイヤの径は、０．１ｍｍφ、０．１５ｍｍφ及び０．２０ｍｍφであった。これらのワイヤを用いて得た各サンプルのうち、樹脂量が均一であったものを１サンプル当たり３枚選択して、下記の各評価に供した。 Example 3: Production example of water-resistant and highly breathable composite sheet according to the present invention (multistage treatment using resin)
In this example, using the refined cellulose fiber / nonwoven fabric composite of Sample 3 obtained in Example 1, water-resistant and highly breathable composite sheets of Samples 10 to 14 according to the present invention were produced according to FIGS. The pre-coating was performed by coating a predetermined surface (MFC surface or SMS surface) using 15 mL of a mixed solvent of ethanol / water = 60/40. Further, as the resin emulsion, SBR latex (made by A & L, catalog number: PA3807) as a resin used in Example 2 was obtained by dispersing in ion-exchanged water, and the solid content was 5%, 10%, and 15%. A resin emulsion was used. The coating with the resin emulsion was performed by coating using a hand coat as in Example 2 above. The diameters of the hand coat wires used for the hand coat were 0.1 mmφ, 0.15 mmφ and 0.20 mmφ. It was. Of each sample obtained using these wires, three samples having a uniform resin amount were selected per sample and subjected to the following evaluations.

　なお、本例において、樹脂エマルジョンを用いた含浸処理は、所定の固形分の濃度の樹脂エマルジョンをステンレスバットに充分量用意し、ハンドコートサイズのＭＦＣ・ＳＭＳ複合体を１分間浸漬することにより、行った。また、含浸量については、浸漬後、濾紙を介助に入れて、ニップロールを通過させた後、含浸量を規定した。また、本例において、風乾、乾燥及びキュアの条件は、下記の通りである。 In this example, the impregnation treatment using the resin emulsion is performed by preparing a sufficient amount of a resin emulsion having a predetermined solid content in a stainless steel bat and immersing the MFC / SMS composite having a hand coat size for 1 minute. went. Moreover, about the amount of impregnation, after the immersion, the filter paper was put in an assistance, passed through a nip roll, and then the amount of impregnation was defined. In this example, the conditions of air drying, drying and curing are as follows.

　［風乾の条件］
　収縮に起因するシワが発生しないように、ハンドコートして得た各サンプルを枠に固定し、１０分間、室温で風乾した
　［乾燥の条件］
　ハンドコートして得た各サンプルを、上記の通り枠に固定したまま、５０℃で１０分間、熱風乾燥機中で乾燥させた
　［キュアの条件］
　乾燥して得た各サンプルを、６０℃に設定したキュア室内で、６時間静置して処理した [Air-drying conditions]
Each sample obtained by hand-coating was fixed to a frame and air-dried at room temperature for 10 minutes so that wrinkles due to shrinkage did not occur. [Drying conditions]
Each sample obtained by hand coating was dried in a hot air dryer at 50 ° C. for 10 minutes while being fixed to the frame as described above. [Cure conditions]
Each sample obtained by drying was allowed to stand for 6 hours in a curing chamber set at 60 ° C.

　このようにして得たサンプル１０～１４の耐水性高通気性複合シートについて、下記の評価方法に従って、評価した。 The water-resistant and highly breathable composite sheets of Samples 10 to 14 thus obtained were evaluated according to the following evaluation method.

Figure JPOXMLDOC01-appb-T000010
Figure JPOXMLDOC01-appb-T000010

　なお、表１０において、「コーティング状態の目視観察」、「透気度」及び「リングテスト」については、表９で説明した通りである。また、「加圧耐水度テスト」は、下記の評価方法に記載の＜加圧下における漏れの発生状態の評価＞に従って、リークの発生時間及びその状況、リークの拡大及びテストの終了時間をそれぞれ評価した。 In Table 10, “visual observation of coating state”, “air permeability” and “ring test” are as described in Table 9. The "Pressurized water resistance test" evaluates the occurrence time and status of the leak, the expansion of the leak, and the end time of the test according to <Evaluation of the occurrence of leakage under pressure> described in the following evaluation method. did.

　この結果、サンプル１０にもまして、多段処理化によって、サンプル１１～１４のように、同じ樹脂量であっても、均一化が進み、表面層と全体層とを組み合わせた効果により、透気度及び耐水性の安定化が行われていることがわかる。 As a result, even with the same amount of resin as in Samples 11 to 14, by the multi-stage treatment over Sample 10, the homogenization progressed, and the air permeability can be improved by the effect of combining the surface layer and the entire layer. It can also be seen that the water resistance is stabilized.

　例４：本発明による耐水性高通気性複合シートの製造例（樹脂及びゼオライトを用いたコーティング）
　本例では、例１で得たサンプル３の微細化セルロース繊維・不織布複合体を用い、図２８及び図２９に示すフローチャートに従って、サンプル１５～１８の本発明による耐水性高通気性複合シートを製造した。本例で用いた樹脂エマルジョンとしては、上記例２に記載の例２で用いた樹脂としてのＳＢＲラテックス（Ａ＆Ｌ社製、カタログ番号：ＰＡ３８０７）を、イオン交換水に分散して得た、固形分５％及び１０％の樹脂エマルジョンを用いた。また、本例で用いたゼオライト含有樹脂エマルジョンとしては、この固形分５％又は１０％の樹脂エマルジョンに、ゼオライトを最終濃度５重量％となるように添加して得たゼオライト含有樹脂エマルジョンを用いた。なお、ゼオライト含有樹脂エマルジョンは、ゼオライトがエマルジョン中で容易に沈殿してしまうことから、コーティング直前に攪拌して、使用するようにした。 Example 4: Production example of water-resistant and highly breathable composite sheet according to the present invention (coating using resin and zeolite)
In this example, using the refined cellulose fiber / nonwoven fabric composite of Sample 3 obtained in Example 1, water-resistant and highly breathable composite sheets of Samples 15 to 18 according to the present invention were produced according to the flowcharts shown in FIGS. did. As the resin emulsion used in this example, solid content obtained by dispersing SBR latex (manufactured by A & L, catalog number: PA3807) as resin used in Example 2 described in Example 2 above in ion-exchanged water, 5% and 10% resin emulsions were used. In addition, as the zeolite-containing resin emulsion used in this example, a zeolite-containing resin emulsion obtained by adding zeolite to the resin emulsion having a solid content of 5% or 10% to a final concentration of 5% by weight was used. . The zeolite-containing resin emulsion was used by stirring immediately before coating because the zeolite easily precipitates in the emulsion.

　なお、プリコート及びコーティングの条件、並びに風乾、乾燥及びキュアの条件は、例３と同様とした。 The precoat and coating conditions, and the air drying, drying and curing conditions were the same as in Example 3.

　このようにして得たサンプル１５～１８の樹脂及びゼオライトを有する耐水性高通気性複合シートについて、下記の評価方法に従って、評価した。 The water-resistant and highly breathable composite sheet having the resin and zeolite of Samples 15 to 18 thus obtained was evaluated according to the following evaluation method.

Figure JPOXMLDOC01-appb-T000011
Figure JPOXMLDOC01-appb-T000011

　なお、表１１において、「透気度」、「５スポットテスト」及び「リングテスト」については、表９で説明した通りであり、「加圧下リークテスト」は、表１０で説明した通りである。 In Table 11, “air permeability”, “5-spot test” and “ring test” are as described in Table 9, and “leak test under pressure” is as described in Table 10. .

　表１１の結果が示すように、ゼオライトのような強親水性の消臭剤を担持させる場合には、できるだけ水の接する表面から離れた位置に配置するのが望ましい。また、ゼオライトのような微粉体を添加すると、透気度は低下する傾向がある。ちなみに、本例と同じような条件でゼオライト添加量を１．５ｇ／ｍ２とした例では、透気度は、７０～８０秒／１００ｍＬとなり、ほぼ倍程度に向上する結果が得られている。 As shown in the results of Table 11, when a strongly hydrophilic deodorant such as zeolite is supported, it is desirable to dispose it as far as possible from the surface in contact with water. Further, when a fine powder such as zeolite is added, the air permeability tends to decrease. Incidentally, in the example in which the amount of zeolite added was 1.5 g / m 2 under the same conditions as in this example, the air permeability was 70 to 80 seconds / 100 mL, and a result that was almost doubled was obtained. .

　（評価方法）
　＜透気度＞
　ガーレー法による通気度測定（ＪＩＳ－Ｐ８１１７）の方法に基づき測定を行った。即ち、安田精機製作所製のＮｏ．３２３Ｇｕｒｌｅｙ　Ｔｙｐｅ　Ｄｅｎｓｏｍｅｔｅｒを用いて、対象となるシートを６４５ｃｍ２の大きさに切り取り、１００ｍＬの空気を通過する時間（秒）をストップウォッチによって測定した。 (Evaluation methods)
<Air permeability>
The measurement was performed based on the method of air permeability measurement by Gurley method (JIS-P8117). That is, No. manufactured by Yasuda Seiki Seisakusho. Using a 323 Gurley Type Densometer, the target sheet was cut to a size of 645 cm 2 and the time (seconds) passing 100 mL of air was measured with a stopwatch.

　＜表面からの拡散性及び浸透性の評価＞
　図２２に示す装置を用いて５スポット法による無荷重下浸透性の評価に準じて行った。具体的には、透明ガラス板上に、サンプルからの水分の漏出を検知するための検知用ろ紙（商品名：ＧＲＡＤＥ２（Ａｄｖａｎｔｅｃ社製）、目付：１２５ｇ／ｍ２、厚さ：０．２６ｍｍ）を載せ、その上に、評価の対象となるサンプルを載せる。このように配置したサンプルの所定の表面（コーティングを直接施した面及びコーティングを直接施していない面）上に、所定量（０．１、０．２、０．４、０．８及び１．５ｍＬ）の染色した生理食塩水をスポットした。一定時間経過後、検知ろ紙及びサンプルの観察を行い、浸透の開始時間、リークの発生の有無及びその時間並びにテスト終了時間を評価した。 <Evaluation of diffusibility and permeability from the surface>
The evaluation was carried out according to the evaluation of permeability under no load by the 5-spot method using the apparatus shown in FIG. Specifically, a filter paper for detection (trade name: GRADE2 (manufactured by Advantec), basis weight: 125 g / m 2 , thickness: 0.26 mm) for detecting leakage of moisture from the sample on a transparent glass plate. And put the sample to be evaluated on it. Predetermined amounts (0.1, 0.2, 0.4, 0.8, and 1.0.1) on predetermined surfaces (surfaces directly coated and uncoated) of the sample thus arranged. 5 mL) of stained saline was spotted. After a lapse of a certain time, the detection filter paper and the sample were observed, and the infiltration start time, the presence / absence of occurrence of leak and the time thereof, and the test end time were evaluated.

　＜フクレの発生と水の浸透状態の評価＞
　図２３に示す装置を用いてリング式シールテストによる表面の浸透安定性の評価に準じて行った。具体的には、透明ガラス板上に、サンプルからの水分の漏出を検知するための検知用ろ紙（商品名：ＧＲＡＤＥ２（Ａｄｖａｎｔｅｃ社製）、目付：１２５ｇ／ｍ２、厚さ：０．２６ｍｍ）を載せ、その上に、評価の対象となるサンプルを載せる。この上に、リング（ステンレス製、重さ５００ｇ、肉厚５ｍｍ、内面積５０ｃｍ２）を載せる。なお、サンプルとリングとの間には、サンプルとリングとの間からの水の漏洩を防止するように、樹脂製の接着剤（商品名：新ポリグリップＳ（アース製薬社製））を配置する。さらに、リング上に、また、押し板（ステンレス製、重さ３ｋｇ）を載せる。また、上記透明ガラス板の下部に、検知用ろ紙の状態を観察し得る観察用ミラーを置く。 <Evaluation of the occurrence of swelling and water penetration>
Using the apparatus shown in FIG. 23, the evaluation was made in accordance with the evaluation of surface penetration stability by a ring seal test. Specifically, a filter paper for detection (trade name: GRADE2 (manufactured by Advantec), basis weight: 125 g / m 2 , thickness: 0.26 mm) for detecting leakage of moisture from the sample on a transparent glass plate. And put the sample to be evaluated on it. A ring (made of stainless steel, weight 500 g, thickness 5 mm, inner area 50 cm 2 ) is placed thereon. A resin adhesive (trade name: New Polygrip S (Earth Pharmaceutical Co., Ltd.)) is placed between the sample and the ring to prevent leakage of water from between the sample and the ring. To do. Further, a push plate (made of stainless steel, weight 3 kg) is placed on the ring. Further, an observation mirror capable of observing the state of the detection filter paper is placed below the transparent glass plate.

　このように配置した装置において、リングの内壁の内側に５０ｍＬの染色した生理食塩水を導入し、所定時間経過後、検知用ろ紙及びサンプルの観察を行い、リークの発生時間（時間）及び発生場所、テスト終了時間（時間）及びその時の検知用ろ紙の状態並びにテスト終了時におけるサンプルの膨化状態をそれぞれ評価した。なお、上記の所定時間としては、テスト開始の２時間後及び／又は６時間後、並びに一昼夜放置した２４時間後を記録した。 In the apparatus arranged in this way, 50 mL of stained physiological saline is introduced inside the inner wall of the ring, and after a predetermined time has elapsed, the detection filter paper and the sample are observed, and the leak occurrence time (time) and location The test end time (time), the state of the detection filter paper at that time, and the expanded state of the sample at the end of the test were evaluated. The predetermined time was recorded 2 hours and / or 6 hours after the start of the test, and 24 hours after being left overnight.

　＜加圧下における漏れの発生状態の評価＞
　図２４に示す装置を用いて耐水性の評価測定法に準じて行った。具体的には、透明ガラス板上に、サンプルからの水分の漏出を検知するための検知用ろ紙（商品名：ＧＲＡＤＥ２（Ａｄｖａｎｔｅｃ社製）、目付：１２５ｇ／ｍ２、厚さ：０．２６ｍｍ）を載せ、その上に、評価の対象となるサンプルを載せた。この上に、サンプルを保護するための保護シート（商品名：ＴＣＦ（二村化学社製））を載せた上に、さらに所定の青色に着色した生理食塩水を吸収した吸液マット（商品名：ＴＣＦ（二村化学社製）、目付：３０ｇ／ｍ２を２０枚重ねにしたマット）を載せ、押し板を介して重し（２．２５ｋｇ（押し板と合わせた重量として））を載せた。また、上記透明ガラス板の下部に、検知用ろ紙の状態を観察し得る観察用ミラーを置いた。なお、上記の加重２．２５ｋｇは、１０ｇ／ｃｍ２の加重に相当する。 <Evaluation of leakage occurrence under pressure>
It carried out according to the water resistance evaluation measurement method using the apparatus shown in FIG. Specifically, a filter paper for detection (trade name: GRADE2 (manufactured by Advantec), basis weight: 125 g / m 2 , thickness: 0.26 mm) for detecting leakage of moisture from the sample on a transparent glass plate. A sample to be evaluated was placed thereon. On top of this, a protective sheet (trade name: TCF (manufactured by Nimura Chemical Co., Ltd.)) for protecting the sample was placed, and a liquid absorption mat (trade name: TCF (manufactured by Nimura Chemical Co., Ltd., weight per mat: 20 mats each having 30 g / m 2 laid on top of each other) was placed, and weight (2.25 kg (as combined with the push plate)) was placed through the push plate. In addition, an observation mirror capable of observing the state of the detection filter paper was placed below the transparent glass plate. The weight of 2.25 kg corresponds to a weight of 10 g / cm 2 .

　このように設置した装置を用いて、サンプルから生理食塩水が最初にリークする時間（リークの発生）、リークが成長拡大した時間（リークの拡大）、リークの発生から成長拡大に要する時間、検知用ろ紙への生理食塩水のリークが限度以上となった時間、及び検知用ろ紙に吸収された生理食塩水の重量等を評価した。なお、テスト開始から８時間経過後にテストを終了した。 Using the equipment installed in this way, the time when the physiological saline solution first leaks from the sample (leak generation), the time when the leak grows and expands (leak expansion), the time required from the occurrence of the leak to the growth expansion, detection The time when the physiological saline leaked to the filter paper exceeded the limit, the weight of the physiological saline absorbed by the detection filter paper, and the like were evaluated. The test was terminated after 8 hours from the start of the test.

　＜塗工面の結合強度の評価＞
　対象となるシートの塗工面に、接着面が１５ｍｍ×１０ｍｍとなるように、１５ｍｍ幅のニチバン製のセロテープを貼り付け、上から軽くフランネルで押さえた後、１ｋｇ／ｃｍ２の荷重を１０分間かけた。その後、９０°又は１８０°の角度で、対象となるシートからセロテープをはがし、セロテープに付着しているシートの構成成分の状態を、目視的に評価した。なお、１８０°の角度で行ったテストを、１８０°ピリングテスト、９０°の角度で行ったテストを、９０°ピリングテストと称する。 <Evaluation of bond strength of coated surface>
A 15 mm wide Nichiban cellophane tape is applied to the coated surface of the target sheet so that the adhesive surface is 15 mm × 10 mm. After lightly pressing with flannel from above, a load of 1 kg / cm 2 is applied for 10 minutes. It was. Thereafter, the cellophane tape was peeled off from the target sheet at an angle of 90 ° or 180 °, and the state of the components of the sheet adhering to the cellotape was visually evaluated. A test performed at an angle of 180 ° is referred to as a 180 ° pilling test, and a test performed at an angle of 90 ° is referred to as a 90 ° pilling test.

　以上、本発明の好適な実施の形態により本発明を説明した。ここでは特定の具体例を示して本発明を説明したが、特許請求の範囲に定義された本発明の広範な趣旨および範囲から逸脱することなく、これら具体例に様々な修正および変更を加えることができることは明らかである。すなわち、具体例の詳細および添付の図面により本発明が限定されるものと解釈してはならない。
　
　
　
　
　 The present invention has been described above by the preferred embodiments of the present invention. While the invention has been described with reference to specific embodiments, various modifications and changes may be made to the embodiments without departing from the broad spirit and scope of the invention as defined in the claims. Obviously you can. In other words, the present invention should not be construed as being limited by the details of the specific examples and the accompanying drawings.




Claims (29)

　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面から裏面に向かって樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、ＭＦＣ・不織布共存層（Ｃ）及び不織布層（Ｄ）の４層構造からなることを特徴とする耐水性高通気性複合シート。 MFC obtained by applying resin processing to a finely divided cellulose fiber / nonwoven fabric composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer Resin layer (A), resin / MFC coexistence layer (B), MFC / nonwoven fabric coexistence layer (C) and non-woven fabric layer (D) when the surface is the upper surface and the nonwoven fabric surface is the lower back surface A water-resistant highly breathable composite sheet characterized by comprising a four-layer structure. 　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面から裏面に向かって樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、樹脂・ＭＦＣ・不織布共存層（Ｅ）及び不織布層（Ｄ）の４層構造からなることを特徴とする耐水性高通気性複合シート。 MFC obtained by applying resin processing to a finely divided cellulose fiber / nonwoven fabric composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer The resin layer (A), resin / MFC coexistence layer (B), resin / MFC / nonwoven coexistence layer (E) and non-woven fabric layer (E) from the front to the back when the surface is the upper surface and the nonwoven fabric surface is the lower back surface A water-resistant and highly breathable composite sheet characterized by comprising the four-layer structure of D) 　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面から裏面に向かって樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、樹脂・ＭＦＣ・不織布共存層（Ｅ）及び樹脂・不織布共存層（Ｆ）の４層構造からなることを特徴とする耐水性高通気性複合シート。 MFC obtained by applying resin processing to a finely divided cellulose fiber / nonwoven fabric composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer Resin layer (A), resin / MFC coexistence layer (B), resin / MFC / nonwoven fabric coexistence layer (E) and resin / nonwoven fabric when the surface is the upper surface and the nonwoven fabric surface is the lower back surface A water-resistant and highly breathable composite sheet characterized by comprising a four-layer structure of a coexisting layer (F). 　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面から裏面に向かって樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、樹脂・ＭＦＣ・不織布共存層（Ｅ）、ＭＦＣ・不織布共存層（Ｃ）及び不織布層（Ｄ）の５層構造からなることを特徴とする耐水性高通気性複合シート。 MFC obtained by applying resin processing to a finely divided cellulose fiber / nonwoven fabric composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer Resin layer (A), resin / MFC coexistence layer (B), resin / MFC / nonwoven coexistence layer (E), MFC / nonwoven fabric, with the upper surface as the upper surface and the non-woven fabric surface as the lower back surface A water-resistant and highly breathable composite sheet comprising a five-layer structure of a coexisting layer (C) and a nonwoven fabric layer (D). 　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面から裏面に向かって樹脂層（Ａ）、樹脂・ＭＦＣ共存層（Ｂ）、樹脂・ＭＦＣ・不織布共存層（Ｅ）、樹脂・不織布共存層（Ｆ）及び不織布層（Ｄ）の５層構造からなることを特徴とする耐水性高通気性複合シート。 MFC obtained by applying resin processing to a finely divided cellulose fiber / nonwoven fabric composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexisting layer and a nonwoven fabric layer Resin layer (A), resin / MFC coexistence layer (B), resin / MFC / nonwoven coexistence layer (E), resin / nonwoven fabric, when the surface is the upper surface and the nonwoven fabric surface is the lower back surface A water-resistant and highly breathable composite sheet comprising a five-layer structure of a coexistence layer (F) and a nonwoven fabric layer (D). 　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ微細化セルロース繊維・不織布複合体に樹脂加工を施すことによって得られる、ＭＦＣ面を上表面、不織布面を下裏面としたときに、表面のＭＦＣ面上に存在する樹脂層（Ａ）と、さらに裏面の不織布面下に存在する樹脂層（Ａ）と上下に２つの樹脂層（Ａ）を備えたことを特徴とする請求項１乃至５のいずれか一項に記載の耐水性高通気性複合シート。 MFC obtained by applying resin processing to a fine cellulose fiber / nonwoven fabric composite having a three-layer structure of MFC layer composed of micronized cellulose fiber (MFC) and nonwoven fabric, MFC / nonwoven fabric coexistence layer and nonwoven fabric layer When the surface is the upper surface and the nonwoven fabric surface is the lower back surface, the resin layer (A) that exists on the MFC surface on the front surface, and the resin layer (A) that exists further below the nonwoven fabric surface on the back surface and two resins above and below The water-resistant and highly breathable composite sheet according to any one of claims 1 to 5, further comprising a layer (A). 　前記Ａ層の上表面に撥水材層（Ｒ）を更に形成させたことを特徴とする請求項１乃至６のいずれか一項に記載の耐水性高通気性複合シート。 The water-resistant and highly breathable composite sheet according to any one of claims 1 to 6, wherein a water repellent layer (R) is further formed on the upper surface of the A layer. 　前記Ａ層は、樹脂と撥水材とを含有する樹脂・撥水材共存層（Ｓ）であることを特徴とする請求項１乃至６のいずれか一項に記載の耐水性高通気性複合シート。 The water-resistant and highly breathable composite according to any one of claims 1 to 6, wherein the layer A is a resin / water-repellent material coexisting layer (S) containing a resin and a water-repellent material. Sheet. 　撥水材層（Ｒ）と樹脂・撥水材共存層（Ｓ）とを併せ持つことを特徴とする請求項１乃至８のいずれか一項に記載の耐水性高通気性複合シート。 The water-resistant and highly breathable composite sheet according to any one of claims 1 to 8, which has a water-repellent material layer (R) and a resin / water-repellent material coexisting layer (S). 　前記Ｂ、Ｃ、Ｄ、Ｅ及びＦ層のいずれかの層には、固形粉体成分が担持されていることを特徴とする請求項１乃至９のいずれか一項に記載の耐水性高通気性複合シート。 The water resistant high ventilation according to any one of claims 1 to 9, wherein a solid powder component is supported on any one of the B, C, D, E, and F layers. Composite sheet. 　前記固形粉体成分は、脱臭剤（臭気吸着剤）であることを特徴とする請求項１０に記載の耐水性高通気性複合シート。 The water-resistant and highly breathable composite sheet according to claim 10, wherein the solid powder component is a deodorizer (odor adsorbent). 　前記微細化セルロース繊維は、脱臭剤と結合されていることを特徴とする請求項１１に記載の耐水性高通気性複合シート。 The water-resistant and highly breathable composite sheet according to claim 11, wherein the refined cellulose fiber is combined with a deodorant. 　ガーレー法による透気度測定で１０秒／１００ｍＬ～１５０秒／１００ｍＬの通気性と、水深１０ｍｍでのリング式テストで６時間以上漏れが生じない耐久耐水性をもったことを特徴とする請求項１乃至１２のいずれか一項に記載の耐水性高通気性複合シート。 The air permeability measured by the Gurley method has a breathability of 10 seconds / 100 mL to 150 seconds / 100 mL, and has a durable water resistance that does not cause leakage for more than 6 hours in a ring test at a water depth of 10 mm. The water-resistant and highly breathable composite sheet according to any one of 1 to 12. 　請求項１乃至１３のいずれか一項に記載の耐水性高通気性複合シートを防漏体として用いてなることを特徴とする吸収体製品。 An absorbent product comprising the water-resistant and highly breathable composite sheet according to any one of claims 1 to 13 as a leak preventer. 　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ複合体に樹脂加工を施すことによって得られる、耐水性高通気性複合シートの製造方法であって、
　樹脂成分が少なくとも前記複合体のＭＦＣ層に行き渡るような樹脂処理（全層樹脂処理）と、
　樹脂成分を前記複合体の上表面層のみにとどめる樹脂処理（表層樹脂処理）と、
　を組合わせて複合体に樹脂加工を施すことを特徴とする耐水性高通気性複合シートの製造方法。 A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of
Resin treatment (all-layer resin treatment) such that the resin component reaches at least the MFC layer of the composite;
Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite;
A method for producing a water-resistant and highly breathable composite sheet, wherein the composite is subjected to resin processing in combination. 　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ複合体に樹脂加工を施すことによって得られる、耐水性高通気性複合シートの製造方法であって、
　樹脂成分が少なくとも前記複合体のＭＦＣ層及びＭＦＣ・不織布共存層に行き渡るような樹脂処理（全層樹脂処理）と、
　樹脂成分を前記複合体の上表面層のみにとどめる樹脂処理（表層樹脂処理）と、
　を組合わせて複合体に樹脂加工を施すことを特徴とする耐水性高通気性複合シートの製造方法。 A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of
Resin treatment (all-layer resin treatment) in which the resin component reaches at least the MFC layer and the MFC / nonwoven fabric coexisting layer of the composite,
Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite;
A method for producing a water-resistant and highly breathable composite sheet, wherein the composite is subjected to resin processing in combination. 　微細化セルロース繊維（ＭＦＣ）と不織布とから構成されるＭＦＣ層、ＭＦＣ・不織布共存層及び不織布層の３層構造をもつ複合体に樹脂加工を施すことによって得られる、耐水性高通気性複合シートの製造方法であって、
　樹脂成分が少なくとも前記複合体の３層全層に行き渡るような樹脂処理（全層樹脂処理）と、
　樹脂成分を前記複合体の上表面層のみにとどめる樹脂処理（表層樹脂処理）と、
　を組合わせて複合体に樹脂加工を施すことを特徴とする耐水性高通気性複合シートの製造方法。 A water-resistant and highly breathable composite sheet obtained by applying resin processing to a composite having a three-layer structure consisting of an MFC layer composed of micronized cellulose fibers (MFC) and a nonwoven fabric, an MFC / nonwoven fabric coexistence layer, and a nonwoven fabric layer A manufacturing method of
Resin treatment in which the resin component spreads over at least the three layers of the composite (all layer resin treatment);
Resin treatment (surface layer resin treatment) to keep the resin component only on the upper surface layer of the composite;
A method for producing a water-resistant and highly breathable composite sheet, wherein the composite is subjected to resin processing in combination. 　前記全層樹脂処理を最初に行い、
　その後、前記表層樹脂処理を行うことを特徴とする請求項１５乃至１７のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 The all layer resin treatment is performed first,
The method for producing a water-resistant and highly breathable composite sheet according to any one of claims 15 to 17, wherein the surface layer resin treatment is performed thereafter. 　前記表層樹脂処理を最初に行い、
　その後、前記全層樹脂処理を行うことを特徴とする請求項１５乃至１７のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 The surface resin treatment is performed first,
The method for producing a water-resistant and highly breathable composite sheet according to any one of claims 15 to 17, wherein the all-layer resin treatment is performed thereafter. 　撥水材を用いた加工処理をさらに行うことを特徴とする請求項１５乃至１９のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 The method for producing a water-resistant and highly breathable composite sheet according to any one of claims 15 to 19, further comprising a processing using a water repellent material. 　前記表層樹脂処理は、前記樹脂に撥水材を混在させて行うことを特徴とする請求項１５乃至２０のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 The method for producing a water-resistant and highly breathable composite sheet according to any one of claims 15 to 20, wherein the surface layer resin treatment is performed by mixing a water repellent material with the resin. 　前記複合体は、該複合体中にあらかじめ脱臭剤層を形成したものであることを特徴とする請求項１５乃至２１のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 The method for producing a water-resistant and highly breathable composite sheet according to any one of claims 15 to 21, wherein the composite is obtained by previously forming a deodorant layer in the composite. 　前記全層樹脂処理は、前記樹脂に脱臭剤を混在させて行うことを特徴とする請求項１５乃至２１のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 The method for producing a water-resistant and highly breathable composite sheet according to any one of claims 15 to 21, wherein the all-layer resin treatment is performed by mixing a deodorant with the resin. 　前記全層樹脂処理は、固形分８％以下の熱可塑性合成樹脂の水系エマルジョンを用いて行われることを特徴とする請求項１５乃至２３のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 The water-resistant and highly breathable composite sheet according to any one of claims 15 to 23, wherein the all-layer resin treatment is performed using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 8% or less. Manufacturing method. 　前記表層樹脂処理は、固形分１０％以上の熱可塑性合成樹脂の水系エマルジョンを用いて行われることを特徴とする請求項１５乃至２４のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 The water-resistant and highly breathable composite sheet according to any one of claims 15 to 24, wherein the surface resin treatment is performed using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 10% or more. Production method. 　前記全層樹脂処理は、固形分８％以下の熱可塑性合成樹脂の水系エマルジョンを用いて、前記複合体の裏面上に対して行われることを特徴とする請求項１５乃至２５のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 26. The all-layer resin treatment is performed on the back surface of the composite using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 8% or less. A method for producing a water-resistant and highly breathable composite sheet as described in 1. 　前記全層樹脂処理は、固形分１％～５％の熱可塑性合成樹脂の水系エマルジョンを用いて行う工程と、
　固形分３％～８％の熱可塑性合成樹脂の水系エマルジョンを用いて行う工程と、
　を有することを特徴とする請求項１５乃至２３のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 The all-layer resin treatment is performed using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 1% to 5%;
A step of using an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 3% to 8%,
The method for producing a water-resistant and highly breathable composite sheet according to any one of claims 15 to 23, comprising: 　前記の撥水材を用いた加工処理は、撥水材の水系エマルジョンを用いて行われることを特徴とする請求項２０乃至２７のいずれか一項に記載の耐水性高通気性複合シートの製造方法。 The water-repellent highly breathable composite sheet according to any one of claims 20 to 27, wherein the processing using the water-repellent material is performed using an aqueous emulsion of the water-repellent material. Method. 　前記表層樹脂処理は、固形分１０％以上の熱可塑性合成樹脂の水系エマルジョンに撥水材の水系エマルジョンを混和した混合エマルジョンを用いて行われることを特徴とする請求項２０乃至２７のいずれか一項に記載の耐水性高通気性複合シートの製造方法。
　 The surface layer resin treatment is performed using a mixed emulsion obtained by mixing an aqueous emulsion of a water-repellent material with an aqueous emulsion of a thermoplastic synthetic resin having a solid content of 10% or more. A method for producing a water-resistant and highly breathable composite sheet according to Item.
PCT/JP2008/068883 2008-10-17 2008-10-17 Water-resistant and high air permeability composite sheet and process for producing the water-resistant and high air permeability sheet Ceased WO2010044169A1 (en)

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