JP2010240513A - Method of manufacturing composite sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method of manufacturing a composite sheet which is feasible at low costs and uses fine cellulose. <P>SOLUTION: The method of manufacturing the composite sheet includes a process of applying a fine cellulose dispersion containing fine cellulose, water and/or a wetting penetrant to the surface of a hydrophobic substrate and a process of drying the hydrophobic substrate applied with the fine cellulose dispersion to obtain a composite sheet composed of fine cellulose and the hydrophobic substrate. The combination of a type of the wetting penetrant and the mass ratio of the wetting penetrant to the combined amount of water and the wetting penetrant is selected from ethyl alcohol in a concentration of ≥20% and <40%, 1-propyl alcohol in a concentration of ≥11% and lower than 40%, isopropyl alcohol in a concentration of ≥11% and <40%, 1-butyl alcohol in a concentration of ≥1% and <8%, 2-butyl alcohol in a concentration of ≥10% and <13%, t-butyl alcohol in a concentration of ≥6% and <40% and 3,5-dimethyl-1-hexyn-3-ol in a concentration of ≥0.5% and <0.9%. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a method for producing a composite sheet.

A sheet-like or film-like material used for sanitary or medical products does not leak liquid, but requires a certain degree of breathability.
Conventionally, as a sheet material such as a diaper back sheet that requires both water resistance and breathability, a phase separation layer is formed by mixing a filler such as calcium carbonate and a different polymer on a hydrophobic film such as polyethylene. A microporous film is used.
However, this microporous film has an air permeability specified by JIS P8117 of 500 seconds / 100 mL or more, and cannot be said to exhibit practically sufficient ventilation performance.
On the other hand, a water-repellent material and a deodorant are laminated on a composite sheet material composed of a nonwoven fabric and fine fibrous cellulose, and the water-repellent material is selected from an olefin-based water repellent and a paraffin-based water repellent. A breathable sheet containing at least one kind, a synthetic resin binder, and a crosslinking agent has been proposed (see Patent Document 1).
Further, it has a hydrophobic nonwoven fabric layer made of a nonwoven fabric and having a water pressure resistance of 100 mmH ₂ O or more, and a cellulose fiber layer made of cellulose fibers laminated on the hydrophobic nonwoven fabric layer, and the main surface is subjected to a water repellent treatment. A highly breathable water-resistant sheet has also been proposed (see Patent Document 2).

International Publication No. 2008/065748 Pamphlet JP 2007-230139 A

However, the breathable sheet described in Patent Document 1 and the highly breathable water-resistant sheet described in Patent Document 2 both use a large amount of ethyl alcohol in the cellulose dispersion used for coating fine cellulose on the nonwoven fabric. In addition, there is a problem that the collection cost and the replenishment cost that cannot be collected become high because the collection is indispensable industrially.
Therefore, an object of this invention is to provide the manufacturing method of the composite sheet using a fine cellulose which can be performed at low cost.

Conventionally, in a method of obtaining a multilayer body by applying the dispersion to the surface of a nonwoven fabric while maintaining a stable dispersion state of fine cellulose, it is possible to use a mixed solvent containing a large amount of an organic solvent in water. It is known to be useful (for example, see JP-A-10-248872).
Actually, as a cellulose dispersion used for application of fine cellulose on a non-woven fabric, a mixed solvent of ethyl alcohol / water = 65/35 (weight ratio) is used in Patent Document 1, and in Patent Document 2, A mixed solvent of ethyl alcohol / water = 50/50 (weight ratio) is used.
The reason why a mixed solvent containing a large amount of an organic solvent in water is considered to be essential for stabilizing a fine cellulose dispersion, and such a mixed solvent is also used. This is because application onto a nonwoven fabric having hydrophobicity and water repellency could be carried out without problems.
Therefore, conventionally, it has been considered essential to use a mixed solvent containing a large amount of an organic solvent in water as a cellulose dispersion used for applying fine cellulose on a nonwoven fabric.

  However, as a result of earnest research to achieve the above object, the present inventor is unlikely to be considered from such conventional technical common sense, but a specific alcohol is finely divided into a specific amount smaller than the conventional amount. When used in a cellulose dispersion, it is possible not only to produce a composite sheet using fine cellulose at a low cost, but also to satisfy various requirements for industrial production of a composite sheet. As a result, the present invention has been completed.

That is, the present invention provides the following (1) to (11).
(1) A fine cellulose application step of applying a fine cellulose dispersion containing fine cellulose, water, a wetting / penetrating agent to the surface of a hydrophobic substrate,
And drying the hydrophobic substrate coated with the fine cellulose dispersion to obtain a composite sheet of the fine cellulose and the hydrophobic substrate. And
The combination of the kind of the wetting / penetrating agent and the mass ratio of the wetting / penetrating agent with respect to the total of the water and the wetting / penetrating agent in the fine cellulose dispersion is from the following (a) to (g): A method for producing a composite sheet selected from the group consisting of:
(A) Ethyl alcohol: Concentration 20% or more and less than 40% (b) 1-Propyl alcohol: Concentration 11% or more and less than 40% (c) Isopropyl alcohol: Concentration 11% or more and less than 40% (d) 1-Butyl alcohol: Concentration 1% to 8% (e) 2-butyl alcohol: concentration 10% to 13% (f) t-butyl alcohol: concentration 6% to less than 40% (g) 3,5-dimethyl-1-hexyne-3 -All: concentration 0.5% or more and 0.9% or less (2) Furthermore, after the coating step and before the drying step,
Including a water-resistant treatment agent coating step before drying, wherein a water-resistant treatment agent dispersion containing a water-resistant treatment agent and water is applied to a portion of the hydrophobic substrate on which the fine cellulose dispersion is applied. The manufacturing method of the composite sheet as described in (1).

(3) a fine cellulose application step of applying a fine cellulose dispersion containing fine cellulose, water, a wetting and penetrating agent to the surface of a hydrophobic substrate;
A first drying step of drying the hydrophobic substrate coated with the fine cellulose dispersion;
A post-drying water-resistant treatment agent application step of applying a water-resistant treatment agent dispersion containing a water-resistant treatment agent, water and a wetting / penetrating agent to the portion of the hydrophobic substrate on which the fine cellulose dispersion is applied When,
A method for producing a composite sheet, comprising: drying the hydrophobic substrate coated with the water-resistant treatment agent dispersion, and obtaining a composite sheet.
In both the fine cellulose coating step and the post-drying water-resistant treatment agent coating step, the type of the wetting / penetrating agent and the water and the wetting / penetrating agent in the fine cellulose dispersion or the water-resistant treatment agent dispersion The method for producing a composite sheet, wherein the combination with the mass ratio of the wetting / penetrating agent to the total is selected from the group consisting of the following (a) to (g).
(A) Ethyl alcohol: Concentration 20% or more and less than 40% (b) 1-Propyl alcohol: Concentration 11% or more and less than 40% (c) Isopropyl alcohol: Concentration 11% or more and less than 40% (d) 1-Butyl alcohol: Concentration 1% to 8% (e) 2-butyl alcohol: concentration 10% to 13% (f) t-butyl alcohol: concentration 6% to less than 40% (g) 3,5-dimethyl-1-hexyne-3 -All: Concentration 0.5% or more and 0.9% or less (4) Furthermore, after the coating step and before the first drying step,
Including a water-resistant treatment agent coating step before drying, wherein a water-resistant treatment agent dispersion containing a water-resistant treatment agent and water is applied to a portion of the hydrophobic substrate on which the fine cellulose dispersion is applied. The manufacturing method of the composite sheet as described in (3).

(5) Further, a water-resistant treatment agent dispersion containing a water-resistant treatment agent, water, and a wetting / penetrating agent is applied to the surface of the hydrophobic substrate opposite to the side on which the fine cellulose dispersion is applied. A method for producing a composite sheet, comprising a water-resistant treatment agent backside coating step,
In the water-resistant treatment agent backside coating step, the combination of the type of the wetting / penetrating agent and the mass ratio of the wetting / penetrating agent to the total of the water and the wetting / penetrating agent in the water-resistant treatment agent dispersion is as follows: The method for producing a composite sheet according to any one of the above (1) to (4), selected from the group consisting of (a) to (g).
(A) Ethyl alcohol: Concentration 20% or more and less than 40% (b) 1-Propyl alcohol: Concentration 11% or more and less than 40% (c) Isopropyl alcohol: Concentration 11% or more and less than 40% (d) 1-Butyl alcohol: Concentration 1% to 8% (e) 2-butyl alcohol: concentration 10% to 13% (f) t-butyl alcohol: concentration 6% to less than 40% (g) 3,5-dimethyl-1-hexyne-3 -All: Concentration 0.5% or more and 0.9% or less (6) The composite sheet according to any one of (1) to (5), wherein the fine cellulose dispersion further contains a water-resistant treatment agent. Manufacturing method.
(7) The method for producing a composite sheet according to (6), wherein at least one of the water-resistant treatment agent is a resin emulsion and / or latex.
(8) The composite sheet according to any one of the above (1) to (7), wherein the fine cellulose has a water retention amount of 10 mL / g or more that represents a volume of water that can be held by the fine cellulose having a unit mass. Production method.
(9) The method for producing a composite sheet according to any one of (1) to (8), wherein the fine cellulose is biocellulose and / or microfibrillated cellulose.
(10) The method for producing a composite sheet according to any one of (1) to (9), wherein the hydrophobic base material is a nonwoven fabric of hydrophobic synthetic fibers having a basis weight of 10 to 50 g / m ² .
(11) The method for producing a composite sheet according to (10), wherein the nonwoven fabric is a spunbond / meltblown composite nonwoven fabric.

  The manufacturing method of the composite sheet of the present invention can be performed not only at low cost but also can satisfy various demands when manufacturing the composite sheet industrially.

FIG. 3 is an explanatory view showing Embodiment 1. FIG. 6 is an explanatory diagram showing a second embodiment. FIG. 10 is an explanatory diagram showing a third embodiment. FIG. 10 is an explanatory diagram showing a fourth embodiment. It is explanatory drawing which shows Embodiment 5 and 6. FIG. It is explanatory drawing of a 45 degree inclination method test. It is explanatory drawing of a ring type seal test. It is a flowchart which shows the outline | summary of the pilot plant used for manufacture of the composite sheet of an Example.

Hereinafter, the composite sheet of the present invention will be described in detail based on preferred embodiments shown in the accompanying drawings.
The first aspect of the present invention is a fine cellulose application step of applying a fine cellulose dispersion containing fine cellulose, water and a wetting / penetrating agent to the surface of a hydrophobic substrate,
And drying the hydrophobic substrate coated with the fine cellulose dispersion to obtain a composite sheet of the fine cellulose and the hydrophobic substrate. And
The combination of the kind of the wetting / penetrating agent and the mass ratio of the wetting / penetrating agent with respect to the total of the water and the wetting / penetrating agent in the fine cellulose dispersion is from the following (a) to (g): A method for producing a composite sheet selected from the group consisting of:
(A) Ethyl alcohol: Concentration 20% or more and less than 40% (b) 1-Propyl alcohol: Concentration 11% or more and less than 40% (c) Isopropyl alcohol: Concentration 11% or more and less than 40% (d) 1-Butyl alcohol: Concentration 1% to 8% (e) 2-butyl alcohol: concentration 10% to 13% (f) t-butyl alcohol: concentration 6% to less than 40% (g) 3,5-dimethyl-1-hexyne-3 -All: Concentration from 0.5% to 0.9%

The second aspect of the present invention is a fine cellulose coating step of applying a fine cellulose dispersion containing fine cellulose, water and a wetting / penetrating agent to the surface of a hydrophobic substrate,
A first drying step of drying the hydrophobic substrate coated with the fine cellulose dispersion;
A post-drying water-resistant treatment agent application step of applying a water-resistant treatment agent dispersion containing a water-resistant treatment agent, water and a wetting / penetrating agent to the portion of the hydrophobic substrate on which the fine cellulose dispersion is applied When,
A method for producing a composite sheet, comprising: drying the hydrophobic substrate coated with the water-resistant treatment agent dispersion, and obtaining a composite sheet.
In both the fine cellulose coating step and the post-drying water-resistant treatment agent coating step, the type of the wetting / penetrating agent and the water and the wetting / penetrating agent in the fine cellulose dispersion or the water-resistant treatment agent dispersion The combination with the mass ratio of the wetting / penetrating agent to the total is a method for producing a composite sheet selected from the group consisting of the above (a) to (g).

In any of the first aspect of the present invention and the second aspect of the present invention, after the coating step and before the drying step (first drying step),
A pre-drying water-resistant treatment agent coating step of applying a water-resistant treatment agent dispersion containing a water-resistant treatment agent and water to a portion of the hydrophobic substrate on which the fine cellulose dispersion is applied. This is one of the preferred embodiments.

In either of the first aspect of the present invention and the second aspect of the present invention,
Applying a water-resistant treatment agent backside solution, which comprises a water-resistant treatment agent dispersion containing a water-resistant treatment agent, water and a wetting / penetrating agent to the surface opposite to the fine cellulose dispersion of the hydrophobic substrate. Comprising steps,
In the water-resistant treatment agent backside coating step, the combination of the kind of the wetting / penetrating agent and the mass ratio of the wetting / penetrating agent with respect to the total of the water and the wetting / penetrating agent in the water-resistant treating agent dispersion is as described above. One of the preferred embodiments is selected from the group consisting of (a) to (g).

  The first aspect of the present invention and the second aspect of the present invention are common in that they comprise a fine cellulose coating step and a drying step (first drying step), and are not in the first aspect of the present invention. The post water-resistant treatment agent coating step and the second drying step are different in that the second aspect of the present invention is provided.

(1) Fine cellulose application process The fine cellulose application process is a process of applying a fine cellulose dispersion containing fine cellulose, water, a wetting / penetrating agent to the surface of a hydrophobic substrate.
Fine cellulose is composed of fibers that are very thin, partly or entirely, specifically, fibers having a microfibril level fineness in which dozens of cellulose chains are bonded. As a method for producing fine cellulose, for example, a method for obtaining biocellulose (bacterial cellulose) by fermentation of acetic acid bacteria, a method for refining pulp using an abrasive plate rubbing apparatus (for example, JP-A-7-310296) A method of treating pulp with a high-pressure homogenizer for a long time, or a method of subjecting a slurry containing pulp having a solid content concentration of 1 to 6 mass% to treatment with a disc refiner 10 times or more (for example, International Publication No. 2004 No. 2004). / Method described in pamphlet of / 009902). In the present invention, the method for producing fine cellulose is not particularly limited, and fine cellulose obtained by any production method can be used.

  Among these, microfibrillated cellulose (MFC) obtained by microfibrillation of biocellulose and / or pulp is preferable, and MFC is more preferable. MFC has unique properties such as hydrogen bonding performance and solid powder adsorption performance due to the fine size of the fibers and strong hydration properties, and when dispersed in water, the dispersion becomes a large non-Newtonian viscosity. Indicates.

The fine cellulose preferably has a water holding amount of 10 mL / g or more, more preferably 15 mL / g or more, and further preferably 20 mL / g or more. Within the above range, the fine cellulose maintains a stable hydrated state in the fine cellulose dispersion, and the fine cellulose dispersion can be easily handled as a coating material.
In the present invention, the “water retention amount” is a value representing the volume of water that can be held by a unit mass of fine cellulose, and is specifically determined as follows.
That is, the amount of water held is taken as 20 g at a temperature of 20 ° C. and 50 mL of an aqueous dispersion containing about 0.5 g of fine cellulose in a centrifuge tube (inner diameter 30 mm × length 100 mm, scale display volume 50 mL). After centrifuging at 3300 rpm for 10 minutes, the volume of the deposit is read, and the value is obtained by the following formula (1). The absolute dry mass of the fine cellulose is obtained by weighing the deposit when it has been dried and reached a constant weight state.

  Amount of water retained (mL / g) = volume of sediment (mL) / absolute dry mass of fine cellulose (g) (1)

The wetting / penetrating agent plays a role of allowing the fine cellulose dispersion to wet well on the surface of the hydrophobic substrate and to penetrate well from the surface of the hydrophobic substrate to the inside.
Since fine cellulose has high hydrophilicity, when the aqueous dispersion is applied to a sheet-like substrate, it easily wets and penetrates easily into substrates made of hydrophilic fibers such as rayon and cotton. Can be applied.
However, when the sheet-like substrate is a hydrophobic substrate such as a spunbond / meltblown composite nonwoven fabric (for example, one using PP), the sheet-like substrate becomes a water droplet. In addition, even if the surface is sufficiently wet with the aqueous dispersion, the aqueous dispersion penetrates into the base material, and the concentration of the dispersed component occurs near the surface, so that the fluidity of the dispersed component is not lost. Flooding (overflow) will occur and coating will not be possible. That is, in order to uniformly apply to such a hydrophobic substrate, it is necessary to improve both wettability and permeability.

In order to improve both wettability and penetrability, generally, a surfactant (for example, a nonionic surfactant) is contained in an aqueous dispersion, or the substrate is preliminarily surface active. A method of treating with an agent is used.
However, in the case of applications where water resistance is required, such as a leak preventer of an absorbent article, the remaining of the surfactant in the base material is a big problem, so the above-described method using the normal surfactant is used. I can't.

Therefore, the present inventor has previously treated a reactive surfactant with a reactive surfactant, and then reacted the remaining reactive surfactant with fine cellulose or a water-resistant treating agent to extinguish the surfactant effect. It was investigated.
However, it has been found that there is a problem that it is difficult to confirm that the reaction of the reactive surfactant is complete.

The present inventor absorbs the wetting agent and penetrant together with water in the step of removing water even if a method of adding a wetting agent and penetrating agent to the aqueous dispersion of fine cellulose is used. It was considered that no problem arises even in applications where water resistance is required, such as leak-proof bodies of body articles.
Therefore, as a result of examining the use of various substances, the present inventor, when a specific substance is contained in an aqueous dispersion of fine cellulose, both wettability and permeability are excellent, and It has been found that the specific substance is extremely volatile and can be easily removed. Since the specific substance is excellent in both wettability and permeability, it is referred to as “wetting / penetrating agent” in the present specification.

Furthermore, the present inventor examined conditions required for the wetting / penetrating agent.
(1) Excellent wettability and penetrability Aqueous dispersion liquid may uniformly wet the entire surface of the base material, not to form a non-wetting part, and then quickly penetrate into the base material. Desired.
(2) Excellent solubility in water In order to uniformly apply the aqueous dispersion, it is preferable that the wetting / penetrating agent is dissolved in the aqueous dispersion.
(3) No interaction with other components in the aqueous dispersion In order to uniformly apply the aqueous dispersion, the wetting / penetrating agent causes aggregation due to contact with the fine cellulose or the water-resistant treatment agent. It is preferable that no chemical reaction occurs.
(4) High volatility It is preferable that after applying an aqueous dispersion to a base material, it is high in volatility and can be easily removed from the base material by the end of the drying step.
(5) Inexpensive or excellent in recoverability When the wetting / penetrating agent is released from the system, it is preferable that it is inexpensive in order to reduce the cost. Further, it is preferable that the wetting / penetrating agent cannot be released out of the system, and in the case of recovery, recovery by distillation recovery or the like is easy.
(6) Excellent safety When the composite sheet is produced industrially, it is preferable that the wetting / penetrating agent is highly safe.

  The present inventor examined various substances by the method described in detail below in order to find out a wetting / penetrating agent satisfying the above conditions. When a specific amount of a specific substance is contained in an aqueous dispersion of fine cellulose, The inventors have found that the above conditions (1) to (6) are satisfied, and have completed the present invention.

<Evaluation of wettability and permeability>
Evaluation of wettability and permeability was performed by a 45 ° gradient method test and a hand coat test developed by the present inventors.
<45 ° tilt test>
FIG. 6 is an explanatory diagram of a 45 ° tilt method test. FIG. 6A is a schematic diagram showing an apparatus used for the 45 ° tilt method test, and FIG. 6B is a schematic diagram showing a result of the 45 ° tilt method test.
First, solutions of candidate substances were prepared in which various substances (hereinafter referred to as “candidate substances”) that are candidates for wetting and penetrating agents were contained in water at various concentrations.
Next, a solution of a candidate substance (not shown) is placed on a hydrophobic nonwoven fabric 2 (two types) placed on an acrylic plate 1 (length: 400 mm) inclined at 45 ° in a 1 mL volume micropipette. 3 was added dropwise in an amount of 0.1 mL.
The droplets of the candidate substance solution flow down the surface of the hydrophobic nonwoven fabric 2 while penetrating and diffusing into the hydrophobic nonwoven fabric 2, and the positions 4 and 4 ′ where the entire amount has been absorbed into the hydrophobic nonwoven fabric 2 and the dripped position The distance 6, 6 'between 5, 5' was measured. It can be said that the shorter this distance is, the better the wetting and penetrating property to the hydrophobic nonwoven fabric.
The results of the measured distance (unit: mm) are shown in Table 1.

From Table 1, among candidate substances, ethyl alcohol, 1-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, t-butyl alcohol, 3,5-dimethyl-1-hexyn-3-ol It can be seen that the wettability and the permeability are excellent. Among these, it can be seen that 1-propyl alcohol, isopropyl alcohol, 1-butyl alcohol, 2-butyl alcohol, and t-butyl alcohol are particularly excellent.
In addition, 3,5-dimethyl-1-hexyn-3-ol is one of acetylene alcohols, and for example, Surfynol 61 manufactured by Air Products Co. can be suitably used.
Further, from Table 1, the concentration of candidate substances having excellent wettability and permeability is also known.

<Hand coat test>
Next, a hand coat test was performed on a part of candidate substances subjected to the 45 ° inclination method test.
First, candidate substance solutions containing various concentrations of the candidate substance in water were prepared and colored by adding a small amount of dye.
Subsequently, the obtained candidate substance solution was hand-coated on a hydrophobic non-woven fabric (PP non-woven fabric, 13 g / m ² ) using a Mayer bar (wire diameter: 0.1 mm).
The state of coloration of the fibers on the surface of the hydrophobic nonwoven fabric was judged visually, and the wettability and permeability were evaluated.
The results are shown in Table 2. The meanings of the symbols in the table are as follows.
◎: Absorbed by hydrophobic nonwoven fabric within 5 seconds after hand coating ○: Fiber is uniformly colored by hand coating △: Fiber is uniformly colored, but fine droplets are floating on the surface ×: The fiber is not colored and the ball-shaped droplets remain

  From Table 2, the concentration of the candidate substance having excellent wettability and permeability is known.

In addition to the evaluation of wettability and penetrability described above, water solubility, volatility (and boiling point), price and recoverability, and safety were evaluated, and a comprehensive evaluation was performed.
The results are shown in Table 3. The meanings of the symbols in the table are as follows.
◎: Extremely good ○: Good △: Usable ×: Unusable

According to various evaluations by the present inventors described above, in the present invention, the following substances (a) to (g) are used as the wetting / penetrating agent, and the following mass ratio (wetting / It became clear that it was preferable to use it at a mass ratio of penetrant).
(A) Ethyl alcohol: Concentration 20% or more and less than 40% (b) 1-Propyl alcohol: Concentration 11% or more and less than 40% (c) Isopropyl alcohol: Concentration 11% or more and less than 40% (d) 1-Butyl alcohol: Concentration 1% to 8% (e) 2-butyl alcohol: concentration 10% to 13% (f) t-butyl alcohol: concentration 6% to less than 40% (g) 3,5-dimethyl-1-hexyne-3 -All: Concentration from 0.5% to 0.9%

The fine cellulose dispersion contains the fine cellulose described above, water, and the wetting / penetrating agent described above.
The content of fine cellulose in the fine cellulose dispersion is, for example, preferably 0.1% by mass or more, more preferably 0.3% by mass or more, although it depends on the water content of fine cellulose. More preferably, it is more than 0.5% by mass, more preferably not more than 2.0% by mass, more preferably not more than 1.5% by mass, still more preferably not more than 1.0% by mass. preferable. If it is in the above range, the dispersion state of fine cellulose is excellent in stability, and the viscosity at the time of application of the fine cellulose dispersion will be in a state of maintaining appropriate fluidity, so the physical properties of the fine cellulose dispersion are suitable for application. It becomes the physical property.

The fine cellulose dispersion can further contain a water-resistant treatment agent. When the water-resistant treatment agent is contained, the water resistance of the resulting composite sheet becomes more excellent.
Although a water-resistant processing agent is not specifically limited, The thing of following (1)-(4) is mentioned suitably.

(1) A material in which a resin or rubber is dispersed or emulsified in a medium such as water or an organic solvent using a dispersant, an emulsifier, etc. For example, an emulsion of acrylic acid and its derivatives, an emulsion of a resin such as an EVA emulsion; Examples include rubber emulsions (latexes) such as SBR; suspensions of resin fine particles such as PE and PP. These are relatively easy to handle.

(2) Solution of water or organic solvent of resin or prepolymer thereof Examples of the solution include an aqueous solution of PVA or a reactive acrylic acid prepolymer, an organic solvent solution of polyurethane or a reactive polyurethane prepolymer. These have strong film-forming properties.

(3) Powdery or granular thermoplastic polymer For example, powders or granular materials such as PE, PP, EVA and the like can be mentioned.

(4) Adhesive synthetic fiber Adhesive synthetic, which is a short fiber of 15 mm or less composed of a so-called Bi-component Fiber combined with a composite component of, for example, PE / PET, PE / PP, easily meltable PET / hardly meltable PET Fibers; PVA fibers; Eval fibers; polyolefin synthetic pulp (for example, SWP (registered trademark) manufactured by Mitsui Chemicals, Inc.).

  Of these, resin emulsions and / or latexes are preferred.

  When the water-resistant treatment agent is contained in the fine cellulose dispersion, the content of the water-resistant treatment agent is preferably 10% by mass or more, more preferably 30% by mass or more, based on the fine cellulose. It is preferably 200% by mass or less, and more preferably 150% by mass or less. Within the above range, a composite sheet having excellent water resistance and appropriate air permeability and flexibility can be obtained.

The fine cellulose dispersion can further contain other additives.
Additives include, for example, odor adsorbents such as activated carbon and zeolite; moisture absorbents such as silica gel and polymer absorbers; metals such as iron powder and silver ion conjugates; antibacterial agents; antifungal agents; Antiviral agents are mentioned. By adding an additive to the fine cellulose dispersion, the additive can be attached to the composite sheet.
An additive may be used independently and may use 2 or more types together.

The production method of the fine cellulose dispersion is not particularly limited. For example, a fine cellulose dispersion can be obtained by a method of adding fine cellulose to water containing a wetting / penetrating agent.
When the fine cellulose dispersion contains a water-resistant treatment agent, a method of adding fine cellulose to water containing a wetting / penetrating agent and then adding the water-resistant treatment agent is preferable.

The hydrophobic substrate is not particularly limited. For example, a nonwoven fabric of synthetic fibers such as polyethylene, polypropylene, polyester, acrylic, and PVA, and a nonwoven fabric of easily meltable composite fibers such as PE / PET, PE / PP, and EVA / PE are available. Can be mentioned. Among these, a hydrophobic synthetic fiber nonwoven fabric is preferable.
Although the thickness of the fiber used for a nonwoven fabric is not specifically limited, It is preferable that it is 0.5-8.0 denier.
The nonwoven fabric used as the hydrophobic substrate preferably has a basis weight of 10 to 50 g / m ² and a thickness of 0.5 mm or less.
The manufacturing method of the nonwoven fabric used as a hydrophobic base material is not specifically limited. For example, spot-bonded non-woven fabric by card method using short fibers as raw material, air-through method non-woven fabric, pulp non-woven fabric by airlaid method, spunbond non-woven fabric which is filament non-woven fabric, meltblown non-woven fabric, spunbond-meltblown composite non-woven fabric (for example, SM (spunbond) / Meltblown) non-woven fabric, SMS (spunbond / meltblown / spunbond) non-woven fabric). Among them, a spunbond / meltblown composite nonwoven fabric is preferable, and an SMS nonwoven fabric is more preferable in terms of mass production, low cost, and excellent water resistance.

In the fine cellulose application step, the fine cellulose dispersion described above is applied to the surface of the hydrophobic substrate described above.
The coating method is not particularly limited, and for example, a conventionally known method can be used.

  When the hydrophobic substrate contains air inside such as a non-woven fabric, the air is preliminarily introduced with water containing a wetting / penetrating agent or a component close to this used as a dispersion medium for the fine cellulose dispersion. If replaced, a more uniform coating is possible. In this specification, such a pretreatment is referred to as “precoat treatment” or “saturation treatment”.

(2) Pre-drying water-resistant treatment agent coating step In the present invention, after the above-mentioned (1) coating step and before the later-described (3) drying step (first drying step), the pre-drying water-resistant treatment agent coating step Performing the process is one of the preferred embodiments. When the pre-drying water-resistant treatment agent coating step is performed, the water resistance of the resulting composite sheet becomes more excellent.

The pre-drying water-resistant treatment agent applying step is a step of applying a water-resistant treatment agent dispersion containing a water-resistant treatment agent and water to a portion of the hydrophobic substrate on which the fine cellulose dispersion is applied. .
The kind of the water resistant treatment agent used in the water resistant treatment agent dispersion is the same as the water resistant treatment agent that can be used in the fine cellulose dispersion described above.
The content of the water-resistant treatment agent in the water-resistant treatment agent dispersion is not particularly limited as long as it is within a range where a stable dispersion state can be maintained.

  The water-resistant treatment agent dispersion liquid can contain a wetting / penetrating agent in addition to water. The kind and content of the wetting / penetrating agent that can be suitably used for the water-resistant treatment agent dispersion are the same as the kind and content of the wetting / penetrating agent in the fine cellulose dispersion.

In the pre-drying water-resistant treatment agent coating step, the above-described water-resistant treatment agent dispersion is applied to the portion of the hydrophobic substrate surface on which the fine cellulose dispersion is applied.
The coating method is not particularly limited, and for example, a conventionally known method can be used.

Fine cellulose has an extremely large hydrogen bonding force, and once dried, it forms a film in cellophane or parchment paper. Therefore, after that, when applying the water-resistant treatment agent dispersion, it takes time to penetrate into the inside of the hydrophobic substrate. Therefore, when applying the water-resistant treatment agent dispersion after drying, it may depend on a method of adding a wetting / penetrating agent to the water-resistant treatment agent dispersion, a method of applying a low-concentration water-resistant treatment agent dispersion multiple times, It becomes preferable.
On the other hand, before drying, that is, in a state where the hydrophobic base material contains water and / or a wetting / penetrating agent and the fine cellulose fibers are not bonded by hydrogen bonding, When applied, there is an advantage that the penetration of the water-resistant treatment agent dispersion into the fine cellulose fiber gaps and the inside of the hydrophobic substrate becomes relatively easy.

(3) Drying step (first drying step)
The drying step is a step of obtaining the composite sheet of the fine cellulose and the hydrophobic substrate by drying the hydrophobic substrate coated with the fine cellulose dispersion.
The drying method is not particularly limited, and examples include a method of conveying hot air in a conveyor, a method of directly contacting the surface of a heating roll such as a Yankee drum, a method of drying using infrared rays, and a method combining these. It is done.
Prior to drying, liquid removal can be performed. The method of liquid removal is not particularly limited, and examples thereof include vacuum liquid removal and press liquid removal.

In the drying step, the wetting / penetrating agent can be recovered.
When collecting the wetting / penetrating agent, it is preferable to remove the liquid before drying to collect water containing the wetting / penetrating agent. The recovered water containing the wetting / penetrating agent can be used for preparing a fine cellulose dispersion, a water-resistant treatment agent dispersion, and the like. In addition, when the amount of water containing the collected wetting / penetrating agent is larger than the amount used for the preparation of fine cellulose dispersion, water-resistant treatment agent dispersion, etc., the wetting / penetrating agent is concentrated by distillation. And can be recovered.
On the other hand, in a case where the amount of the wetting / penetrating agent is small, the environmental load is small even if it is discharged as waste liquid, and the cost becomes high if it is recovered, it is one of the preferred embodiments that the recovery is not performed. In addition, when not collect | recovering, it is preferable to discharge | emit the water containing the wetting / penetrating agent discharged | emitted by liquid removal and drying through an activated sludge process.

If the amount of wetting and penetrating agent remaining on the hydrophobic base material is large even after dehydration, and if it reaches the explosive limit in the drying process, it is generated by heating nitrogen gas and performing sealed oxygen-free drying. The concentrated wet / penetrant gas is preferably washed with cooling water in a washing tower, then condensed and recovered as dilution water. For example, in the case of exhaust gas from a vacuum pump, it is preferable to collect it as dilution water by a washing tower when the concentration of the wetting / penetrating agent is high.
As described above, the treatment of the dilution water is preferably concentrated and recovered by distillation when the concentration is relatively high and the cost does not increase.

In the drying step, it is preferable not to generate dry wrinkles.
When the content of water and the wetting / penetrating agent in the hydrophobic substrate is 50% by mass or less, particularly 30% by mass or less, shrinkage due to drying tends to occur. In the latter stage of such drying, it is preferable to dry in a state where tension is applied in the width direction and the length direction so that the hydrophobic substrate does not shrink.
Examples of a method of applying tension in the width direction include a method of installing a press roll on a conveyor and a method of completing drying in a state where the press roll is pressed onto the heating roll. Examples of a method for applying tension in the length direction include conventionally known methods.

The drying step may have other purposes in addition to drying the hydrophobic substrate described above.
For example, when a water-resistant treatment agent that requires crosslinking is used, the crosslinking reaction can be terminated or cured in the drying step.
Moreover, when finishing processes, such as a surface mirror surface process and a thin film forming process, are required, a finishing process can be performed online in a drying process. The finishing process can also be performed on the composite sheet obtained by drying.

  By drying, the fine cellulose adheres firmly to the hydrophobic substrate, and a composite sheet is obtained. When the fine cellulose dispersion contains a water-resistant treatment agent and when a pre-drying water-resistant treatment agent is applied, the fine cellulose and the water-resistant treatment agent adhere to the hydrophobic substrate by drying, and a composite sheet is obtained. .

  In the second aspect of the present invention, that is, when the post-drying water-resistant treatment agent coating step and the second drying step are sequentially performed after this step, this step is performed in the post-drying water-resistant treatment agent coating step. It is sufficient that the drying is performed to such an extent that the water resistant treatment agent dispersion can be applied. For example, although a very thin part of the surface is in a dry state, water and a wetting / penetrating agent may still remain inside, or water and wetting / penetrating agent of the entire hydrophobic substrate may be left. The content may be in the range of about 0 to 80% by mass.

(4) Water-resistant treatment agent coating step after drying In the second aspect of the present invention, the (3) drying step is performed as the first drying step, and then (4) the water-resistant treatment agent coating step after drying and (5) The second drying step is sequentially performed.
In the post-drying water-resistant treatment agent coating step, a water-resistant treatment agent dispersion containing a water-resistant treatment agent, water and a wetting / penetrating agent is applied to a portion where the fine cellulose dispersion on the surface of the hydrophobic substrate is applied. It is a process of applying.
The kind of the water resistant treatment agent used in the water resistant treatment agent dispersion is the same as the water resistant treatment agent that can be used in the fine cellulose dispersion described above.
The content of the water-resistant treatment agent in the water-resistant treatment agent dispersion is not particularly limited. For example, a commercially available resin emulsion or rubber emulsion (latex) generally has a solid content concentration of 40 to 80% by mass. Therefore, the undiluted solution can be used as it is or diluted so that the solid content concentration is 5 to 30% by mass.

The kind and content of the wetting / penetrating agent used in the water-resistant treating agent dispersion are the same as the kind and content of the wetting / penetrating agent in the fine cellulose dispersion. The wetting / penetrating agent used for the fine cellulose dispersion and the wetting / penetrating agent used for the water-resistant treatment agent dispersion may be the same or different, but are preferably the same.
The wetting / penetrating agent used in the water-resistant treatment agent dispersion makes it easy to wet and infiltrate the water-resistant treatment agent dispersion onto the surface of the hydrophobic substrate dried in the first drying step.

In the post-drying water-resistant treatment agent coating step, the above-mentioned water-resistant treatment agent dispersion is applied to the portion of the hydrophobic substrate surface on which the fine cellulose dispersion is applied.
The coating method is not particularly limited, and for example, a conventionally known method can be used.

  When performing the pre-drying water-resistant treatment agent application step, in the pre-drying water-resistant treatment agent application step, infiltrate the water-resistant treatment agent from the surface to a relatively deep part, and in the post-drying water-resistant treatment agent application step, It is preferable to penetrate the water-resistant treatment agent from the surface to a shallow portion.

(5) Second drying step The second drying step is a step of obtaining a composite sheet by drying the hydrophobic substrate coated with the water-resistant treatment agent dispersion in the post-drying water-resistant treatment agent coating step.
A 2nd drying process can be performed by the method similar to the drying process (1st drying process) mentioned above.
By drying, the fine cellulose adheres to the hydrophobic base material, and further the water-resistant treatment agent adheres to obtain a composite sheet.

(6) Water-resistant treatment agent back side coating step The water-resistant treatment agent back side coating step comprises a water-resistant treatment agent dispersion containing a water-resistant treatment agent, water and a wetting / penetrating agent, and the fine cellulose dispersion of the hydrophobic substrate. This is a step of applying to the surface on the opposite side (hereinafter also referred to as “back side”).
The order of the water-resistant treatment agent back side coating step and the above steps is not particularly limited.

The kind of the water resistant treatment agent used in the water resistant treatment agent dispersion is the same as the water resistant treatment agent that can be used in the fine cellulose dispersion described above.
The content of the water-resistant treatment agent in the water-resistant treatment agent dispersion is not particularly limited. For example, a commercially available resin emulsion or rubber emulsion (latex) generally has a solid content concentration of 40 to 80% by mass. Therefore, the undiluted solution can be used as it is or diluted so that the solid content concentration is 5 to 30% by mass.

  The kind and content of the wetting / penetrating agent that can be suitably used for the water-resistant treatment agent dispersion are the same as the kind and content of the wetting / penetrating agent in the fine cellulose dispersion. The wetting / penetrating agent used for the fine cellulose dispersion and the wetting / penetrating agent used for the water-resistant treatment agent dispersion may be the same or different.

In the water-resistant treatment agent back side coating step, the above-described water-resistant treatment agent dispersion is applied to the surface of the hydrophobic substrate back side.
The coating method is not particularly limited, and for example, a conventionally known method can be used.

  After the water-resistant treatment agent back side coating step, it is preferable to dry the hydrophobic substrate coated with the water-resistant treatment agent dispersion. Drying can be performed by a method similar to the above-described drying step (first drying step).

  Hereinafter, preferred embodiments of the present invention will be described with reference to the drawings.

<Embodiment 1 by the combination of steps (1) and (3)>
FIG. 1 is an explanatory diagram showing the first embodiment. Embodiment 1 is by a combination of steps (1) and (3).
First, a high-concentration MFC aqueous dispersion is added to a mixture of isopropyl alcohol (IPA) and water, and then an SBR emulsion (an aqueous dispersion of SBR, for example, a solid content concentration of 50% by mass) is added. To obtain a fine cellulose dispersion containing MFC, SBR, IPA and water (for example, MFC content 1 mass%, SBR content 0.8 mass%, IPA / water = 25/75 (mass ratio)). .
Next, this fine cellulose dispersion is applied to the surface of the SMS nonwoven fabric (application step).
Thereafter, the SMS nonwoven fabric coated with the fine cellulose dispersion is drained by suction and further dried by hot air to obtain a composite sheet of MFC, SBR and SMS nonwoven fabric (drying step).

<Embodiment 2 by a combination of steps (1), (2) and (3)>
FIG. 2 is an explanatory view showing the second embodiment. Embodiment 2 is by a combination of steps (1), (2) and (3).
First, a high-concentration MFC aqueous dispersion is added to a mixture of IPA and water, and a fine cellulose dispersion containing MFC, IPA and water (for example, an MFC content of 0.8 mass%, IPA / Water = 25/75 (mass ratio)) is obtained.
Next, this fine cellulose dispersion is applied to the surface of the SMS nonwoven fabric (application step).
Thereafter, the SMS nonwoven fabric coated with the fine cellulose dispersion is drained by suction.
Further, an SBR emulsion (an aqueous dispersion of SBR. For example, a solid content concentration of 20% by mass) is spray-applied to a portion of the surface of the SMS nonwoven fabric on which the fine cellulose dispersion is applied (waterproofing agent before drying) Application process).
Then, it is dried with hot air to obtain a composite sheet of MFC, SBR and SMS nonwoven fabric (drying step).

<Embodiment 3 by a combination of steps (1), (3), (4) and (5)>
FIG. 3 is an explanatory view showing the third embodiment. Embodiment 3 is based on a combination of steps (1), (3), (4) and (5).
First, a high-concentration MFC aqueous dispersion is added to a mixture of IPA and water, and a fine cellulose dispersion containing MFC, IPA and water (for example, an MFC content of 0.8 mass%, IPA / Water = 25/75 (mass ratio)) is obtained.
Next, this fine cellulose dispersion is applied to the surface of the SMS nonwoven fabric (application step).
Thereafter, the SMS nonwoven fabric coated with the fine cellulose dispersion is drained by suction, and the surface of the SMS nonwoven fabric is further dried by a heating roll (first drying step).
Furthermore, the SBR IPA / water mixed solvent dispersion (for example, solid content concentration of 15% by mass, IPA / water = 20/80 (mass ratio)) was applied to the surface of the SMS nonwoven fabric with a fine cellulose dispersion. It applies to the part which is done (waterproofing agent application process after drying).
Then, it dries with hot air to obtain a composite sheet of MFC, SBR, and SMS nonwoven fabric (second drying step).

<Embodiment 4 by a combination of steps (1), (3), (4) and (5)>
FIG. 4 is an explanatory view showing the fourth embodiment. Embodiment 4 is by a combination of steps (1), (3), (4) and (5).
First, a high-concentration MFC aqueous dispersion is added to a mixture of IPA and water, and an SBR emulsion (an aqueous dispersion of SBR. For example, a solid content concentration of 50% by mass) is added to the MFC. A fine cellulose dispersion containing SBR, IPA and water (for example, MFC content 1 mass%, SBR content 0.8 mass%, IPA / water = 25/75 (mass ratio)) is obtained.
Next, this fine cellulose dispersion is applied to the surface of the SMS nonwoven fabric (application step).
Thereafter, the SMS nonwoven fabric coated with the fine cellulose dispersion is drained by suction, and the surface of the SMS nonwoven fabric is further dried by a heating roll (first drying step).
In addition, a SBR IPA / water mixed solvent dispersion (for example, solid content concentration of 15% by mass, IPA / water = 30/70 (mass ratio)) is applied to a fine cellulose dispersion on the surface of an SMS nonwoven fabric with a dried surface. It applies to the part which is done (waterproofing agent application process after drying).
Then, it dries with hot air to obtain a composite sheet of MFC, SBR, and SMS nonwoven fabric (second drying step).

<Embodiment 5 by a combination of steps (1), (2), (3), (4) and (5) and a combination of steps (1), (2), (3), (6) and (5) Embodiment 6>
FIG. 5 is an explanatory view showing Embodiments 5 and 6. In FIG. Embodiment 5 is a combination of steps (1), (2), (3), (4) and (5), and embodiment 6 is a combination of steps (1), (2), (3) and (6). And by the combination of (5).
First, a high-concentration MFC aqueous dispersion is added to a mixture of IPA and water, and a fine cellulose dispersion containing MFC, IPA and water (for example, an MFC content of 0.8 mass%, IPA / Water = 25/75 (mass ratio)) is obtained.
Next, this fine cellulose dispersion is applied to the surface of the SMS nonwoven fabric (application step).
Thereafter, the SMS nonwoven fabric coated with the fine cellulose dispersion is drained by suction.
Further, an SBR emulsion (an aqueous dispersion of SBR. For example, a solid content concentration of 10% by mass) is spray-applied to a portion of the surface of the SMS nonwoven fabric on which the fine cellulose dispersion is applied (waterproofing agent before drying) Application process).
Then, it is dried with hot air (first drying step).
In the embodiment 5, the SBR IPA / water mixed solvent dispersion (for example, solid content concentration of 15% by mass, IPA / water = 25/75 (mass ratio)) is further applied to the fine cellulose on the surface of the dried SMS nonwoven fabric. The dispersion is applied to the applied part (after drying, a water-resistant treatment agent application step). In Embodiment 6, an IPA / water mixed solvent dispersion of SBR (for example, a solid content concentration of 15% by mass, IPA / water = 25/75 (mass ratio)) is further applied to the back surface of the dried SMS nonwoven fabric. Apply (waterproofing agent backside coating process).
Then, it dries with hot air to obtain a composite sheet of MFC, SBR, and SMS nonwoven fabric (second drying step).

  As mentioned above, although the manufacturing method of the composite sheet of this invention was mentioned taking the preferred embodiment as an example, this invention is not limited to these.

  The use of the composite sheet obtained by the method for producing a composite sheet of the present invention is not particularly limited. The various properties of the composite sheet can be utilized for various applications.

(1) Surface (surface layer) hydrophilization function Fine cellulose is combined on the surface or surface layer of a hydrophobic substrate (for example, PE nonwoven fabric, PP nonwoven fabric, PE / PP composite fiber nonwoven fabric, PE / PET composite fiber nonwoven fabric). Therefore, the surface or surface layer of the hydrophobic substrate is permanently hydrophilic. This composite sheet can be applied to fields where both hydrophilicity and hydrophobicity are required.
For example, it is suitable for bio-barrier applications such as surgical clothes and cover cloths that do not generate static electricity and exhibit hygroscopicity; suitable for water-absorbing sealants and food packaging materials that prevent dew condensation and have both peelability and sealing properties. .

(2) Air permeability and water barrier property imparting function Using a hydrophobic base material having air permeability (eg, spunbond / meltblown composite nonwoven fabric such as PE or PP; water resistant nonwoven fabric such as SMMS), fine cellulose and water resistant treatment When the agent is combined, liquid water is not permeated, but gas such as water vapor and air is permeated. This composite sheet can be applied to fields that require both high air permeability and water barrier resistance.
For example, it is suitably used for wrapping for sterilization; back sheets of absorbent products such as paper diapers and napkins.

(3) Surface area increasing function Since fine cellulose has an extremely large internal surface area, the composite sheet can hold a large amount of electrolytes on the surface thereof.
For example, it is suitably used for a battery (eg, lithium battery) separator.

(4) Additive holding function The composite sheet can hold an additive (for example, an adsorbent, an absorber).
For example, it can be suitably used as a constituent material such as a dust mask and an influenza mask;

Hereinafter, the present invention will be specifically described with reference to examples. However, the present invention is not limited to these.
1. Manufacture of composite sheet by hand coating (Part 1)
(1) Preparation of MFC dispersion liquid Pulp made from hardwood (LBKP, St. Croix, manufactured by US Waterer) was disaggregated with a pulper, and the resulting pulp water dispersion (solid content concentration 3% by mass) was obtained. 50 cycles were performed using a double disc refiner (manufactured by Aikawa Tekko Co., Ltd.) to obtain an MFC aqueous dispersion (solid content concentration 3 mass%). MFC had a number average fiber length of 0.15 mm and a water holding amount of 25 mL / g.

IPA (primary reagent) and ion-exchanged water were added to the MFC aqueous dispersion (solid content concentration of 3% by mass) obtained above to prepare the following five types of MFC dispersions A to E. .
MFC dispersion A: MFC solid content concentration 0.8 mass%, IPA / water = 20/80 (mass ratio)
MFC dispersion B: MFC solid content concentration 0.8 mass%, IPA / water = 15/85 (mass ratio)
MFC dispersion C: MFC solid content concentration 0.8 mass%, IPA / water = 10/90 (mass ratio)
MFC dispersion D: MFC solid content concentration 0.8 mass%, IPA / water = 5/95 (mass ratio)
MFC dispersion E: MFC solid content concentration 0.8 mass%, IPA / water = 0/100 (mass ratio)

(2) Application of MFC dispersion to SMS nonwoven fabric (fine cellulose coating process)
Using a hand coater, an IPA / water mixture (IPA) was applied to the surface of an SMS nonwoven fabric (PP SMS nonwoven fabric, 13 g / m ² , Avgor, 250 mm wide × 1,000 mm long) placed on a glass plate. / Water = 20/80), and then the MFC dispersion obtained above was applied using a hand coater. The lip clearance upon application of the MFC dispersion was 1.2 mm.

The state of each coated surface immediately after coating was as follows.
Example 1 (using MFC dispersion A): a very smooth and homogeneous coating surface was obtained Example 2 (using MFC dispersion B): a uniform coating surface was obtained throughout Example 3 (using MFC dispersion C) : Almost uniform coated surface but partially thickened and thinned Example 4 (using MFC dispersion D): Pinhole-shaped repelled portion was observed on an unevenly coated surface Example 5 ( MFC dispersion E was used): The liquid was repelled throughout and no coating film was formed.

(3) Liquid removal and drying (drying process)
The SMS non-woven fabric coated with the MFC dispersion was placed on several sheets of water-absorbing paper and drained, then transferred to another water-absorbing paper, left to dry, and the MFC and SMS non-woven fabric. A composite sheet was obtained.

  About the obtained composite sheet, the MFC coating amount and the Gurley air permeability were measured, and the surface was visually observed. In addition, the Gurley air permeability measured 10 places of each sample, and calculated | required the average value.

The results were as follows.
Example 1: MFC coating amount 8.0 g / m ² , Gurley air permeability 96 sec / 100 mL, homogeneous coating surface Example 2: MFC coating amount 8.2 g / m ² , Gurley air permeability 90 sec / 100 mL, homogeneous Example 3: MFC coating amount 8.1 g / m ² , Gurley air permeability 24 sec / 100 mL, pinholes were slightly present in the MFC coating part Example 4: MFC coating amount 7.6 g / m ² , Gurley air permeability of 8 sec / 100 mL, large coating unevenness was observed. Example 5: Coating could not be performed and a composite sheet could not be obtained.

As is apparent from the above results, according to the method for producing a composite sheet of the present invention (Examples 1 and 2), uniform coating can be performed.
On the other hand, when the IPA / water is 10/90 (Example 3), the IPA / water is 5/95 (Example 4), and 0/100 (Example 5) in the MFC dispersion, it is homogeneous. Coating was not possible.

2. Manufacture of composite sheet by hand coating (Part 2)
(1) Preparation of MFC Dispersion IPA (primary reagent) was added to an MFC aqueous dispersion (solid content concentration 3% by mass) obtained by the same method as “1. Production of composite sheet by hand coating (Part 1)”. ) And ion-exchanged water, and further SBR emulsion (Smartex PA-3807, manufactured by Nippon A & L Co., Ltd., solid content concentration 48.3 mass%), and the following five types of MFC dispersions F to J were prepared.
MFC dispersion F: MFC solid content concentration 0.8 mass%, SBR solid content concentration 0.8 mass%, IPA / water = 45/55 (mass ratio)
MFC dispersion G: MFC solid content concentration 0.8 mass%, SBR solid content concentration 0.8 mass%, IPA / water = 30/70 (mass ratio)
MFC dispersion H: MFC solid content concentration 0.8 mass%, SBR solid content concentration 0.8 mass%, IPA / water = 15/85 (mass ratio)
MFC dispersion I: MFC solid content concentration 0.8 mass%, SBR solid content concentration 0.8 mass%, IPA / water = 5/95 (mass ratio)
MFC dispersion J: MFC solid content concentration 0.8 mass%, SBR solid content concentration 0.8 mass%, IPA / water = 0/100 (mass ratio)

(2) Application of MFC dispersion to SMS nonwoven fabric (fine cellulose coating process)
Using a hand coater, an IPA / water mixture (IPA / water) was applied to the surface of an SMS nonwoven fabric (PP nonwoven fabric made of PP, 13 g / m ² , Avgor, width 250 mm × length 1000 mm) placed on a glass plate. = 20/80), and the MFC dispersion obtained above was further applied using a hand coater. The lip clearance upon application of the MFC dispersion was 1.2 mm.

The state of each coated surface immediately after coating was as follows.
Example 6 (using MFC dispersion F): Agglomerates of SBR appeared on the entire surface, resulting in a rough application surface. Example 7 (using MFC dispersion G): An extremely smooth and homogeneous application surface was obtained. Example 8 (Using MFC dispersion H): A uniform coated surface was obtained throughout Example 9 (using MFC dispersion I): Thickness of coating film and generation of pinholes were observed throughout Example 10 (MFC dispersion J Use): The liquid was repelled on the whole, and the coating film was not formed.

(3) Liquid removal and drying (drying process)
The SMS nonwoven fabric coated with the MFC dispersion is placed on several sheets of water-absorbing paper, drained, then transferred to another water-absorbing paper, left to dry, and MFC, SBR, and SMS nonwoven fabric. A composite sheet was obtained.

  About the obtained composite sheet, MFC and SBR total coating amount and Gurley air permeability were measured, and the surface was visually observed. In addition, the Gurley air permeability measured 10 places of each sample, and calculated | required the average value.

The results were as follows.
Example 6: MFC and SBR total coating amount 14.8 g / m ² , Gurley permeability 8 sec / 100 mL, a large amount of aggregates and pinholes were generated Example 7: MFC and SBR total coating amount 15.3 g / m ² , Gurley permeability 70 sec / 100 mL, uniform coated surface Example 8: MFC and SBR total coating amount 15.6 g / m ² , Gurley permeability 67 sec / 100 mL, uniform coated surface Example 9: MFC And SBR total coating amount 15.2 g / m ² , Gurley air permeability 24 sec / 100 mL, large coating unevenness was observed. Example 10: Coating could not be performed and a composite sheet could not be obtained.

As is apparent from the above results, according to the method for producing a composite sheet of the present invention (Examples 7 and 8), uniform coating can be performed.
On the other hand, in the MFC dispersion, when IPA / water was 45/55 (Example 6), the resin of the SBR emulsion aggregated, and a uniform coated surface could not be obtained. Further, in the MFC dispersion liquid, when IPA / water was 5/95 (Example 9) and 0/100 (Example 10), uniform coating could not be performed.

3. Manufacture of composite sheet by hand coating (Part 3)
(1) Preparation of SBR dispersion liquid A mixture of t-butyl alcohol (primary reagent) and water was added to an SBR emulsion (Smartex PA-3807, manufactured by Nippon A & L Co., Ltd., solid content concentration 48.3 mass%). Thus, five types of SBR dispersions as described below were prepared.
SBR dispersion a: SBR solid content concentration 10% by mass, t-butyl alcohol / water = 20/80
SBR dispersion b: SBR solid content concentration 10% by mass, t-butyl alcohol / water = 15/85
SBR dispersion c: SBR solid content concentration 10% by mass, t-butyl alcohol / water = 10/90
SBR dispersion d: SBR solid content concentration 10% by mass, t-butyl alcohol / water = 5/95
SBR dispersion e: SBR solid content concentration 10% by mass, t-butyl alcohol / water = 0/100

(2) Application of SBR dispersion to SMS nonwoven fabric coated with MFC (waterproofing agent coating process after drying)
The composite sheet obtained in Example 1 (not coated with SBR) and the composite sheet obtained in Example 7 (SBR coating amount 7.3 g / m ² ) were cut into a size of 170 mm wide × 400 mm long, respectively. The SBR dispersion obtained above was applied to the surface of the MFC application surface using a Mayer bar (wire diameter 0.3 mm).

The state of each coated surface immediately after coating was as follows.
Example 11 (use of composite sheet and SBR dispersion a obtained in Example 1): SBR dispersion was absorbed very quickly on a very homogeneous coated surface Example 12 (composite sheet and SBR obtained in Example 1) Dispersion b used): SBR dispersion was absorbed very quickly on a very homogeneous coated surface Example 13 (use of composite sheet and SBR dispersion c obtained in Example 1): SBR dispersion on a homogeneous coated surface Example 14 (using the composite sheet and SBR dispersion d obtained in Example 1): SBR dispersion was gently absorbed on the homogeneous coated surface Example 15 (composite obtained in Example 1) Body sheet and SBR dispersion e): The SBR dispersion became droplets and remained on the surface, and did not become a film.

Example 16 (use of composite sheet and SBR dispersion a obtained in Example 7): SBR dispersion was absorbed very quickly on a very homogeneous coated surface Example 17 (composite sheet and SBR obtained in Example 7) Dispersion b was used): SBR dispersion was quickly absorbed on the homogeneous coated surface. Example 18 (use of composite sheet and SBR dispersion c obtained in Example 7): A homogeneous coated surface was formed immediately after coating. However, after that, a portion where the SBR dispersion was partially accumulated Example 19 (use of the composite sheet obtained in Example 7 and the SBR dispersion d): Example where many portions where the SBR dispersion was repelled occurred 20 (use of the composite sheet obtained in Example 7 and the SBR dispersion e): The SBR dispersion was repelled and could not be applied.

(3) Drying (second drying step)
The SMS nonwoven fabric coated with the SBR dispersion was placed on a plywood board that had been cut to the same size so that shrinkage due to drying would not occur, and the four corners were fixed to the plywood board with clips, and dried with hot air at 80 ° C. It was dried with a machine for 30 minutes to obtain a composite sheet of MFC, SBR and SMS nonwoven fabric.

  About the obtained composite sheet, SBR coating amount and Gurley air permeability were measured, and a ring type seal test developed by the present inventor described later was performed to evaluate water resistance. In addition, the Gurley air permeability measured 10 places of each sample, and calculated | required the average value.

<Ring seal test>
FIG. 7 is an explanatory diagram of the ring seal test. FIG. 7A is a schematic perspective view showing a ring used for the ring type seal test, and FIG. 7B is a schematic front view showing an apparatus used for the ring type seal test.
The ring 11 used in the ring seal test shown in FIG. 7A is made of stainless steel, and has an inner diameter of 80 mm, a height of 50 mm, and a weight of 500 g.
As shown in FIG. 7B, a detection filter paper 14 (GRADE2, manufactured by Advantec, basis weight 125 g / m ² , thickness 0 on the transparent glass plate 12 for detecting leakage of water from the sample 13. 26 mm) and the sample 13 is placed on the detection filter paper 14.
Next, the ring 11 is placed on the sample 13. A resin adhesive (new polygrip S, manufactured by Earth Pharmaceutical Co., Ltd.) is applied to the contact surface of the ring 11 with the sample 13 in advance so as to prevent leakage of water from between the sample 13 and the ring 11. Keep it.
An observation mirror 15 for observing the state of the detection filter paper 14 is provided below the transparent glass plate 12.
In the above apparatus, 50 mL of dye water 16 is introduced into the space formed by the inner wall of the ring 11 and the surface of the sample 13, and at the time of introduction and after a predetermined time (after 2, 6 and 24 hours). In addition, whether or not the dye water 16 has permeated through the sample 13 and leaked into the detection filter paper 14 was observed with the observation mirror 15.

  The ring-type seal test was also performed on the sheets to which the SBR dispersion was not applied (composite sheets obtained in Examples 1 and 7).

Example 11: SBR coating amount 5.9 g / m ² , Gurley permeability 156 sec / 100 mL, trace amount of leakage after 24 hours Example 12: SBR coating amount 5.7 g / m ² , Gurley permeability 150 sec / 100 mL, 24 Small amount of leakage after time Example 13: SBR coating amount 4.2 g / m ² , Gurley air permeability 130 sec / 100 mL, spot leakage after 6 hours Example 14: SBR coating amount 3.9 g / m ² , Gurley permeability Leakage 126 sec / 100 mL, spot-like leakage after 2 hours Example 15: Gurley permeability 100 sec / 100 mL, leakage occurred after several minutes Example 1: Gurley permeability 96 sec / 100 mL, leakage after several minutes

Example 16: SBR coating amount 4.2 g / m ² , Gurley permeability 305 sec / 100 mL, no leakage after 24 hours Example 17: SBR coating amount 4.0 g / m ² , Gurley permeability 280 sec / 100 mL, 24 hours No occurrence of after-leakage Example 18: SBR application amount 3.3 g / m ² , Gurley permeability 223 sec / 100 mL, no leakage after 24 hours Example 19: SBR application amount 3.1 g / m ² , Gurley permeability 106 sec / 100 mL, spot leak after 24 hours Example 20: Gurley permeability 76 sec / 100 mL, spot leak after 6 hours Example 7: Gurley permeability 70 sec / 100 mL, spot leak after 6 hours

As is clear from the above results, according to the method for producing a composite sheet of the present invention (Examples 11 to 13 and 16 to 18), uniform coating can be performed.
On the other hand, in the SBR dispersion, when t-butyl alcohol / water was 5/95 (Examples 14 and 19) and 0/100 (Examples 15 and 20), uniform coating could not be performed.

Moreover, in the application by the Mayer bar, generally, the application amount tends to increase as the application liquid has better permeability to the substrate.
Therefore, the SBR coating amount in Examples 11 and 12 is larger than the SBR coating amount in Example 13, indicating that the SBR dispersion used in Examples 11 and 12 is more permeable than the dispersion used in Example 13. It shows that. Similarly, the SBR coating amount in Examples 16 and 17 is larger than the SBR coating amount in Example 18 because the SBR dispersion used in Examples 16 and 17 is more permeable than the dispersion used in Example 18. Indicates that it was.

  Furthermore, when SBR was contained in the MFC dispersion used in the fine cellulose coating step (Examples 16 to 18), when SBR was not contained in the MFC dispersion used in the fine cellulose coating step (Example 11). Compared to ˜13), the SBR coating amount in the post-drying water-resistant treatment agent coating step was small, but the water resistance was excellent.

4). Manufacture of composite sheet by pilot plant (Part 1)
(1) Outline of Pilot Plant FIG. 8 is a flowchart showing an outline of the pilot plant used for manufacturing the composite sheet.
A hydrophobic substrate (width 500 mm) is fed from a rewinder, guided to a precoater by a net conveyor (endless), and precoated with a precoat solution (eg, IPA / water mixture). The precoat liquid is supplied from a precoat tank (poly tank) that stores the precoat liquid to a precoat tank provided in the precoater, and is applied to the hydrophobic substrate. The surplus precoat liquid that could not be absorbed by the hydrophobic base material is collected in a plastic tank.
The hydrophobic substrate is guided to the slurry coater after the precoater, and is coated with the MFC dispersion. The slurry coater is equipped with a slurry header to maintain the coating stability, and the MFC dispersion liquid is always supplied from the MFC slurry tank (with agitator) that stores the MFC dispersion liquid via the slurry pump. The liquid application head is controlled. The overflowed MFC dispersion returns to the MFC slurry tank. That is, the MFC dispersion is circulated between the slurry header and the MFC slurry tank.
The hydrophobic substrate coated with the MFC dispersion is guided to vacuum suction and drained. The vacuum suction is equipped with a gas-liquid separator.
The drained hydrophobic substrate is guided to a drum dryer and dried.
The dried hydrophobic substrate is directed to a spray coater and optionally sprayed with an SBR dispersion.
The hydrophobic substrate coated with the SBR dispersion is guided to a hot air dryer, dried as desired, and then wound up by a winder.

(2) Preparation of MFC dispersion IPA (primary reagent) was added to an MFC aqueous dispersion (solid content concentration 3% by mass) obtained by the same method as in “1. Production of composite sheet by hand coating (Part 1)”. ) And ion-exchanged water were added to prepare an MFC dispersion having an MFC solid content concentration of 1% by mass and IPA / water = 25/75 (mass ratio).

(3) Application of MFC dispersion to spunbonded nonwoven fabric (fine cellulose coating process)
The MFC dispersion liquid was applied to the spunbonded nonwoven fabric by the pilot plant shown in FIG.
After pre-coating an IPA / water mixture (IPA / water = 20/80) on the surface of a spunbond nonwoven fabric (PE spunbond nonwoven fabric, 15.5 g / m ² , manufactured by Idemitsu Unitech Co., Ltd., about 2 denier constituent fibers) Further, the MFC dispersion obtained above was applied using a slurry coater. The roll clearance during application of the MFC dispersion was 0.9 mm.
As a result, a smooth and uniform coated surface was obtained.

(4) Liquid removal and drying (drying process)
Subsequently, drainage and drying were performed by the pilot plant shown in FIG.
The spunbonded nonwoven fabric coated with the MFC dispersion is drained by vacuum suction, and then the coated surface is applied to a heated drum dryer with a Teflon (registered trademark) coating on the surface with a liquid content of 120% by mass. It was made to adhere and dry, and also it was made to dry with hot air, the composite sheet was obtained, and this was wound up by the winder.
The surface temperature of the heating drum was 105 ° C., and the hot air temperature was 80 ° C. The resulting composite sheet had a moisture content of 7% by mass, but no residual odor of IPA was detected.

About the obtained composite sheet, the MFC coating amount and the Gurley air permeability were measured. The Gurley air permeability was measured at 10 locations, and the average value was obtained.
In addition, the Gurley gas permeability can be obtained in the same manner as described above for a film formed by heat-sealing at 130 ° C. while applying pressure to the coated surface of the obtained composite sheet and melting the surface of the spunbond nonwoven fabric. The degree was measured.
As a result, the application amount of MFC was 8.0 g / m ² and the Gurley air permeability was 76 sec / 100 mL. After the heat welding treatment, the Gurley air permeability was about 3000 sec / 100 mL. Therefore, it was found that the air permeability is greatly reduced by the heat welding process.

5). Production of composite sheet by pilot plant (Part 2)
(1) Preparation of MFC dispersion A PE resin dispersion was added to an MFC aqueous dispersion (solid content concentration 3% by mass) obtained by the same method as in “1. Production of composite sheet by hand coating (Part 1)”. (Hydrocer 257, manufactured by Shamrock Technology, dispersion of low molecular weight polyethylene), IPA (primary reagent) and ion-exchanged water were added, MFC solid content concentration 0.8 mass%, PE resin solid content concentration 1.5 mass %, IPA / water = 20/80 (mass ratio) MFC dispersion. This MFC dispersion did not cause phase separation or precipitation even after standing for a long time. This is considered to be due to the extremely stable dispersion state due to the thickening effect of MFC.

(2) Application of MFC dispersion to SMS nonwoven fabric (fine cellulose coating process)
The MFC dispersion was applied to the SMS nonwoven fabric by the pilot plant shown in FIG.
After pre-coating an IPA / water mixture (IPA / water = 20/80) on the surface of the SMS nonwoven fabric (PP SMS nonwoven fabric, 13.2 g / m ² , Avgor), the above was further performed using a slurry coater. The MFC dispersion obtained in (1) was applied. The roll clearance during application of the MFC dispersion was 1.2 mm.
As a result, a smooth and uniform coated surface was obtained.

(3) Liquid removal and drying (drying process)
Subsequently, drainage and drying were performed by the pilot plant shown in FIG.
After the SMS nonwoven fabric coated with the MFC dispersion is drained by vacuum suction, the coated surface is in close contact with a heated drum dryer with a Teflon (registered trademark) coating on the surface with a liquid content of 98% by mass. And then dried with hot air to obtain a composite sheet, which was wound around a winder.
The surface temperature of the heating drum was 103 ° C., and the hot air temperature was 82 ° C. The obtained composite sheet had a water content of 10% by mass, but no residual odor of IPA was detected.

About the obtained composite sheet, the MFC coating amount, the PE resin coating amount, and the Gurley air permeability were measured, and the surface state was visually observed. The Gurley air permeability was measured at 10 locations, and the average value was obtained.
In addition, the Gurley air permeability can be obtained by applying the heat treatment at 130 ° C. while applying pressure to the coated surface of the obtained composite sheet, and melting the surface of the SMS nonwoven fabric to form a film by the same method as described above. Was measured.
As a result, the MFC coating amount was 6.8 g / m ² , the PE resin coating amount was 12.0 g / m ² , and the Gurley air permeability was 30 sec / 100 mL. After the heat welding treatment, the Gurley air permeability was about 5000 sec / 100 mL. Therefore, it was found that the air permeability is greatly reduced by the heat welding process.
Further, in the obtained composite sheet, MFC and PE resin were integrated, and peeling between these and the SMS nonwoven fabric did not occur. The PE resin did not reach a molten state, and had a soft non-woven appearance due to the adhesive effect of the PE resin to the SMS non-woven fabric. After the heat welding treatment, the MFC was impregnated with the melted PE resin, resulting in a cloudy film.

6). Production of composite sheet by pilot plant (Part 3)
(1) Preparation of MFC dispersion MFC aqueous dispersion (solid content concentration: 3% by mass) obtained by the same method as in “1. Production of composite sheet by hand coating (Part 1)” and IPA (primary grade) Reagent) and ion-exchanged water were added to prepare an MFC dispersion having an MFC solid content concentration of 1% by mass and IPA / water = 25/75 (mass ratio).

(2) Preparation of SBR dispersion liquid A mixture of IPA (primary reagent) and water was added to SBR emulsion (Smartex PA-3807, manufactured by Nippon A & L Co., Ltd., solid content concentration 48.3 mass%), and SBR was added. An SBR dispersion having a solid content concentration of 10% by mass and IPA / water = 20/80 (mass ratio) was prepared.

(3) Application of MFC dispersion to SMS nonwoven fabric (fine cellulose coating process)
The MFC dispersion was applied to the SMS nonwoven fabric by the pilot plant shown in FIG.
After pre-coating an IPA / water mixture (IPA / water = 20/80) on the surface of the SMS nonwoven fabric (PP SMS nonwoven fabric, 13.2 g / m ² , Avgor), the above was further performed using a slurry coater. The MFC dispersion obtained in (1) was applied. The roll clearance during application of the MFC dispersion was 0.9 mm.
As a result, a smooth and uniform coated surface was obtained.

(4) Liquid removal and drying (first drying step)
Subsequently, drainage and drying were performed by the pilot plant shown in FIG.
After the SMS nonwoven fabric coated with the MFC dispersion was drained by vacuum suction, the coated surface was in close contact with a heated drum dryer with a Teflon (registered trademark) coating on the surface with a liquid content of 110% by mass. It was made to dry, and also it was made to dry by ventilation, and was pre-dried to the state of 65 mass% of liquid contents.
The surface temperature of the heating drum was 80 ° C., and the blowing temperature was room temperature.

(5) Application of SBR dispersion liquid to SMS nonwoven fabric coated with MFC (waterproofing agent coating process after drying)
Subsequently, the SBR dispersion was applied by the pilot plant shown in FIG.
The SBR dispersion obtained above was applied to the surface of the MFC-coated surface of the SMS nonwoven fabric after the preliminary drying using a spray coater so that the coating amount was 50 g / m ² (solid).

(6) Drying (second drying step)
Subsequently, drying was performed by a pilot plant shown in FIG.
The SMS nonwoven fabric coated with the SBR dispersion was dried with hot air to obtain a composite sheet, which was wound around a winder.
The hot air temperature was 85 ° C. The obtained composite sheet had a water content of 10% by mass, but no residual odor of IPA was detected.
About the obtained composite sheet, the MFC coating amount, the SBR coating amount, and the Gurley air permeability were measured, and a ring seal test was performed to evaluate the water resistance. In addition, the Gurley air permeability measured 10 places of each sample and calculated | required the average value.
As a result, the MFC coating amount was 8.0 g / m ² , the SBR coating amount was 4.8 g / m ² , and the Gurley air permeability was 53 sec / 100 mL. The water resistance was a slight amount of leakage after 24 hours.

DESCRIPTION OF SYMBOLS 1 Acrylic board 2 Hydrophobic nonwoven fabric 3 1 mL capacity micropipette 4, 4 'Position where all the droplets have been absorbed into the nonwoven fabric 5, 5' Location where the droplets have been dropped 6, 6 'Total amount of the droplets within the nonwoven fabric Distance between the position where the liquid is completely absorbed and the position where the droplet is dropped 11 ring 12 transparent glass plate 13 sample 14 filter paper for detection 15 mirror for observation 16 dye water

Claims (11)

A fine cellulose application step of applying a fine cellulose dispersion containing fine cellulose, water and a wetting / penetrating agent to the surface of the hydrophobic substrate;
And drying the hydrophobic substrate coated with the fine cellulose dispersion to obtain a composite sheet of the fine cellulose and the hydrophobic substrate. And
The combination of the kind of the wetting / penetrating agent and the mass ratio of the wetting / penetrating agent with respect to the total of the water and the wetting / penetrating agent in the fine cellulose dispersion is from the following (a) to (g): A method for producing a composite sheet selected from the group consisting of:
(A) Ethyl alcohol: Concentration 20% or more and less than 40% (b) 1-Propyl alcohol: Concentration 11% or more and less than 40% (c) Isopropyl alcohol: Concentration 11% or more and less than 40% (d) 1-Butyl alcohol: Concentration 1% to 8% (e) 2-butyl alcohol: concentration 10% to 13% (f) t-butyl alcohol: concentration 6% to less than 40% (g) 3,5-dimethyl-1-hexyne-3 -All: Concentration from 0.5% to 0.9% Furthermore, after the coating step and before the drying step,
A pre-drying water-resistant treatment agent coating step of applying a water-resistant treatment agent dispersion containing a water-resistant treatment agent and water to a portion of the hydrophobic substrate on which the fine cellulose dispersion is applied. Item 2. A method for producing a composite sheet according to Item 1. A fine cellulose application step of applying a fine cellulose dispersion containing fine cellulose, water and a wetting / penetrating agent to the surface of the hydrophobic substrate;
A first drying step of drying the hydrophobic substrate coated with the fine cellulose dispersion;
A post-drying water-resistant treatment agent application step of applying a water-resistant treatment agent dispersion containing a water-resistant treatment agent, water and a wetting / penetrating agent to the portion of the hydrophobic substrate on which the fine cellulose dispersion is applied When,
A method for producing a composite sheet, comprising: drying the hydrophobic substrate coated with the water-resistant treatment agent dispersion, and obtaining a composite sheet.
In both the fine cellulose coating step and the post-drying water-resistant treatment agent coating step, the type of the wetting / penetrating agent and the water and the wetting / penetrating agent in the fine cellulose dispersion or the water-resistant treatment agent dispersion The method for producing a composite sheet, wherein the combination with the mass ratio of the wetting / penetrating agent to the total is selected from the group consisting of the following (a) to (g).
(A) Ethyl alcohol: Concentration 20% or more and less than 40% (b) 1-Propyl alcohol: Concentration 11% or more and less than 40% (c) Isopropyl alcohol: Concentration 11% or more and less than 40% (d) 1-Butyl alcohol: Concentration 1% to 8% (e) 2-butyl alcohol: concentration 10% to 13% (f) t-butyl alcohol: concentration 6% to less than 40% (g) 3,5-dimethyl-1-hexyne-3 -All: Concentration from 0.5% to 0.9% Furthermore, after the coating step and before the first drying step,
A pre-drying water-resistant treatment agent coating step of applying a water-resistant treatment agent dispersion containing a water-resistant treatment agent and water to a portion of the hydrophobic substrate on which the fine cellulose dispersion is applied. Item 4. A method for producing a composite sheet according to Item 3. Further, a water-resistant treatment agent for applying a water-resistant treatment agent dispersion containing a water-resistant treatment agent, water and a wetting / penetrating agent to the surface of the hydrophobic substrate opposite to the one on which the fine cellulose dispersion is applied. A method for producing a composite sheet comprising a backside coating process,
In the water-resistant treatment agent backside coating step, the combination of the type of the wetting / penetrating agent and the mass ratio of the wetting / penetrating agent to the total of the water and the wetting / penetrating agent in the water-resistant treatment agent dispersion is as follows: The manufacturing method of the composite sheet in any one of Claims 1-4 selected from the group which consists of (a)-(g).
(A) Ethyl alcohol: Concentration 20% or more and less than 40% (b) 1-Propyl alcohol: Concentration 11% or more and less than 40% (c) Isopropyl alcohol: Concentration 11% or more and less than 40% (d) 1-Butyl alcohol: Concentration 1% to 8% (e) 2-butyl alcohol: concentration 10% to 13% (f) t-butyl alcohol: concentration 6% to less than 40% (g) 3,5-dimethyl-1-hexyne-3 -All: Concentration from 0.5% to 0.9%   The method for producing a composite sheet according to any one of claims 1 to 5, wherein the fine cellulose dispersion further contains a water-resistant treatment agent.   The method for producing a composite sheet according to claim 6, wherein at least one of the water-resistant treatment agent is a resin emulsion and / or latex.   The method for producing a composite sheet according to any one of claims 1 to 7, wherein the fine cellulose has a water holding amount of 10 mL / g or more that represents a volume of water that can be held by the fine cellulose having a unit mass.   The method for producing a composite sheet according to any one of claims 1 to 8, wherein the fine cellulose is biocellulose and / or microfibrillated cellulose. The manufacturing method of the composite sheet in any one of Claims 1-9 whose said hydrophobic base material is a nonwoven fabric of the hydrophobic synthetic fiber of 10-50 g / m < ² > of fabric weights.   The method for producing a composite sheet according to claim 10, wherein the non-woven fabric is a spunbond / meltblown composite non-woven fabric.

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