JP2018171730A - Laminated sheet - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fine fibrous cellulose-containing sheet having excellent channel functionality and capable of preventing sample contamination.SOLUTION: This invention relates to a laminated sheet that has a fiber layer containing fibrous cellulose with a fiber width of 1000 nm or less, and a coating layer on at least one side of the fiber layer. The laminated sheet has internal cavities, and outer peripheral walls forming the individual internal cavities are formed from the fiber layer and coating layer.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a laminated sheet. Specifically, the present invention relates to a laminated sheet including a fiber layer containing fine fibrous cellulose and a coating layer.

  In recent years, materials that use reproducible natural fibers have attracted attention due to the substitution of petroleum resources and the growing environmental awareness. Among natural fibers, fibrous cellulose having a fiber diameter of 10 μm or more and 50 μm or less, in particular, fibrous cellulose (pulp) derived from wood has been widely used mainly as a paper product so far.

  As the fibrous cellulose, fine fibrous cellulose having a fiber diameter of 1 μm or less is also known. And the sheet | seat comprised from such a fine fibrous cellulose and the composite sheet containing a fine fibrous cellulose containing sheet | seat and a resin layer are developed. Known composite sheets include a sheet obtained by dispersing and curing fine fibrous cellulose in a resin composition, and a sheet obtained by impregnating a resin component into a fine fibrous cellulose sheet. In addition, a laminated sheet obtained by laminating a resin sheet and a fine fibrous cellulose sheet is also known.

  In the sheet containing fine fibrous cellulose as described above, it has been studied to exhibit desired properties by forming an uneven shape on the sheet surface or the laminated surface of the sheet. For example, Patent Document 1 discloses a cellulose nanometer having a base material having a groove-shaped pattern and a cellulose nanofiber layer formed by applying a coating liquid containing cellulose nanofibers on the surface on which the groove shape is formed. A fiber laminate is disclosed. In the cellulose nanofiber laminate of Patent Document 1, the boundary surface between the base material and the cellulose nanofiber layer is formed to have an uneven shape, and by adopting such a structure, a laminate excellent in gas barrier properties. It is being considered to manufacture.

  Since the fine fibrous cellulose sheet has excellent transparency, application to an optical sheet is also being studied. For example, Patent Document 2 discloses an optical film including a transparent film and a hard coat layer having a concavo-convex structure on the surface, and the hard coat layer includes a curable resin precursor and cellulose nanofibers. Patent Document 3 discloses an organic EL element in which a curable resin layer, a transparent conductive layer, an organic layer, and a metal electrode layer are laminated on a transparent substrate. In the organic EL element disclosed in Patent Document 3, the transparent substrate includes cellulose nanofibers, and a concavo-convex pattern shape is formed on the surface of the curable resin layer opposite to the surface in contact with the transparent substrate.

JP 2014-65233 A JP 2014-92551 A JP 2012-28307 A

A sheet containing fine fibrous cellulose and having a concavo-convex shape is expected to be applied to various applications, and when the concavo-convex concave portion becomes a groove, the groove is good as a flow path. It may be required to function. Depending on the application, sample contamination (contamination) may be a problem when a fluid is allowed to flow through the groove.
Therefore, in order to solve the problems of the prior art, the present inventors have a fine fibrous cellulose-containing sheet having a concavo-convex shape, have excellent flow path functionality, and suppress sample contamination. Investigations have been made for the purpose of providing a sheet containing fine fibrous cellulose.

As a result of intensive studies to solve the above problems, the present inventors have found that in a laminated sheet having a fiber layer containing fibrous cellulose having a fiber width of 1000 nm or less and a coating layer, the outer peripheral wall is a fiber. It has been found that a laminated sheet having excellent flow path functionality and suppressing sample contamination can be obtained by forming an internal void formed from a layer and a coating layer.
Specifically, the present invention has the following configuration.

[1] A laminated sheet comprising a fiber layer containing fibrous cellulose having a fiber width of 1000 nm or less, and a coating layer on at least one surface of the fiber layer, the laminated sheet having internal voids, The outer peripheral wall that forms the internal void of the laminated sheet is formed from a fiber layer and a coating layer.
[2] The laminated sheet according to [1], wherein the internal void includes a concave portion of the fiber layer.
[3] The laminated sheet according to [1] or [2], wherein the internal void is configured by a concave portion of the fiber layer and a concave portion of the coating layer.
[4] The laminated sheet according to any one of [1] to [3], wherein the coating layer includes fibrous cellulose having a fiber width of 1000 nm or less.
[5] The laminated sheet according to any one of [1] to [4], wherein the internal gap extends in a planar direction, and the maximum width of the internal gap is 1 μm or more and 10 mm or less.
[6] The internal space extends in the plane direction, and when the maximum width of the internal space is W and the height of the internal space is T, the value represented by W / T is 0.1 or more and 1000 The laminated sheet according to any one of [1] to [5], which is as follows.
[7] The laminated sheet according to any one of [1] to [6], wherein the internal gap is a flow path for flowing a fluid.
[8] The laminated sheet according to any one of [1] to [7], further including a resin layer on one surface of the fiber layer and on the surface opposite to the surface on which the coating layer is provided. .

  According to the present invention, it is possible to obtain a laminated sheet having excellent flow path functionality and capable of suppressing sample contamination.

FIG. 1 is a cross-sectional view of an embodiment of the sheet of the present invention. FIG. 2 is a plan view for explaining the form of the concave portion of the sheet of the present invention. FIG. 3 is a cross-sectional view illustrating the cross-sectional shape of the concave portion of the sheet of the present invention. FIG. 4 is a graph showing the relationship between the amount of dropped NaOH and electrical conductivity for a fiber raw material having a phosphate group. FIG. 5 is a graph showing the relationship between the amount of NaOH dropped and the electrical conductivity for a fiber material having a carboxyl group. FIG. 6 is a cross-sectional view of one embodiment of the sheet of the present invention.

  Hereinafter, the present invention will be described in detail. The description of the constituent elements described below may be made based on representative embodiments and specific examples, but the present invention is not limited to such embodiments.

(Laminated sheet)
The present invention relates to a laminated sheet comprising a fiber layer containing fibrous cellulose having a fiber width of 1000 nm or less and a coating layer on at least one surface of the fiber layer. The laminated sheet of the present invention has internal voids, and the outer peripheral wall forming each internal void is formed of a fiber layer and a coating layer.

  FIG. 1 is a cross-sectional view illustrating the configuration of the laminated sheet of the present invention. As shown in FIGS. 1A to 1C, the laminated sheet 10 has a coating layer 14 on one surface of the fiber layer 12. And the lamination sheet 10 has the internal space | gap 20, and this internal space | gap 20 is formed so that the interface of the fiber layer 12 and the coating layer 14 may be included, or the interface of the fiber layer 12 and the coating layer 14 Is formed to be the outer peripheral wall of the internal space 20. That is, the outer peripheral wall forming each internal void 20 is formed from the fiber layer 12 and the coating layer 14. In the present specification, the boundary surface between the fiber layer 12 and the coating layer 14 is a boundary surface between the fiber layer 12 and the coating layer 14 at a location where the internal void 20 is not present. A virtual surface obtained by extending a boundary surface at a location where no slab exists in a direction orthogonal to the thickness direction is referred to as a boundary surface.

In FIG. 1A, concave portions having the same shape are formed at the same interval in both the fiber layer 12 and the covering layer 14, and one concave portion formed in the fiber layer 12 and 1 formed in the covering layer 14. By connecting the two concave portions, one internal space 20 is formed. FIGS. 1B and 1C show a mode in which the internal void 20 includes the boundary surface between the fiber layer 12 and the coating layer 14 as an outer peripheral wall. In FIG. 1B, a concave portion is formed only in the fiber layer 12, and the internal void 20 is formed by laminating the coating layer 14 so as to close the internal space of the concave portion. On the other hand, in FIG.1 (c), the recessed part is formed only in the coating layer 14, and the internal space | gap 20 is formed by laminating | stacking the fiber layer 12 so that the internal space of this recessed part may be block | closed.
Especially, in this invention, it is preferable to set it as the aspect of FIG. 1 (a) and (b), and it is preferable that the internal space | gap 20 contains the recessed part of the fiber layer 20. FIG. Furthermore, the internal space 20 is more preferably in the form of FIG. 1A, and the internal space 20 is more preferably composed of a concave portion of the fiber layer and a concave portion of the coating layer.

  Since the laminated sheet of the present invention has the above-described configuration, it has excellent flow path functionality and suppresses sample contamination (contamination) when a sample such as a fluid is allowed to flow down into the internal space. it can. Here, the flow path functionality of the laminated sheet can be determined by whether or not the fluid smoothly flows through the internal space of the laminated sheet. Specifically, when a fluid is dropped on one end region in the longitudinal direction of the internal gap and the laminated sheet is tilted by 20 ° so that the end region is located above, the other end in the longitudinal direction of the internal gap It is preferable that the fluid reaches the partial area. At this time, it is more preferable that the diffusion of the fluid stays only in the inner space and the area around the inner space, and it is more preferable that the fluid stays only in the inner space. Moreover, it is preferable that the diffusion in the thickness direction is small, and it is preferable that the fluid does not reach the back surface of the fiber layer of the laminated sheet. For example, an organic solvent such as isopropyl alcohol can be used as the fluid used for evaluating the flow path functionality of the laminated sheet.

  Sample contamination (contamination) means that the sample (fluid, etc.) provided in the internal space of the laminated sheet is contaminated with foreign matter or microorganisms. The suppression of sample contamination can be evaluated by the following method. it can. First, the evaluation sheet is put in an autoclave (Tomy Seiko Co., Ltd., LBS-325) and sterilized at 121 ° C. for 15 minutes. Next, the evaluation sheet is allowed to stand in a temperature / humidity adjustment chamber at 23 ° C. and a relative humidity of 50% for 5 minutes. Thereafter, the evaluation sheet is transferred into a clean bench, and the coating layer is preliminarily flame sterilized (the tip is flamed). Remove with tweezers and scissors. Then, the inner wall of the recess formed in the fiber layer of the evaluation sheet is scratched 10 times with a toothpick that has been subjected to a flame sterilization treatment in advance, and then the toothpick is immersed in 10 mL of sterile water and shaken. 1 mL of the sterilized water is dropped on a glass bottom petri dish (diameter: 12 cm) containing a standard agar medium using a micropipette, and is diffused throughout the medium using a conage rod that has been subjected to flame sterilization. Thereafter, culture is performed at 32 ° C. for 48 hours, and the number of microbial colonies formed after the culture is confirmed. At this time, the number of colonies formed is preferably less than 100, and more preferably less than 10.

  Moreover, the laminated sheet of the present invention has sufficient tensile resistance. The tensile strength of the laminated sheet is a test piece obtained by cutting the laminated sheet into a length of 7 cm and a width of 15 mm, and conforms to JIS P 8113 except that the distance between chucks is 50 mm. A tensile tester (manufactured by L & W, Tensile Tester CODE). SE-064) is used to measure the tensile strength (unit: N / m) at a temperature of 23 ° C. and a relative humidity of 50%. The tensile strength is divided by the thickness of the test piece (the thickness of the entire laminated sheet measured in a region where no internal voids are present) to obtain the tensile strength (unit: MPa). When the internal gap of the laminated sheet extends in one direction in the plane direction, when cutting out the test piece, it is cut so that the extending direction of the internal gap and the length direction of the test piece are orthogonal to each other. . The tensile strength measured in this manner is preferably 35 MPa or more, more preferably 50 MPa or more, and further preferably 65 MPa or more. In addition, although the upper limit of the tensile strength of a lamination sheet is not specifically limited, For example, it can be 500 MPa.

  Since the laminated sheet of the present invention has a fiber layer containing fibrous cellulose having a fiber width of 1000 nm or less, it is also characterized in that the moldability (dimensional stability) of internal voids formed in the laminated sheet is good. . In the present invention, since the fiber layer functions to suppress distortion of the internal voids, the moldability (dimensional stability) of the internal voids can be effectively improved.

  In the present invention, the internal void 20 preferably extends in the planar direction, and more preferably extends along one direction in the planar direction. In FIG. 2, a cross-sectional shape of the internal space 20 exposed on a plane when the coating layer 14 is removed from the laminated sheet 10 is illustrated. The internal space 20 may have a single tunnel shape as shown in FIG. Further, as shown in FIG. 2B, a plurality of tunnel-shaped internal voids 20 may be formed. Note that one end and the other end of the tunnel-shaped internal gap 20 may coincide with the end face of the laminated sheet, or may exist inside the end face of the laminated sheet.

  Further, as shown in FIG. 2 (c), the tunnel-shaped internal gap 20 can be structured such that the width thereof is narrowed from one end to the other end in the longitudinal direction, as shown in FIG. 2 (d). As can be seen, the shape can meander. A structure in which two or more internal voids 20 merge at one place or a crossing structure can also be employed.

  When the internal void 20 has a tunnel shape, for example, the longitudinal direction of the internal void 20 may be inclined by giving a gradient to the thickness of the fiber layer 12. By adopting such a structure, the fluid can easily flow along the longitudinal direction of the internal space 20.

  The cross-sectional shape of the internal gap in the thickness direction is not particularly limited, and can be a polygon or a circle. For example, FIG. 3A shows an example in which the cross-sectional shape in the thickness direction of the internal void 20 is a square shape. Here, the outer peripheral wall forming the internal space 20 is composed of two side surfaces, an upper surface and a bottom surface. In FIG. 3A, each side surface of the outer peripheral wall forming the internal space 20 is composed of the fiber layer 12 and the covering layer 14, the upper surface of the outer peripheral wall is composed of the covering layer 14, and the bottom surface of the outer peripheral wall is It is composed of a fiber layer 12. FIG. 3B shows an example in which the cross-sectional shape in the thickness direction of the internal space 20 is a shape (circular shape) surrounded by a curved surface. Here, the lower part of the outer peripheral wall is constituted by the fiber layer 12, and the upper part of the outer peripheral wall is constituted by the covering layer 14. FIG. 3C shows an example where the cross-sectional shape in the thickness direction of the internal void 20 is a rhombus. In FIG. 3C, two sides disposed on the lower side portion of the outer peripheral wall are configured from the fiber layer 12, and two sides disposed on the upper side portion of the outer peripheral wall are configured from the coating layer 14.

  The maximum width of the internal void 20 can be appropriately adjusted depending on the use of the laminated sheet. For example, it is preferably 1 μm or more and 10 mm or less, more preferably 5 μm or more and 5 mm or less, and 5 μm or more and 2 mm or less. More preferably. Here, the maximum width of the internal void 20 is the width in the parallel direction indicated by W in FIGS. 3A to 3C, and the maximum width in the cross section in the thickness direction of the internal void 20. When measuring the maximum width of the internal void 20, the cross-section in the thickness direction of the internal void 20 of the laminated sheet is observed with an optical microscope, the maximum width of the internal void 20 at any 10 points is measured, and the average value is calculated. The maximum width of the internal space 20 is calculated.

  When the maximum width of the internal void is W and the height of the internal void is T, the value represented by W / T is preferably 0.1 or more and 1000 or less, and is 0.1 or more and 500 or less. More preferably, it is 0.2 or more and 250 or less. The value represented by W / T can also be referred to as the aspect ratio of the cross-sectional shape in the thickness direction of the internal void. By setting the value represented by W / T within the above range, it is possible to improve the flow when flowing the fluid through the internal gap.

  The thickness of the entire laminated sheet of the present invention is preferably 10 μm or more, more preferably 20 μm or more, and further preferably 30 μm or more. Moreover, it is preferable that the thickness of the whole lamination sheet is 3000 micrometers or less, It is more preferable that it is 2000 micrometers or less, It is further more preferable that it is 1000 micrometers or less.

  The height of the internal void is preferably 1 μm or more, more preferably 3 μm or more, further preferably 5 μm or more, and further preferably 10 μm or more. In addition, the height of the internal void is preferably 200 μm or less, more preferably 50 μm or less, and further preferably 30 μm or less. By setting the thickness of the entire laminated sheet and the height of the internal voids within the above ranges, the tensile resistance of the laminated sheet can be increased. When measuring the height of the internal void, observe the cross section in the thickness direction of the internal void of the laminated sheet with an optical microscope, measure the height of the internal void at any 10 points, and calculate the average value And the height of the internal void.

  As described above, since the internal gap can flow down the fluid, it is preferably used as a flow path for flowing the fluid. That is, the laminated sheet of the present invention is preferably a flow path containing sheet.

(Fiber layer)
The fiber layer is a layer containing fibrous cellulose having a fiber width of 1000 nm or less. In the present specification, fibrous cellulose having a fiber width of 1000 nm or less is also referred to as fine fibrous cellulose.

  In the present invention, the content of fibrous cellulose having a fiber width of 1000 nm or less (fine fibrous cellulose) contained in the fiber layer is preferably 60% by mass or more based on the total mass of the fiber layer, 70 More preferably, the content is at least 80% by mass, and even more preferably at least 80% by mass. Moreover, 100 mass% may be sufficient as content of the fine fibrous cellulose contained in a fiber layer.

  The thickness of the fiber layer is preferably 5 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, and further preferably 30 μm or more. Although the upper limit of the thickness of a fiber layer is not specifically limited, For example, it is preferable to set it as 1000 micrometers. In addition, when the recessed part is formed in the fiber layer, the thickness of a fiber layer is the thickness of the fiber layer of the area | region in which the recessed part is not formed.

  The fiber layer may further contain other optional components in addition to the fine fibrous cellulose. As an arbitrary component, an oxygen-containing organic compound (however, the said cellulose fiber is excluded) can be mentioned, for example. The oxygen-containing organic compound is preferably a hydrophilic organic compound. The hydrophilic oxygen-containing organic compound can improve the strength, density and chemical resistance of the fiber layer.

  Examples of the oxygen-containing organic compound include polyethylene glycol, polyethylene oxide, casein, dextrin, starch, modified starch, polyvinyl alcohol, modified polyvinyl alcohol (such as acetoacetylated polyvinyl alcohol), polyvinyl pyrrolidone, polyvinyl methyl ether, and polyacrylates. , Hydrophilic polymers such as polyacrylamide, alkyl acrylate copolymer, urethane copolymer, cellulose derivatives (hydroxyethyl cellulose, carboxyethyl cellulose, carboxymethyl cellulose, etc.); hydrophilic low molecules such as glycerin, sorbitol, ethylene glycol, etc. Is mentioned. Among these, polyethylene glycol, polyethylene oxide, glycerin, sorbitol, and polyvinyl alcohol are preferable from the viewpoint of improving the strength, density, chemical resistance, and the like of the fiber layer, and at least one selected from polyethylene glycol, polyvinyl alcohol, and polyethylene oxide. More preferably it is a seed.

  The oxygen-containing organic compound is preferably an organic compound polymer having a molecular weight of 50,000 to 8,000,000. The molecular weight of the oxygen-containing organic compound is preferably 100,000 to 5,000,000, but may be a low molecule having a molecular weight of less than 1,000, for example.

  Moreover, an organic ion can also be mentioned as an arbitrary component. Examples of organic ions include tetraalkylammonium ions and tetraalkylphosphonium ions. Examples of tetraalkylammonium ions include tetramethylammonium ion, tetraethylammonium ion, tetrapropylammonium ion, tetrabutylammonium ion, tetrapentylammonium ion, tetrahexylammonium ion, tetraheptylammonium ion, tributylmethylammonium ion, and lauryltrimethyl. Examples include ammonium ion, cetyltrimethylammonium ion, stearyltrimethylammonium ion, octyldimethylethylammonium ion, lauryldimethylethylammonium ion, didecyldimethylammonium ion, lauryldimethylbenzylammonium ion, and tributylbenzylammonium ion. Examples of tetraalkylphosphonium ions include tetramethylphosphonium ions, tetraethylphosphonium ions, tetrapropylphosphonium ions, tetrabutylphosphonium ions, and lauryltrimethylphosphonium ions. In addition, examples of the tetrapropylonium ion and the tetrabutylonium ion include a tetra n-propylonium ion and a tetra n-butylonium ion, respectively.

  In addition, the fiber layer has optional components such as coupling agents, inorganic layered compounds, inorganic compounds, leveling agents, antifoaming agents, organic particles, lubricants, antistatic agents, UV protection agents, dyes, pigments, stabilizers, and magnetic materials. You may contain a powder, an orientation promoter, a plasticizer, a crosslinking agent, etc.

  The content of the optional component contained in the fiber layer is preferably 40 parts by mass or less, more preferably 30 parts by mass or less, with respect to 100 parts by mass of the fine fibrous cellulose contained in the fiber layer. More preferably, it is at most part by mass. By setting the content of the optional component within the above range, a laminated sheet having high transparency and strength can be formed.

  The fiber layer preferably includes a recess that constitutes an internal space, and the recess is more preferably a groove. A laminated sheet having internal voids can be obtained by laminating a coating layer, which will be described later, on the concave surface of the fiber layer having such concave portions.

<Fine fibrous cellulose>
Although it does not specifically limit as a fibrous cellulose raw material for obtaining a fine fibrous cellulose, It is preferable to use a pulp from the point of being easy to acquire and cheap. Examples of the pulp include wood pulp, non-wood pulp, and deinked pulp. Examples of wood pulp include hardwood kraft pulp (LBKP), softwood kraft pulp (NBKP), sulfite pulp (SP), dissolved pulp (DP), soda pulp (AP), unbleached kraft pulp (UKP), oxygen bleached craft Chemical pulps such as pulp (OKP) are listed. Further, semi-chemical pulps such as semi-chemical pulp (SCP) and chemiground wood pulp (CGP), mechanical pulps such as ground wood pulp (GP), and thermomechanical pulp (TMP, BCTMP) are exemplified, but not limited thereto. Non-wood pulp includes cotton pulp such as cotton linter and cotton lint, non-wood pulp such as hemp, straw and bagasse, cellulose isolated from sea squirts and seaweed, chitin, chitosan, etc., but is not particularly limited. . The deinking pulp includes deinking pulp made from waste paper, but is not particularly limited. The pulp of this embodiment may be used alone or in combination of two or more. Among the above pulps, wood pulp containing cellulose and deinked pulp are preferable in terms of availability. Among wood pulps, chemical pulp has a large cellulose ratio, so the yield of fine fibrous cellulose during fiber refinement (defibration) is high, and the degradation of cellulose in the pulp is small, and the fineness of long fibers with a large axial ratio is high. It is preferable at the point from which fibrous cellulose is obtained. Of these, kraft pulp and sulfite pulp are most preferably selected.

  The average fiber width of the fine fibrous cellulose is 1000 nm or less as observed with an electron microscope. The average fiber width is preferably 2 nm or more and 1000 nm or less, more preferably 2 nm or more and 100 nm or less, more preferably 2 nm or more and 50 nm or less, and further preferably 2 nm or more and 10 nm or less, but is not particularly limited. When the average fiber width of the fine fibrous cellulose is less than 2 nm, the physical properties (strength, rigidity, dimensional stability) as the fine fibrous cellulose tend to be difficult to be expressed because the cellulose molecules are dissolved in water. . The fine fibrous cellulose is monofilamentous cellulose having a fiber width of 1000 nm or less, for example.

  Measurement of the fiber width of the fine fibrous cellulose by electron microscope observation is performed as follows. An aqueous suspension of fine fibrous cellulose having a concentration of 0.05% by mass or more and 0.1% by mass or less is prepared, and the suspension is cast on a carbon film-coated grid subjected to a hydrophilic treatment to prepare a sample for TEM observation. To do. When a wide fiber is included, an SEM image of the surface cast on glass may be observed. Observation with an electron microscope image is performed at a magnification of 1000 times, 5000 times, 10000 times, or 50000 times depending on the width of the constituent fibers. However, the sample, observation conditions, and magnification are adjusted to satisfy the following conditions.

(1) One straight line X is drawn at an arbitrary location in the observation image, and 20 or more fibers intersect the straight line X.
(2) A straight line Y perpendicular to the straight line is drawn in the same image, and 20 or more fibers intersect the straight line Y.

  The width of the fiber that intersects with the straight line X and the straight line Y is visually read from the observation image that satisfies the above conditions. In this way, at least three sets of images of the surface portion that do not overlap each other are observed, and the width of the fiber intersecting the straight line X and the straight line Y is read for each image. Thus, at least 20 × 2 × 3 = 120 fiber widths are read. The average fiber width of the fine fibrous cellulose is an average value of the fiber widths read in this way.

  The fiber length of the fine fibrous cellulose is not particularly limited, but is preferably 0.1 μm or more and 1000 μm or less, more preferably 0.1 μm or more and 800 μm or less, and particularly preferably 0.1 μm or more and 600 μm or less. By making the fiber length within the above range, the destruction of the crystalline region of the fine fibrous cellulose can be suppressed, and the slurry viscosity of the fine fibrous cellulose can be made an appropriate range. Note that the fiber length of the fine fibrous cellulose can be determined by image analysis using TEM, SEM, or AFM.

The fine fibrous cellulose preferably has an I-type crystal structure. Here, the fact that the fine fibrous cellulose has a type I crystal structure can be identified in a diffraction profile obtained from a wide-angle X-ray diffraction photograph using CuKα (λ = 1.5418Å) monochromatized with graphite. Specifically, it can be identified by having typical peaks at two positions of 2θ = 14 ° to 17 ° and 2θ = 22 ° to 23 °.
The proportion of the I-type crystal structure in the fine fibrous cellulose is preferably 30% or more, more preferably 50% or more, and further preferably 70% or more. In this case, further superior performance can be expected in terms of heat resistance and low linear thermal expansion coefficient. The degree of crystallinity is obtained by measuring an X-ray diffraction profile and determining the crystallinity by a conventional method (Seagal et al., Textile Research Journal, 29, 786, 1959).

  The fine fibrous cellulose is preferably one having an ionic functional group. The ionic functional group is preferably an anionic group. Examples of such an ionic functional group include a phosphate group or a substituent derived from a phosphate group (sometimes simply referred to as a phosphate group), a carboxyl group, and the like. Or a substituent derived from a carboxyl group (sometimes simply referred to as a carboxyl group) and at least one selected from a sulfone group or a substituent derived from a sulfone group (sometimes simply referred to as a sulfone group) Preferably, at least one selected from a phosphate group and a carboxyl group is more preferable, and a phosphate group is particularly preferable.

The phosphoric acid group is a divalent functional group equivalent to the phosphoric acid obtained by removing the hydroxyl group. Specifically, it is a group represented by —PO ₃ H ₂ . Substituents derived from phosphoric acid groups include substituents such as groups obtained by polycondensation of phosphoric acid groups, salts of phosphoric acid groups, and phosphoric acid ester groups. It may be a group.

In the present invention, the phosphate group or the substituent derived from the phosphate group may be a substituent represented by the following formula (1).

  In formula (1), a, b, m and n each independently represent an integer of 1 or more (provided that a = b × m); α and α ′ each independently represent R or OR. R represents a hydrogen atom, a saturated-linear hydrocarbon group, a saturated-branched hydrocarbon group, a saturated-cyclic hydrocarbon group, an unsaturated-linear hydrocarbon group, an unsaturated-branched hydrocarbon group. , An aromatic group, or a derivative group thereof; β is a monovalent or higher cation composed of an organic substance or an inorganic substance.

<Phosphate group introduction process>
In the phosphate group introduction step, the fiber raw material containing cellulose is reacted with at least one selected from a compound having a phosphate group and a salt thereof (hereinafter referred to as “phosphorylation reagent” or “compound A”). Can be performed. Such a phosphorylating reagent may be mixed in a powder or aqueous solution with a dry or wet fiber raw material. As another example, a phosphorylating reagent powder or an aqueous solution may be added to the fiber raw material slurry.

  The phosphoric acid group introduction step can be performed by reacting at least one selected from a compound having a phosphoric acid group and a salt thereof (a phosphorylating reagent or compound A) with a fiber raw material containing cellulose. This reaction may be carried out in the presence of at least one selected from urea and derivatives thereof (hereinafter referred to as “compound B”).

  As an example of a method for causing compound A to act on a fiber raw material in the presence of compound B, a method of mixing powder or an aqueous solution of compound A and compound B with a dry or wet fiber raw material can be mentioned. Another example is a method in which powders and aqueous solutions of Compound A and Compound B are added to the fiber raw material slurry. Among these, since the uniformity of the reaction is high, a method of adding an aqueous solution of Compound A and Compound B to a dry fiber material, or a powder or an aqueous solution of Compound A and Compound B to a wet fiber material The method is preferred. Moreover, the compound A and the compound B may be added simultaneously, or may be added separately. Moreover, you may add the compound A and the compound B first used for reaction as aqueous solution, and remove an excess chemical | medical solution by pressing. The form of the fiber raw material is preferably cotton or thin sheet, but is not particularly limited.

Compound A used in this embodiment is at least one selected from a compound having a phosphate group and a salt thereof.
Examples of the compound having a phosphate group include, but are not limited to, phosphoric acid, lithium salt of phosphoric acid, sodium salt of phosphoric acid, potassium salt of phosphoric acid, ammonium salt of phosphoric acid, and the like. Examples of the lithium salt of phosphoric acid include lithium dihydrogen phosphate, dilithium hydrogen phosphate, trilithium phosphate, lithium pyrophosphate, and lithium polyphosphate. Examples of the sodium salt of phosphoric acid include sodium dihydrogen phosphate, disodium hydrogen phosphate, trisodium phosphate, sodium pyrophosphate, and sodium polyphosphate. Examples of the potassium salt of phosphoric acid include potassium dihydrogen phosphate, dipotassium hydrogen phosphate, tripotassium phosphate, potassium pyrophosphate, and potassium polyphosphate. Examples of the ammonium salt of phosphoric acid include ammonium dihydrogen phosphate, diammonium hydrogen phosphate, triammonium phosphate, ammonium pyrophosphate, and ammonium polyphosphate.

  Among these, phosphoric acid and phosphoric acid are introduced efficiently from the viewpoint that the introduction efficiency of phosphate groups is high, the fibrillation efficiency is easily improved in the fibrillation process described later, the cost is low, and the industrial application is easy. Sodium salt, potassium salt of phosphoric acid, and ammonium salt of phosphoric acid are preferable. Sodium dihydrogen phosphate or disodium hydrogen phosphate is more preferable.

  In addition, compound A is preferably used as an aqueous solution because the uniformity of the reaction is increased and the efficiency of introduction of phosphate groups is increased. The pH of the aqueous solution of Compound A is not particularly limited, but is preferably 7 or less because the efficiency of introduction of phosphate groups is increased, and more preferably pH 3 or more and pH 7 or less from the viewpoint of suppressing the hydrolysis of pulp fibers. The pH of the aqueous solution of Compound A may be adjusted by, for example, using a phosphoric acid group-containing compound that exhibits acidity and an alkalinity, and changing the amount ratio thereof. You may adjust pH of the aqueous solution of the compound A by adding an inorganic alkali or an organic alkali to the thing which shows acidity among the compounds which have a phosphoric acid group.

  The amount of compound A added to the fiber raw material is not particularly limited, but when the amount of compound A added is converted to phosphorus atomic weight, the amount of phosphorus atom added to the fiber raw material (absolute dry mass) is 0.5 mass% to 100 mass%. Or less, more preferably 1% by mass or more and 50% by mass or less, and most preferably 2% by mass or more and 30% by mass or less. If the amount of phosphorus atoms added to the fiber raw material is within the above range, the yield of fine fibrous cellulose can be further improved. When the addition amount of phosphorus atoms with respect to the fiber raw material exceeds 100% by mass, the effect of improving the yield reaches a peak and the cost of the compound A to be used increases. On the other hand, a yield can be raised by making the addition amount of the phosphorus atom with respect to a fiber raw material more than the said lower limit.

  Examples of the compound B used in this embodiment include urea, biuret, 1-phenylurea, 1-benzylurea, 1-methylurea, 1-ethylurea and the like.

  Compound B is preferably used as an aqueous solution in the same manner as Compound A. Moreover, since the uniformity of reaction increases, it is preferable to use the aqueous solution in which both compound A and compound B are dissolved. The amount of Compound B added to the fiber raw material (absolute dry mass) is preferably 1% by mass or more and 500% by mass or less, more preferably 10% by mass or more and 400% by mass or less, and 100% by mass or more and 350% by mass or less. More preferably, it is more preferably 150% by mass or more and 300% by mass or less.

  In addition to Compound A and Compound B, amides or amines may be included in the reaction system. Examples of amides include formamide, dimethylformamide, acetamide, dimethylacetamide and the like. Examples of amines include methylamine, ethylamine, trimethylamine, triethylamine, monoethanolamine, diethanolamine, triethanolamine, pyridine, ethylenediamine, hexamethylenediamine, and the like. Among these, triethylamine is known to work as a good reaction catalyst.

  In the phosphoric acid group introduction step, it is preferable to perform a heat treatment. As the heat treatment temperature, it is preferable to select a temperature at which a phosphate group can be efficiently introduced while suppressing thermal decomposition and hydrolysis reaction of the fiber. Specifically, it is preferably 50 ° C. or higher and 300 ° C. or lower, more preferably 100 ° C. or higher and 250 ° C. or lower, and further preferably 150 ° C. or higher and 200 ° C. or lower. Moreover, you may use a vacuum dryer, an infrared heating apparatus, and a microwave heating apparatus for a heating.

  During the heat treatment, while water is contained in the fiber raw material slurry to which compound A is added, if the time for allowing the fiber raw material to stand still becomes long, the compound A dissolved with water molecules moves to the fiber raw material surface with drying. To do. Therefore, the concentration of the compound A in the fiber raw material may be uneven, and the introduction of phosphate groups on the fiber surface may not proceed uniformly. In order to suppress the occurrence of unevenness in concentration of Compound A in the fiber material due to drying, a very thin sheet-like fiber material is used, or the fiber material and Compound A are kneaded or stirred with a kneader or the like and dried by heating or reduced pressure. The method should be taken.

  The heating device used for the heat treatment is preferably a device that can always discharge the moisture retained by the slurry and the moisture generated by the addition reaction of the fibers such as phosphate groups to the hydroxyl group of the fiber, such as a blower oven. Etc. are preferred. If water in the system is always discharged, the hydrolysis reaction of the phosphate ester bond, which is the reverse reaction of the esterification, can be suppressed, and the acid hydrolysis of the sugar chain in the fiber can also be suppressed. A fine fiber having a high axial ratio can be obtained.

  The heat treatment time is also affected by the heating temperature, but it is preferably 1 second or more and 300 minutes or less, preferably 1 second or more and 1000 seconds or less after moisture is substantially removed from the fiber raw material slurry. Preferably, it is 10 seconds or more and 800 seconds or less. In the present invention, the amount of phosphate groups introduced can be within a preferred range by setting the heating temperature and the heating time to appropriate ranges.

  The content of phosphate groups (the amount of phosphate groups introduced) is preferably 0.10 mmol / g or more, more preferably 0.20 mmol / g or more per 1 g (mass) of fine fibrous cellulose. More preferably, it is 0.50 mmol / g or more. Further, the content of phosphate groups is preferably 3.65 mmol / g or less, more preferably 3.50 mmol / g or less, and 3.00 mmol / g or less per 1 g (mass) of fine fibrous cellulose. More preferably. By making content of a phosphate group into the said range, refinement | miniaturization of a fiber raw material can be made easy and stability of a fine fibrous cellulose can be improved. In addition, in this specification, content of the phosphoric acid group which a fine fibrous cellulose has (introduction amount of a phosphoric acid group) is equal to the strongly acidic group amount of the phosphoric acid group which a fine fibrous cellulose has so that it may mention later.

  The amount of phosphate group introduced into the fiber material can be measured by a conductivity titration method. Specifically, by performing the defibration process step, after treating the resulting fine fibrous cellulose-containing slurry with an ion exchange resin, by determining the change in electrical conductivity while adding an aqueous sodium hydroxide solution, The amount introduced can be measured.

  In conductivity titration, the curve shown in FIG. 4 is given when alkali is added. Initially, the electrical conductivity rapidly decreases (hereinafter referred to as “first region”). Thereafter, the conductivity starts to increase slightly (hereinafter referred to as “second region”). Thereafter, the conductivity increment increases (hereinafter referred to as “third region”). That is, three areas appear. The boundary point between the second region and the third region is defined as a point at which the amount of change in conductivity twice, that is, the increase (inclination) in conductivity is maximized. Among these, the amount of alkali required in the first region is equal to the amount of strongly acidic groups in the slurry used for titration, and the amount of alkali required in the second region is the amount of weakly acidic groups in the slurry used for titration. Will be equal. When the phosphoric acid group undergoes condensation, apparently weakly acidic groups are lost, and the amount of alkali required in the second region is reduced compared to the amount of alkali required in the first region. On the other hand, the amount of strongly acidic groups coincides with the amount of phosphorus atoms regardless of the presence or absence of condensation, so that the amount of phosphate groups introduced (or the amount of phosphate groups) or the amount of substituent introduced (or the amount of substituents) is simply When said, it represents the amount of strongly acidic group. That is, the alkali amount (mmol) required in the first region of the curve shown in FIG. 4 is divided by the solid content (g) in the titration target slurry to obtain the substituent introduction amount (mmol / g).

  The phosphate group introduction step may be performed at least once, but may be repeated a plurality of times. In this case, more phosphoric acid groups are introduced, which is preferable.

<Carboxyl group introduction process>
In the present invention, when the fine fibrous cellulose has a carboxyl group, for example, the fiber raw material is subjected to an oxidation treatment such as a TEMPO oxidation treatment, a compound having a carboxylic acid-derived group, a derivative thereof, or an acid thereof. Carboxyl groups can be introduced by treatment with an anhydride or derivative thereof.

  The compound having a carboxyl group is not particularly limited, and examples thereof include dicarboxylic acid compounds such as maleic acid, succinic acid, phthalic acid, fumaric acid, glutaric acid, adipic acid and itaconic acid, and tricarboxylic acid compounds such as citric acid and aconitic acid. It is done.

  The acid anhydride of the compound having a carboxyl group is not particularly limited, but examples thereof include acid anhydrides of dicarboxylic acid compounds such as maleic anhydride, succinic anhydride, phthalic anhydride, glutaric anhydride, adipic anhydride, and itaconic anhydride. It is done.

  Although it does not specifically limit as a derivative of the compound which has a carboxyl group, The derivative of the acid anhydride of the compound which has a carboxyl group and the acid anhydride imidation of a compound which has a carboxyl group are mentioned. Although it does not specifically limit as an acid anhydride imidation thing of a compound which has a carboxyl group, Imidation thing of dicarboxylic acid compounds, such as maleimide, succinic acid imide, and phthalic acid imide, is mentioned.

  The acid anhydride derivative of the compound having a carboxyl group is not particularly limited. For example, at least some of the hydrogen atoms of the acid anhydride of the compound having a carboxyl group, such as dimethylmaleic anhydride, diethylmaleic anhydride, diphenylmaleic anhydride, etc. are substituted (for example, alkyl group, phenyl group, etc. ) Are substituted.

The amount of carboxyl groups introduced is preferably 0.10 mmol / g or more, more preferably 0.20 mmol / g or more, and 0.50 mmol / g or more per 1 g (mass) of fine fibrous cellulose. Is more preferable. The carboxyl group content is preferably 3.65 mmol / g or less, more preferably 3.50 mmol / g or less, and 3.00 mmol / g or less per 1 g (mass) of fine fibrous cellulose. More preferably it is.
The amount of carboxyl group introduced into the fiber material can be measured by a conductivity titration method. In conductivity titration, when alkali is added, the curve shown in FIG. 5 is given. The alkali amount (mmol) required in the first region of the curve shown in FIG. 5 is divided by the solid content (g) in the slurry to be titrated to obtain the substituent introduction amount (mmol / g).

<Alkali treatment>
In the case of producing fine fibrous cellulose, an alkali treatment may be performed between an ionic substituent introduction step such as a phosphate group introduction step or a carboxyl group introduction step and a defibration treatment step described later. Although it does not specifically limit as a method of an alkali treatment, For example, the method of immersing an ionic substituent introduction | transduction fiber in an alkaline solution is mentioned.
The alkali compound contained in the alkali solution is not particularly limited, but may be an inorganic alkali compound or an organic alkali compound. The solvent in the alkaline solution may be either water or an organic solvent. The solvent is preferably a polar solvent (polar organic solvent such as water or alcohol), and more preferably an aqueous solvent containing at least water.
Of the alkaline solutions, a sodium hydroxide aqueous solution or a potassium hydroxide aqueous solution is particularly preferred because of its high versatility.

Although the temperature of the alkali solution in an alkali treatment process is not specifically limited, 5 to 80 degreeC is preferable and 10 to 60 degreeC is more preferable.
The immersion time in the alkaline solution in the alkali treatment step is not particularly limited, but is preferably 5 minutes or longer and 30 minutes or shorter, and more preferably 10 minutes or longer and 20 minutes or shorter.
Although the usage-amount of the alkali solution in an alkali treatment is not specifically limited, It is preferable that it is 100 mass% or more and 100,000 mass% or less with respect to the absolute dry mass of an ionic substituent introduction | transduction fiber, and is 1000 mass% or more and 10,000 mass% or less More preferably.

  In order to reduce the amount of the alkaline solution used in the alkali treatment step, the ionic substituent-introduced fiber may be washed with water or an organic solvent before the alkali treatment step. After the alkali treatment, in order to improve the handleability, it is preferable to wash the alkali-treated ionic substituent-introduced fiber with water or an organic solvent before the defibrating treatment step.

<Defibration process>
The ionic substituent-introduced fiber is defibrated in the defibrating process. In the defibrating process, the fiber is usually defibrated using a defibrating apparatus to obtain a fine fibrous cellulose-containing slurry, but the processing apparatus and the processing method are not particularly limited.
As the defibrating apparatus, a high-speed defibrator, a grinder (stone mill type pulverizer), a high-pressure homogenizer, an ultra-high pressure homogenizer, a high-pressure collision type pulverizer, a ball mill, a bead mill, or the like can be used. Alternatively, as a defibrating apparatus, a device for wet grinding such as a disk type refiner, a conical refiner, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, or a beater should be used. You can also. The defibrating apparatus is not limited to the above. Preferable defibrating treatment methods include a high-speed defibrator, a high-pressure homogenizer, and an ultra-high pressure homogenizer that are less affected by the grinding media and less worried about contamination.

  In the defibrating process, it is preferable to dilute the fiber raw material with water and an organic solvent alone or in combination to form a slurry, but there is no particular limitation. As the dispersion medium, a polar organic solvent can be used in addition to water. Preferable polar organic solvents include alcohols, ketones, ethers, dimethyl sulfoxide (DMSO), dimethylformamide (DMF), dimethylacetamide (DMAc) and the like, but are not particularly limited. Examples of alcohols include methanol, ethanol, n-propanol, isopropanol, n-butanol, and t-butyl alcohol. Examples of ketones include acetone and methyl ethyl ketone (MEK). Examples of ethers include diethyl ether and tetrahydrofuran (THF). The dispersion medium may be one type or two or more types. Further, the dispersion medium may contain a solid content other than the fiber raw material, such as urea having hydrogen bonding property.

  In the present invention, the fibrillation treatment may be performed after the fine fibrous cellulose is concentrated and dried. In this case, the concentration and drying methods are not particularly limited, and examples thereof include a method of adding a concentrating agent to a slurry containing fine fibrous cellulose, a generally used dehydrator, a press, and a method using a dryer. Moreover, a well-known method, for example, the method described in WO2014 / 024876, WO2012 / 107642, and WO2013 / 121086 can be used. Further, the concentrated fine fibrous cellulose may be formed into a sheet. The sheet can be pulverized to perform a defibrating process.

  The equipment used for pulverization of fine fibrous cellulose includes high-speed fibrillators, grinders (stone mill type pulverizers), high-pressure homogenizers, ultra-high pressure homogenizers, high-pressure collision type pulverizers, ball mills, bead mills, disk type refiners, and conicals. An apparatus for wet pulverization such as a refiner, a twin-screw kneader, a vibration mill, a homomixer under high-speed rotation, an ultrasonic disperser, a beater, and the like can be used, but is not particularly limited.

(Coating layer)
The laminated sheet of the present invention includes a coating layer on at least one surface of the fiber layer described above.

  The coating layer may contain a resin component. Examples of the resin component constituting the coating layer include an acrylic resin, a polycarbonate resin, a polyvinyl alcohol resin, an olefin resin, a polyester resin, a styrene resin, Examples thereof include a urethane resin, a phenol resin, a fluorine resin, an epoxy resin, a polyamide resin, a polyimide resin, and a silicon resin. The resin component may be a copolymer of monomers constituting the above-described resin, or a mixture of the above-described resins. Moreover, it is preferable that the resin component which comprises a coating layer contains hydrophobic resin. In the present specification, the hydrophobic resin is defined as a resin having a contact angle with water of 60 degrees or more in a dry state. Here, “in the dry state” means to exclude a state in which the hydrophobic resin has an affinity for water, such as when the hydrophobic resin is in an emulsion state.

  When the coating layer contains a resin component, the content of the resin component contained in the coating layer is preferably 60% by mass or more, more preferably 70% by mass or more, and 80% by mass or more. Is more preferable, and it is still more preferable that it is 90 mass% or more.

  Moreover, the coating layer may contain fibrous cellulose having a fiber width of 1000 nm or less. In this case, the content of fibrous cellulose (fine fibrous cellulose) having a fiber width of 1000 nm or less contained in the coating layer is preferably 60% by mass or more, and 70% by mass with respect to the total mass of the coating layer. More preferably, it is more preferably 80% by mass or more. Moreover, 100 mass% may be sufficient as content of the fine fibrous cellulose contained in a coating layer.

  The coating layer may further contain other optional components in addition to the fine fibrous cellulose. As an arbitrary component, the arbitrary component which a fiber layer can contain can be mentioned. Moreover, when a coating layer contains fine fibrous cellulose, it is also preferable to further contain the resin component mentioned above.

  The thickness of the coating layer is preferably 5 μm or more, more preferably 10 μm or more, further preferably 20 μm or more, and further preferably 30 μm or more. The upper limit value of the thickness of the coating layer is not particularly limited, but is preferably set to 1000 μm, for example. In addition, when the recessed part is formed in the coating layer, the thickness of a coating layer is the thickness of the coating layer of the area | region in which the recessed part is not formed.

  The coating layer does not need to have a concave portion that constitutes the internal void, but may include a concave portion that constitutes the internal void. When a coating layer contains a recessed part, it is preferable that the recessed part of a coating layer is formed in the same shape and the same space | interval as the recessed part formed in a fiber layer. And it is preferable that one internal space | gap is formed by connecting one recessed part formed in the fiber layer, and one recessed part formed in the coating layer. In this way, a laminated sheet having internal voids is obtained.

  When bonding a fiber layer and a coating layer, you may use an adhesive agent for a coating layer. Examples of the adhesive include acrylic resins, polycarbonate resins, polyvinyl alcohol resins, olefin resins, polyester resins, styrene resins, urethane resins, epoxy resins, silicone resins, polysaccharides, and the like. Can do. Among them, it is preferable to use a thermosetting adhesive or an ultraviolet curable adhesive as the adhesive. In addition, when using an adhesive agent when bonding a fiber layer and a coating layer, the adhesive bond layer after adhesion | attachment will be included as a part of coating layer. That is, the coating layer may be a layer further including an adhesive layer.

  Moreover, when bonding a fiber layer and a coating layer, you may use the method of heat-melting and adhering a fiber layer and / or a coating layer.

(Resin layer)
The laminated sheet of the present invention may further have a resin layer on one surface of the fiber layer and on the surface opposite to the surface on which the coating layer is provided. FIG. 6 is a cross-sectional view illustrating the configuration of the laminated sheet 10 in which the resin layer 16 is laminated on one surface of the fiber layer 12. The resin layer 16 is laminated on one surface of the fiber layer 12 and on the surface opposite to the surface on which the coating layer 14 is provided. By providing the resin layer 16 as shown in FIG. 6 on the fiber layer 12, the flow path functionality of the laminated sheet 10 can be enhanced. Moreover, the provision of the resin layer 16 can increase the tensile resistance of the laminated sheet.

  As a resin component which comprises a resin layer, the resin component similar to a coating layer can be mentioned. When the coating layer contains a resin component, the resin component constituting the coating layer and the resin component constituting the resin layer may be the same resin component or different resin components.

  Especially, it is preferable that a resin layer contains acrylic resin as a resin component. Examples of the acrylic monomer constituting the acrylic resin include 1,4-butanediol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neopentyl glycol di (meth) acrylate, polyethylene glycol di ( (Meth) acrylate, neopentyl glycol adipate di (meth) acrylate, hydroxypivalic acid neopentyl glycol di (meth) acrylate, dicyclopentanyl di (meth) acrylate, caprolactone modified dicyclopentenyl di (meth) acrylate, EO modified phosphorus Acid di (meth) acrylate, allylated cyclohexyl di (meth) acrylate, isocyanurate di (meth) acrylate, trimethylolpropane tri (meth) acrylate, ethylene oxide modified trimer Roll propane tri (meth) acrylate, dipentaerythritol tri (meth) acrylate, propionic acid modified dipentaerythritol tri (meth) acrylate, pentaerythritol tri (meth) acrylate, PO modified trimethylolpropane tri (meth) acrylate, tris ( Acryloxyethyl) isocyanurate, pentaerythritol tetraacrylate, ditrimethylolpropane tetraacrylate, dipentaerythritol penta (meth) acrylate propionic acid modified dipentaerythritol penta (meth) acrylate, dipentaerythritol hexa (meth) acrylate, caprolactone modified di Examples include pentaerythritol hexa (meth) acrylate and 1,10-decanediol diacrylate. You can.

  Moreover, it is also preferable to use together monofunctional alkyl (meth) acrylate with the polyfunctional acrylic monomer mentioned above as an acrylic monomer. Examples of monofunctional alkyl (meth) acrylates include pentyl (meth) acrylate, hexyl (meth) acrylate, heptyl (meth) acrylate, n-octyl (meth) acrylate, isooctyl (meth) acrylate, N-nonyl (meth) acrylate, isononyl (meth) acrylate, n-decyl (meth) acrylate, isodecyl (meth) acrylate, n-undecyl (meth) acrylate, lauryl (meth) acrylate, (meth ) Stearyl acrylate, isostearyl (meth) acrylate, isobornyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, and the like.

  The thickness of the resin layer is preferably 1 μm or more, more preferably 3 μm or more, further preferably 5 μm or more, and further preferably 10 μm or more. The upper limit value of the thickness of the resin layer is not particularly limited, but is preferably 500 μm, for example.

  The content of the resin component contained in the resin layer is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90% by mass or more. More preferably.

  The resin layer may contain an optional component, and examples of the optional component include the same components as the optional component that can be included in the coating layer.

(Laminated sheet manufacturing method)
The method for producing a laminated sheet of the present invention includes a step of obtaining a fiber layer having a recess and / or a step of obtaining a coating layer having a recess, a step of forming an internal void by bonding the fiber layer and the coating layer, including.

<Step of obtaining fiber layer>
The manufacturing method of the lamination sheet of this invention includes the process of obtaining the fiber layer containing a fine fibrous cellulose. The step of obtaining the fiber layer includes a step of coating the fine fibrous cellulose-containing slurry on the substrate, or a step of making a paper of the fine fibrous cellulose-containing slurry. Especially, it is preferable that the process of obtaining the fiber layer containing a fine fibrous cellulose includes the process of apply | coating a fine fibrous cellulose containing slurry on a base material. When a fiber layer is a fiber layer which has a recessed part, the process of obtaining a fiber layer further includes the process of forming a recessed part in the obtained fiber layer.

<Coating process>
In the coating process, a fine fibrous cellulose-containing slurry is applied onto a substrate, and the fine fibrous cellulose-containing sheet formed by drying this is peeled from the substrate to obtain a sheet (fiber layer). It is a process. By using a coating apparatus and a long base material, sheets can be continuously produced. Although the density | concentration of the slurry to apply is not specifically limited, 0.05 mass% or more and 5 mass% or less are preferable.

  The quality of the base material used in the coating process is not particularly limited, but the one with higher wettability to the fine fibrous cellulose-containing slurry may be able to suppress the sheet shrinkage during drying, but is formed after drying. It is preferable to select a sheet that can be easily peeled off. Among them, a resin plate or a metal plate is preferable, but is not particularly limited. For example, resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates, iron plates, etc., and their surfaces oxidized, stainless steel A plate, a brass plate or the like can be used.

  In the coating process, when the viscosity of the fine fibrous cellulose-containing slurry is low and expands on the base material, to obtain a fine fibrous cellulose-containing sheet of a predetermined thickness and basis weight, for damming on the base material The frame may be fixed and used. The quality of the damming frame is not particularly limited, but it is preferable to select one that can easily peel off the edge of the sheet attached after drying. Among them, a molded resin plate or metal plate is preferable, but is not particularly limited. For example, resin plates such as acrylic plates, polyethylene terephthalate plates, vinyl chloride plates, polystyrene plates, polyvinylidene chloride plates, metal plates such as aluminum plates, zinc plates, copper plates, iron plates, etc., and their surfaces oxidized, stainless steel A molded plate, brass plate, or the like can be used.

  As a coating machine for coating the fine fibrous cellulose-containing slurry, for example, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater, or the like can be used. A die coater, a curtain coater, and a spray coater are preferable because the thickness can be made more uniform.

  The coating temperature is not particularly limited, but is preferably 20 ° C or higher and 45 ° C or lower, more preferably 25 ° C or higher and 40 ° C or lower, and further preferably 27 ° C or higher and 35 ° C or lower. If the coating temperature is equal to or higher than the above lower limit value, the fine fibrous cellulose-containing slurry can be easily applied. If the coating temperature is equal to or lower than the upper limit value, volatilization of the dispersion medium during the coating can be suppressed.

In the coating step, it is preferable to apply the slurry so that the finished basis weight of the sheet (fiber layer) is 10 g / m ² or more and 100 g / m ² or less. By coating so that the basis weight falls within the above range, a fiber layer having excellent strength can be obtained.

  The step of obtaining a fiber layer containing fine fibrous cellulose preferably includes a step of drying the fine fibrous cellulose-containing slurry coated on the substrate. Although it does not specifically limit as a drying method, Either a non-contact drying method or the method of drying while restraining a sheet | seat may be sufficient, and these may be combined.

  The non-contact drying method is not particularly limited, but a method of drying by heating with hot air, infrared rays, far infrared rays or near infrared rays (heating drying method) or a method of drying in vacuum (vacuum drying method) is applied. Can do. Although the heat drying method and the vacuum drying method may be combined, the heat drying method is usually applied. Although drying by infrared rays, far infrared rays, or near infrared rays can be performed using an infrared device, a far infrared device, or a near infrared device, it is not particularly limited. The heating temperature in the heat drying method is not particularly limited, but is preferably 20 ° C. or higher and 120 ° C. or lower, and more preferably 25 ° C. or higher and 105 ° C. or lower. If the heating temperature is not less than the above lower limit value, the dispersion medium can be volatilized quickly, and if it is not more than the above upper limit value, it is possible to suppress the cost required for heating and to prevent the fine fibrous cellulose from being discolored by heat. .

  After drying, the obtained fine fibrous cellulose-containing sheet is peeled off from the base material, but when the base material is a sheet, the fine fibrous cellulose-containing sheet and the base material are wound while being laminated to form a fine fibrous form. The fine fibrous cellulose-containing sheet may be peeled from the process substrate immediately before use of the cellulose-containing sheet.

<Paper making process>
The step of obtaining a fiber layer containing fine fibrous cellulose may include a step of papermaking the fine fibrous cellulose-containing slurry. Examples of the paper machine in the paper making process include a continuous paper machine such as a long-mesh type, a circular net type, and an inclined type, and a multi-layered paper machine combining these. In the paper making process, known paper making such as hand making may be performed.

  In the papermaking process, the fine fibrous cellulose-containing slurry is filtered and dehydrated on a wire to obtain a wet paper sheet, and then the sheet is obtained by pressing and drying. Although the density | concentration of a slurry is not specifically limited, 0.05 mass% or more and 5 mass% or less are preferable. When the slurry is filtered and dehydrated, the filter cloth at the time of filtration is not particularly limited, but it is important that the fine fibrous cellulose does not pass through and the filtration rate does not become too slow. Although it does not specifically limit as such a filter cloth, The sheet | seat, fabric, and porous film which consist of organic polymers are preferable. The organic polymer is not particularly limited, but non-cellulosic organic polymers such as polyethylene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene (PTFE) and the like are preferable. Specific examples include a porous film of polytetrafluoroethylene having a pore size of 0.1 μm to 20 μm, for example, 1 μm, polyethylene terephthalate or polyethylene woven fabric having a pore size of 0.1 μm to 20 μm, for example, 1 μm, but is not particularly limited.

  Although it does not specifically limit as a method of manufacturing a sheet | seat from a fine fibrous cellulose containing slurry, For example, the method of using the manufacturing apparatus of WO2011 / 013567, etc. are mentioned. This manufacturing apparatus discharges a slurry containing fine fibrous cellulose onto the upper surface of an endless belt, squeezes a dispersion medium from the discharged slurry, generates a web, and dries the web to dry the fiber sheet. And a drying section to produce. An endless belt is disposed from the squeezing section to the drying section, and the web generated in the squeezing section is conveyed to the drying section while being placed on the endless belt.

  Although it does not specifically limit as the dehydration method which can be used in this invention, The dehydration method normally used by manufacture of paper is mentioned, After dehydrating with a long net, a circular net, a slanted wire, etc., it dehydrates with a roll press. Is preferred. The drying method is not particularly limited, and examples thereof include methods used in paper production. For example, methods such as a cylinder dryer, a Yankee dryer, hot air drying, a near infrared heater, and an infrared heater are preferable.

<Recess formation process>
When a fiber layer is a fiber layer which has a recessed part, the process of forming a recessed part in the fiber layer obtained by the method mentioned above is further included. More preferably, the step of forming such a recess is a step of forming a groove. Examples of the method for forming the concave portion in the fiber layer include a method in which a mold having a convex portion is pressed and hot pressed. It is preferable that the metal mold | die which has the convex part used in this case is a metal mold | die provided with the convex part arrange | positioned regularly. The width of each convex portion is preferably 1 μm or more and 10 mm or less, more preferably 5 μm or more and 5 mm or less, and further preferably 5 μm or more and 2 mm or less. Moreover, the height of each convex part is preferably 1 μm or more, more preferably 3 μm or more, further preferably 5 μm or more, and further preferably 10 μm or more. In addition, the height of the convex portion is preferably 200 μm or less, more preferably 50 μm or less, and further preferably 30 μm or less.

  In the step of forming the concave portion, a mold having the convex portion is pressed against one surface of the fiber layer. The temperature during hot pressing is preferably from 100 ° C. to 300 ° C., and the pressure is preferably from 0.3 MPa to 10 MPa.

  Further, in the step of forming the recesses in the fiber layer, a method of performing plasma etching treatment on a portion where the recesses are to be formed, a method of cutting with sharp metal, a method of cutting by laser processing, a method of etching with short wavelength ultraviolet rays, etc. Can also be adopted.

<Step of obtaining a coating layer>
The manufacturing method of the lamination sheet of this invention includes the process of obtaining a coating layer. When the coating layer is a coating layer having a recess, the step of obtaining the coating layer further includes a step of forming a recess in the obtained coating layer.

  A resin sheet can be used as the coating layer. In this case, the resin sheet may be obtained by applying a resin composition for forming a coating layer on a release sheet and curing the resin composition, or a commercially available resin sheet may be used.

  When forming a resin sheet from the resin composition for forming a coating layer, the resin composition for forming a coating layer preferably contains a polymerization initiator. In this case, since at least a part of the polymerization initiator remains in the coating layer, the coating layer preferably contains a polymerization initiator. In addition, as a polymerization initiator added to the resin composition for coating layer formation, a thermal polymerization initiator and a photoinitiator can be illustrated.

  Examples of the thermal polymerization initiator include hydroperoxide, dialkyl peroxide, peroxyester, diacyl peroxide, peroxycarbonate, peroxyketal, and ketone peroxide. Specifically, benzoyl peroxide, diisopropyl peroxy carbonate, t-butyl peroxy (2-ethylhexanoate) dicumyl peroxide, di-t-butyl peroxide, t-butyl peroxybenzoate, t-butyl hydro Peroxide, diisopropylbenzene hydroperoxide, 1,1,3,3-tetramethylbutyl hydroperoxide, or the like can be used. These polymerization initiators may be used alone or in combination of two or more.

Examples of the photopolymerization initiator include a photoradical generator and a photocationic polymerization initiator. A photoinitiator may be used independently or may use 2 or more types together.
Examples of the photo radical generator include benzophenone, benzoin methyl ether, benzoin propyl ether, diethoxyacetophenone, 1-hydroxycyclohexyl phenyl ketone, 2,6-dimethylbenzoyldiphenylphosphine oxide, or 2,4,6-trimethylbenzoyldiphenyl. Hosifin oxide and the like can be mentioned. Among these, benzophenone or 2,4,6-trimethylbenzoyldiphenylphosphine oxide can be mentioned.
A photocationic polymerization initiator is a compound that initiates cationic polymerization upon irradiation with radiation such as ultraviolet rays or electron beams. For example, aromatic sulfonium salts, aromatic iodonium salts, aromatic diazonium salts, aromatic ammonium salts, etc. Can be mentioned.

  The content of the polymerization initiator is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more, based on the total mass of the resin composition for forming a coating layer. Moreover, it is preferable that content of a polymerization initiator is 10 mass% or less with respect to the total mass of the resin composition for coating layer formation.

  The resin composition for forming a coating layer may further contain an isocyanate compound. Examples of the isocyanate compound include tolylene diisocyanate, xylylene diisocyanate, hexamethylene diisocyanate, and isophorone diisocyanate. The isocyanate compound includes polyisocyanates such as biuret type, nurate type, and adduct type, and such polyisocyanate can also be used.

  It is preferable that content of an isocyanate compound is 1 mass% or more with respect to the total mass of the resin composition for coating layer formation, and it is more preferable that it is 5 mass% or more. Moreover, it is preferable that content of an isocyanate compound is 50 mass% or less with respect to the total mass of the resin composition for coating layer formation.

In addition, since the thermal polymerization initiator, the photopolymerization initiator, and a part of the isocyanate compound as described above remain in an unreacted state, they are also included in the coating layer after curing.
The content of the polymerization initiator in the coating layer is preferably 0.5% by mass or more and 20% by mass or less, and more preferably 1% by mass or more and 10% by mass or less with respect to the total mass of the coating layer. preferable.
Further, the content of the isocyanate compound in the coating layer is preferably 3% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 30% by mass or less with respect to the total mass of the coating layer. .

  The resin composition for forming a coating layer may further contain a solvent. Solvents include esters such as ethyl acetate, butyl acetate and propyl acetate, ketones such as methyl ethyl ketone, methyl isobutyl, dibutyl ketone and cyclohexanone, aromatics and hydrocarbons such as toluene, xylene and hexane, 1-propanol, etc. Organic solvents such as alcohols.

  The content of the solvent contained in the resin composition for forming a coating layer is preferably 10% by mass or more and more preferably 20% by mass or more with respect to the total mass of the resin composition for forming a coating layer. Preferably, it is more preferably 30% by mass or more. Moreover, it is preferable that content of a solvent is 80 mass% or less with respect to the total mass of the resin composition for coating layer formation.

  In the step of applying the coating layer forming resin composition, for example, the coating layer forming resin composition is applied on the surface of the release sheet. As a coating machine that can be used in the step of coating the resin composition for forming a coating layer, for example, a bar coater, a roll coater, a gravure coater, a die coater, a curtain coater, an air doctor coater, or the like can be used.

In the step of curing the coating layer forming resin composition, the entire coating layer forming resin composition is cured. When the resin composition for forming a coating layer is cured using ultraviolet rays, the amount of ultraviolet rays to be irradiated is not particularly limited. For example, ultraviolet rays having a wavelength of 300 nm or more and 450 nm or less are applied at 10 mJ / cm ² or more and 1000 mJ. Irradiation is preferably performed in the range of / cm ² or less. Moreover, it is also preferable to irradiate the radiation by dividing it into two or more times. Specific examples of the lamp used for radiation irradiation include a metal halide lamp, a high pressure mercury lamp, an ultraviolet LED lamp, and an electrodeless mercury lamp.

  When the resin composition for forming a coating layer is cured using heat, it is preferable to heat the coating film of the resin composition for forming a coating layer in a temperature range of 70 ° C. or higher and 200 ° C. or lower. The heating time can be 10 minutes or more and 10 hours or less.

<Recess formation process>
When a coating layer is a coating layer which has a recessed part, the process of forming a recessed part further in the coating layer obtained by the method mentioned above or the commercially available resin sheet (coating layer) is further included. More preferably, the step of forming such a recess is a step of forming a groove. Examples of the method for forming the concave portion in the coating layer include a method of pressing a mold having a convex portion and hot pressing. As the mold having the convex portions used in this case, the above-described mold can be used, and it is preferable to adopt the above-described conditions for the hot press conditions.

  Further, in the step of forming the recesses in the coating layer, a method of performing plasma etching treatment on a portion where the recesses are to be formed, a method of cutting with sharp metal, a method of cutting by laser processing, a method of etching with short wavelength ultraviolet rays, etc. Can also be adopted.

<The process of bonding a fiber layer and a coating layer>
After the step of obtaining the fiber layer having the recesses and / or the step of obtaining the coating layer having the recesses, a step of forming an internal void by bonding the fiber layer and the coating layer is provided. Examples of the method for bonding the fiber layer and the coating layer include a method of bonding using an adhesive. As the adhesive, for example, a thermosetting adhesive or an ultraviolet curable adhesive can be used.

  When bonding a fiber layer and a coating layer using an adhesive, it is preferable to apply the adhesive to a region (convex region) where the concave portion of the fiber layer and / or the coating layer is not formed. When the concave portion is formed only in one of the fiber layer and the coating layer, it is preferable to apply an adhesive to the convex region of the layer in which the concave portion is formed. After apply | coating an adhesive agent, a fiber layer and a coating layer can be joined by bonding a fiber layer and a coating layer. In addition, when the recessed part is formed in both a fiber layer and a coating layer, when bonding a fiber layer and a coating layer, it bonds so that the position of the recessed part formed in each layer may correspond. In this way, an internal space composed of a recess formed in each layer is formed.

  Moreover, when bonding a fiber layer and a coating layer, you may use the method of heat-melting and adhering a fiber layer and / or a coating layer. Examples of the method of bonding by heat melting include a method of holding and heating the fiber layer and the coating layer in an overlapped state.

(Process of forming resin layer)
In the manufacturing method of a lamination sheet, you may further provide the process of forming a resin layer. In this case, the step of forming the resin layer may be provided before the step of forming the recess in the fiber layer, or may be provided after the step of forming the recess in the fiber layer. The step of forming the resin layer includes the step of applying the resin composition for forming the resin layer on one side of the fiber layer and on the side opposite to the side on which the coating layer is provided, and resin layer formation Curing the resin composition. Examples of the coating machine that can be used in the step of coating the resin composition for forming a resin layer include the coating machines described above.

  The resin composition for forming a resin layer preferably contains a polymerization initiator. Moreover, the resin composition for forming a resin layer may contain an isocyanate compound. As a polymerization initiator and an isocyanate compound, the polymerization initiator and isocyanate compound which were mentioned above can be mentioned. The content of the polymerization initiator is preferably 0.1% by mass or more, and more preferably 0.5% by mass or more with respect to the total mass of the resin composition for forming a resin layer. Moreover, it is preferable that content of a polymerization initiator is 10 mass% or less with respect to the total mass of the resin composition for resin layer formation. Moreover, it is preferable that it is 1 mass% or more with respect to the total mass of the resin composition for resin layer formation, and, as for content of an isocyanate compound, it is more preferable that it is 5 mass% or more. Moreover, it is preferable that content of an isocyanate compound is 50 mass% or less with respect to the total mass of the resin composition for resin layer formation.

In addition, since a part of thermal polymerization initiator, photoinitiator, and isocyanate compound as described above remain in an unreacted state, they are also included in the cured resin layer.
The content of the polymerization initiator in the resin layer is preferably 0.5% by mass or more and 10% by mass or less, and more preferably 1% by mass or more and 5% by mass or less with respect to the total mass of the resin layer. preferable.
Further, the content of the isocyanate compound in the resin layer is preferably 20% by mass or more and 90% by mass or less, and more preferably 30% by mass or more and 70% by mass or less with respect to the total mass of the resin layer. .

  It is preferable that the resin composition for forming a resin layer further contains a solvent. Examples of the solvent include the solvents described above.

  As a curing method in the step of curing the resin composition for forming a resin layer, for example, heat curing or ultraviolet curing can be employed. Thermal curing and ultraviolet curing can be performed simultaneously.

  When the resin composition for forming a resin layer is cured by thermosetting, it is preferable to heat the coating film of the resin composition for forming a resin layer in a temperature range of 70 ° C. or higher and 200 ° C. or lower. The heating time can be 10 minutes or more and 10 hours or less.

When the resin composition for forming a resin layer is cured by ultraviolet curing, the amount of ultraviolet rays to be irradiated is not particularly limited. For example, ultraviolet rays having a wavelength of 300 nm or more and 450 nm or less are applied at 10 mJ / cm ² or more and 1000 mJ. Irradiation is preferably performed in the range of / cm ² or less. Moreover, it is also preferable to irradiate the radiation by dividing it into two or more times. Specific examples of the lamp used for radiation irradiation include a metal halide lamp, a high pressure mercury lamp, an ultraviolet LED lamp, and an electrodeless mercury lamp.

(Use)
The laminated sheet of the present invention can be used, for example, as an analytical measurement sheet. Specifically, a fluid or the like can be caused to flow into the internal space of the laminated sheet of the present invention, and the physical properties of the fluid, the type of the content, the amount of the content, and the like can be analyzed. In this case, a reagent or the like suitable for each measurement may be bonded to the inner wall of the internal space. Especially, it is preferable to use the laminated sheet of this invention as a biosensor. In this case, for example, an antibody suitable for each measurement is joined to the inner wall of the internal cavity, and a biological liquid sample such as blood is dropped into the internal cavity to identify the substance contained in the biological liquid sample or Quantification can be performed.

  The laminated sheet of the present invention can be used for substrates of electronic devices, electronic device members, optical members, various vehicles and building window materials, interior materials, exterior materials, packaging materials, etc., in addition to the above applications. it can.

  The features of the present invention will be described more specifically with reference to examples and comparative examples. The materials, amounts used, ratios, processing details, processing procedures, and the like shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention should not be construed as being limited by the specific examples shown below.

[Example 1]
<Production of phosphate group-introduced cellulose fiber>
Pulp made from Oji Paper as softwood kraft pulp (sheet content with a solid content of 93% by weight and a basis weight of 208 g / m ² , a Canadian standard freeness (CSF) of 700 ml measured by disaggregation and measured according to JIS P 8121) Was used as a raw material. 100 parts by mass (absolute dry mass) of the above-mentioned softwood kraft pulp is impregnated with a mixed aqueous solution of ammonium dihydrogen phosphate and urea, and compressed to 49 parts by mass of ammonium dihydrogen phosphate and 130 parts by mass of urea. Pulp was obtained. The obtained chemical solution-impregnated pulp was dried with a dryer at 105 ° C. to evaporate the moisture and pre-dried. Then, it heated for 10 minutes with the ventilation dryer set to 140 degreeC, the phosphate group was introduce | transduced into the cellulose in a pulp, and the phosphorylated pulp was obtained.

  The obtained phosphorylated pulp was fractionated by 100 g, and 10 L of ion-exchanged water was poured, stirred and dispersed uniformly, and then subjected to filtration and dehydration to obtain a dehydrated sheet, which was repeated twice. Next, the obtained dehydrated sheet was diluted with 10 L of ion-exchanged water, and a 1N sodium hydroxide aqueous solution was added little by little while stirring to obtain a pulp slurry having a pH of 12 or more and 13 or less. Thereafter, the pulp slurry was dehydrated to obtain a dehydrated sheet, and then 10 L of ion exchange water was added. The step of stirring and dispersing uniformly, followed by filtration and dehydration to obtain a dehydrated sheet was repeated twice.

In the same manner as described above, the step of introducing phosphate groups and the step of filtration and dehydration were repeated on the obtained dehydrated sheet to obtain a twice-phosphorylated cellulose dehydrated sheet. The infrared absorption spectrum of the obtained dehydration sheet was measured by FT-IR. As a result, absorption based on phosphate groups was observed at 1230 cm ⁻¹ or more and 1290 cm ⁻¹ or less, and addition of phosphate groups was confirmed.

<Defibration processing>
Ion exchange water was added to the obtained double-phosphorylated cellulose dehydrated sheet to prepare a slurry having a solid content concentration of 2% by mass. This slurry was treated three times at a pressure of 245 MPa with a wet atomization apparatus (manufactured by Sugino Machine, Optimizer) to obtain a fine fibrous cellulose dispersion.

<Measurement of substituent amount>
The amount of substituent introduction is the amount of phosphate groups introduced into the fiber material, and the larger this value, the more phosphate groups are introduced. The amount of substituent introduced was measured by diluting the target fine fibrous cellulose with ion-exchanged water so that the content was 0.2% by mass, and then treating with ion-exchange resin and titration with alkali. In the treatment with an ion exchange resin, 1/10 by volume of a strongly acidic ion exchange resin (Amberjet 1024; Organo Corporation, conditioned) is added to a 0.2 mass% fibrous cellulose-containing slurry and shaken for 1 hour. Went. Thereafter, the mixture was poured onto a mesh having an opening of 90 μm to separate the resin and the slurry. In titration using an alkali, a change in the value of electrical conductivity exhibited by the slurry was measured while adding a 0.1N sodium hydroxide aqueous solution to the fibrous cellulose-containing slurry after ion exchange. That is, the alkali amount (mmol) required in the first region of the curve shown in FIG. 4 (phosphate group) is divided by the solid content (g) in the slurry to be titrated to introduce the substituent introduction amount (mmol / g). As a result of calculation, it was 0.98 mmol / g.

<Measurement of fiber width>
The fiber width of the fine fibrous cellulose was measured by the following method.
The supernatant of the fine fibrous cellulose dispersion was diluted with water so that the concentration was 0.01% by mass or more and 0.1% by mass or less, and dropped onto a hydrophilic carbon grid membrane. After drying, it was stained with uranyl acetate and observed with a transmission electron microscope (JEOL-2000EX, manufactured by JEOL Ltd.). This confirmed that it was a fine fibrous cellulose having a width of about 4 nm.

<Sheet>
Polyethylene oxide (manufactured by Wako Pure Chemical Industries, Ltd., molecular weight: 4 million) was added to the fine fibrous cellulose dispersion so as to be 40 parts by mass with respect to 100 parts by mass of the fine fibrous cellulose. Thereafter, the concentration was adjusted so that the solid content concentration was 0.6% by mass. The dispersion was weighed so that the finished basis weight of the sheet was 100 g / m ² , applied to a commercially available acrylic plate, and dried with a dryer at 70 ° C. for 24 hours. In addition, the board for damming was arrange | positioned on the acrylic board so that it might become predetermined | prescribed basic weight. The sheet (A) used as a fiber layer was obtained by the above procedure, and the thickness was 65 micrometers.

<Lamination of resin layer>
100 parts by mass of an acrylic resin grafted with an acryloyl group (manufactured by Taisei Fine Chemical Co., Ltd., Acryt 8KX-012C: acrylic resin component 39.0% by mass, 1-propanol 30.5% by mass, butyl acetate 30.5% by mass), poly 38 parts by mass of an isocyanate compound (Asahi Kasei Chemicals, TPA-100) and 2 parts by mass of a radical polymerization initiator (BASF, Irgacure 184) were mixed to obtain a resin composition for forming a resin layer. Next, the resin composition for forming a resin layer was applied to one surface of the sheet (A) with a bar coater, and then heated and cured at 100 ° C. for 1 hour to form a resin layer. By the above procedure, the sheet | seat (B) in which the resin layer was formed on one surface of a fiber layer was formed, and the thickness of the resin layer was 10 micrometers.

<Formation of recess in fiber layer>
Mold having regular convex portions on one side (material: silicon, convex width: 2000 μm, convex height: 20 μm, convex pitch: 5000 μm, molding area: 100 mm × 100 mm, mold area 100 mm × 100 mm) was coated with a release spray (AGC Seikagaku Co., Ltd., aerosol type spray, model number: MRF-6758-AL). Next, the sheet (B) was cut into 120 mm × 120 mm and allowed to stand on the mold so that the centers of the mold and the sheet (B) coincided. At this time, the fiber layer of the sheet (B) was placed so as to face the surface provided with the convex portions of the mold. Further, the mold and the cut sheet (B) are set in a press machine (manufactured by Aida Engineering Co., Ltd., 160 mm square mini test press with a cooler) and pressed at a pressure of 3 MPa and a temperature of 180 ° C. for 1 minute. Was cooled to 30 ° C., and the sheet (B) was peeled from the mold. By the above procedure, a sheet (C) having a recess formed in the fiber layer was obtained.

<Formation of recess in coating layer>
Mold having regular convex portions on one side (material: silicon, convex width: 2000 μm, convex height: 20 μm, convex pitch: 5000 μm, molding area: 100 mm × 100 mm, mold area 100 mm × 100 mm) was coated with a release spray (AGC Seikagaku Co., Ltd., aerosol type spray, model number: MRF-6758-AL). Next, a polycarbonate sheet (Teijin Limited, Panlite PC-2151, thickness 125 μm) was cut into a length of 95 mm × width of 120 mm, and the center line in the width direction (longitudinal direction) of the mold and the polycarbonate were placed on the mold. It left still so that the center line of the width direction (longitudinal direction) of a sheet | seat might correspond, and the lower end side of a metal mold | die and the lower end side of a polycarbonate sheet might correspond. Here, the width direction of the mold is a direction orthogonal to the convex portion provided on the mold. Further, the lower end side is a side parallel to the width direction. Furthermore, the mold and the cut polycarbonate sheet were set in a press machine (manufactured by Aida Engineering Co., Ltd., 160 mm square mini test press with a cooler), pressed at a pressure of 3 MPa and a temperature of 180 ° C. for 1 minute, and then the temperature of the mold Was cooled to 30 ° C., and the polycarbonate sheet was peeled from the mold. By the above procedure, the sheet | seat for coating layers in which the recessed part was formed was obtained.

<Bonding of fiber layer and coating layer>
A UV curable adhesive (Z-587-16, manufactured by Aika Kogyo Co., Ltd.) is applied to the end region of the fiber layer in which the concave portion of the sheet (C) is formed and the convex region of the fiber layer of the sheet (C). It applied using. In addition, the edge part area | region of a fiber layer is the site | part (20 mm width part of an edge part) located outside the shaping | molding area of the metal mold | die in <formation of the recessed part to a fiber layer>. Subsequently, the sheet | seat for coating layers and the sheet | seat (C) were piled up so that the position of the recessed part of the sheet | seat for coating layers and the position of the recessed part of a sheet | seat (C) might correspond, and recessed parts might come inside. At this time, the lower end sides of the sheet (C) and the coating layer sheet were made to coincide (in this state, a part of the upper end of the sheet (C) was exposed). Here, the lower end side is a side orthogonal to the extending direction of the recess. Further, a PET film (manufactured by Toray Industries, Inc., Lumirror S10, thickness 50 μm) was placed on the exposed surface of the coating layer and pressed with a rubber roller. Next, the PET film was peeled off, and the UV curable adhesive was cured by irradiating with 500 mJ / cm ² ultraviolet rays using a UV conveyor device (ECS-4011GX, manufactured by Eye Graphics Co., Ltd.). By the above procedure, a laminated sheet in which the resin layer, the fiber layer, and the coating layer were laminated in this order was obtained.

<Cut out the evaluation sheet>
When the edge of the sheet (C) where the coating layer is not laminated and the surface is partially exposed is the upper edge, the sheet is removed by cutting an area from the lower edge facing the upper edge to 2.5 cm. did. At this time, the cut surface was orthogonal to the concave portion of the laminated sheet. By the above procedure, an evaluation sheet (95 mm × 120 mm) having an internal void constituted by a fiber layer and a coating layer was obtained.

[Example 2]
In <Formation of recesses in coating layer> in Example 1, the mold was not pressed, and only the polycarbonate sheet was cut to obtain a coating layer sheet. An evaluation sheet was obtained in the same manner as in Example 1 except for the above.

[Example 3]
An evaluation sheet was obtained in the same manner as in Example 1 except that the sheet (A) was used in place of the polycarbonate sheet in <Formation of recesses in the coating layer> in Example 1.

[Example 4]
Evaluation sheet in the same manner as in Example 1 except that a polyurethane film (made by Takeda Sangyo Co., Ltd., Tough Grace, thickness of 100 μm) was used in place of the polycarbonate sheet in <Formation of recesses in the coating layer> in Example 1. Got.

[Example 5]
An evaluation sheet was obtained in the same manner as in Example 1 except that <Lamination of resin layer> was not performed in Example 1.

[Example 6]
In <Formation of concave portion on fiber layer> and <Formation of concave portion on coating layer> in Example 1, a mold having a smaller convex portion width (material: silicon, convex portion width: 20 μm, convex portion height) : 20 μm, convex pitch: 5000 μm, molding area: 100 mm × 100 mm, mold area 100 mm × 100 mm) was used in the same manner as in Example 1 to obtain an evaluation sheet.

[Comparative Example 1]
In Example 1, <bonding of the fiber layer and the coating layer> was not performed, and <cutting out the evaluation sheet> was performed on the sheet (C). Except the above, it carried out similarly to Example 1, and obtained the sheet | seat for evaluation in which the recessed part was formed in the fiber layer.

[Comparative Example 2]
In <Sheetization> of Example 1, a fibrous cellulose suspension was used instead of the fine fibrous cellulose dispersion. In addition, the said fibrous cellulose suspension was manufactured as follows. Ion-exchanged water is added to softwood bleached kraft pulp (moisture 50 mass%, Canadian standard freeness (CSF) 700 ml measured according to JIS P 8121) to obtain a 1.0 mass% pulp suspension. did. This pulp suspension was treated with a laboratory refiner (manufactured by Aikawa Tekko Co., Ltd.) at 10,000 rpm for 5 hours to obtain a fibrous cellulose suspension. The average fiber width of the fibrous cellulose contained in this fibrous cellulose suspension was 3 μm. The finished basis weight of the sheet was 70 g / m ² , and the thickness of the obtained sheet was 65 μm. An evaluation sheet was obtained in the same manner as in Example 1 except for the above.

<Measurement>
The evaluation sheets obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were measured according to the following method.

[Maximum width W of internal void or recess]
The cross section of the evaluation sheet was cut out with an ultramicrotome UC-7 (manufactured by JEOL), and the cross section was observed with an optical microscope. The average value of the maximum width of 10 internal voids or recesses existing in the cross section was defined as the maximum width of the internal voids or recesses.

[Height T of internal void or recess]
The cross section of the evaluation sheet was cut out with an ultramicrotome UC-7 (manufactured by JEOL), and the cross section was observed with an optical microscope. The average value of the heights of the internal voids or the depths of the recesses at 10 points existing in the cross section was defined as the height of the internal voids or the depth of the recesses.

[Aspect ratio W / T of internal void or recess]
The aspect ratio (W / T) of the internal void was calculated by dividing the maximum width of the internal void or recess by the height of the internal void or the depth of the recess.

<Evaluation>
The evaluation sheets obtained in Examples 1 to 6 and Comparative Examples 1 and 2 were evaluated according to the following methods.

[Inhibition of sample contamination]
The evaluation sheet was placed in an autoclave (LBS-325, manufactured by Tommy Seiko Co., Ltd.) and sterilized at 121 ° C. for 15 minutes. Subsequently, the evaluation sheet was allowed to stand for 5 minutes in a temperature / humidity adjustment chamber at 23 ° C. and a relative humidity of 50%. Thereafter, the evaluation sheet was transferred into a clean bench, and in the evaluation sheets obtained in Examples 1 to 6 and Comparative Example 2, the coating layer was preliminarily subjected to flame sterilization treatment (blow the tip with a flame). Removed with tweezers and scissors. Further, the inner wall of the recess formed in the fiber layer of the evaluation sheet was scratched 10 times with a toothpick that had been subjected to a flame sterilization treatment in advance, and then the toothpick was immersed in 10 mL of sterile water and shaken. 1 mL of the sterilized water was dropped onto a glass bottom petri dish (diameter: 12 cm) containing a standard agar medium using a micropipette, and was diffused throughout the medium using a flame sterilized preliminarily. Then, it culture | cultivated at 32 degreeC for 48 hours, and evaluated according to the following reference | standard by confirming the formation number of the microbial colony after culture | cultivation.
A: Less than 10 colonies formed.
A: The number of colonies formed is 10 or more and less than 100.
Δ: The number of colonies formed is 100 or more and less than 500.
X: The number of colonies formed is 500 or more.

[Function of internal void or recess as flow path]
95 parts by mass of 2-propanol and 5 parts by mass of a dye (CI Acid Red 52, manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed to prepare a test solution. Subsequently, 50 microliters of test solutions were dripped with the micropipette to the edge part by which the fiber layer of the internal space | gap of the sheet | seat for evaluation obtained in Examples 1-6 and Comparative Example 2 was exposed. In Comparative Example 1, 50 μL of the test solution was dropped onto one end of the recess (groove) with a micropipette. Further, the evaluation sheet was tilted by 20 °, and the evaluation sheet was observed after 1 minute, and evaluated according to the following criteria.
A: The test solution is observed only in the internal voids or recesses, and the test solution reaches the other end.
◯: The test solution is observed only in the internal void or recess and the periphery thereof, and the test solution reaches the other end.
Δ: The test solution is observed on the back surface of the fiber layer, but the test solution reaches the other end.
X: The test solution is observed on the back surface of the fiber layer, and the test solution does not reach the other end.

As is clear from Table 1, in the example in which the laminated sheet was provided with a fiber layer and a coating layer, and internal voids were constituted by the fiber layer and the coating layer, a laminated sheet capable of suppressing sample contamination was obtained. Moreover, in the Example, it was suggested that an internal space | gap functions effectively also as a flow path of a fluid.
On the other hand, in the comparative example 1 which does not have a coating layer, it resulted from the sample layer contamination resulting from the exposed fiber layer. In Comparative Example 2 in which fibrous cellulose having a larger fiber width was used instead of fine fibrous cellulose, the function of the internal voids as a flow path was significantly reduced.

DESCRIPTION OF SYMBOLS 10 Laminated sheet 12 Fiber layer 14 Coating layer 16 Resin layer 20 Internal space | gap

Claims (8)

A fiber sheet comprising fibrous cellulose having a fiber width of 1000 nm or less, and a covering layer on at least one surface of the fiber layer,
The laminated sheet has internal voids,
The outer peripheral wall which forms each internal space | gap is a lamination sheet formed from the said fiber layer and the said coating layer.   The laminated sheet according to claim 1, wherein the internal void includes a concave portion of the fiber layer.   The laminated sheet according to claim 1 or 2, wherein the internal void is configured by a concave portion of the fiber layer and a concave portion of the coating layer.   The said covering layer is a laminated sheet of any one of Claims 1-3 containing the fibrous cellulose whose fiber width is 1000 nm or less. The internal void extends in a planar direction,
The laminated sheet according to any one of claims 1 to 4, wherein a maximum width of the internal void is 1 µm or more and 10 mm or less. The internal void extends in a planar direction,
The value represented by W / T is 0.1 or more and 1000 or less, where W is the maximum width of the internal gap and T is the height of the internal gap. The laminated sheet as described.   The laminated sheet according to any one of claims 1 to 6, wherein the internal gap is a flow path for flowing a fluid.   The laminated sheet according to any one of claims 1 to 7, further comprising a resin layer on one surface of the fiber layer and on a surface opposite to the surface on which the coating layer is provided.

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