Laminate and ship equipped with laminate

Abstract

To provide a laminate that can easily remove any adherents thereon even if the adherents are organisms having strong adhesion, such as barnacles, and a vessel including the laminate.SOLUTION: A laminate includes a resin layer including soluble resin, and a film including (A) cellulose fibers having a modifying group and (B) an organic compound being non-volatile at 25°C and 1 atmospheric pressure. Preferably, the film further includes component (C): polyether-modified silicone. There is also provided a vessel including the laminate.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a laminate. The present invention also relates to a ship equipped with the laminate. [Background technology]

[0002] Conventionally, antifouling coating compositions have been known that form antifouling coating films that have a coating wear rate and exhibit excellent antifouling properties over a long period of time in order to prevent aquatic organisms from attaching to the bottom of ships (Patent Document 1). [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2011-118526 Brochure Summary of the Invention [Problem to be solved by the invention]

[0004] A laminate coated with such an antifouling coating composition can maintain a clean surface free of deposits by dissolving the coating film itself, even if only a small amount of deposits are attached. However, once organisms with strong adhesive power, such as barnacles, attach to the surface, they are difficult to remove and ultimately must be removed using tools. Removing barnacles using tools requires a great deal of effort, and there are also issues with exposing the base material of the laminate, resulting in a decrease in performance and a deterioration in appearance.

[0005] Therefore, an object of the present invention is to provide a laminate that allows easy removal of adhesions even when organisms with strong adhesive power, such as barnacles, are attached to it. [Means for solving the problem]

[0006] The present invention relates to the following [1] to [4]. [1] A laminate comprising a resin layer containing a soluble resin, and a film containing the following component (A) and component (B): (A) Cellulose fibers with modified groups (B) Non-volatile organic compounds at 25°C and 1 atmosphere [2] A method for removing the layer containing the membrane from the laminate according to [1] above using a water jet. [3] A ship equipped with a resin layer containing a soluble resin and a laminate including a film containing the following component (A) and component (B): (A) Cellulose fibers with modified groups (B) Non-volatile organic compounds at 25°C and 1 atmosphere [4] A method for removing the layer including the membrane from a ship equipped with the laminate described in [3] above by using a water flow. [Effects of the Invention]

[0007] According to the present invention, it is possible to provide a laminate from which the attachment can be easily removed even when organisms with strong adhesive power, such as barnacles, are attached. [Brief explanation of the drawings]

[0008] [Figure 1] FIG. 1 is a schematic diagram showing the cross-sectional structure of a laminate according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0009] 1.Laminate The laminate in this specification includes a resin layer containing a soluble resin and a film containing component (A) and component (B). The laminate in this specification may be further formed on a substrate. For example, as shown in Figure 1, there is a structure in which "substrate 1 - resin layer 2 - film 3" are laminated. Furthermore, in the laminate herein, an optional film may be formed on the surface of the film containing component (A) and component (B), and an optional film may be formed between the film and the resin layer, or between the substrate and the resin layer.

[0010] The laminate of the present invention has a film with synovial properties on its surface, and therefore can be used as components that come into contact with seawater or freshwater, such as ship hulls and propellers, bridge frameworks, piping, quays, cooling towers, tank interior surfaces, offshore facilities and observation equipment, and fishing nets.

[0011] <Resin layer> The resin layer is a layer formed from a resin, and preferably contains a soluble resin. The thickness of the resin layer is preferably 1 μm or more, more preferably 10 μm or more, and even more preferably 50 μm or more, from the viewpoint of easily removing deposits from the film, and is preferably 1 mm or less, more preferably 500 μm or less, and even more preferably 200 μm or less, from the viewpoint of improving productivity.

[0012] The resin layer may contain any optional component that does not impair the effects of the present invention.

[0013] [Dissolved resin] The soluble resin is a material for the resin layer, and is preferred because the use of the soluble resin allows for easy peeling and renewal of the resin layer or film from the substrate.

[0014] A resin that is soluble in contact with flowing water is defined herein as a "soluble resin." In the emulsion composition of the present invention, the soluble resin plays a role in improving the durability of the synovial fluid performance of the membrane and renewing the membrane surface by dissolving.

[0015] In the present invention, the use of a soluble resin is preferred because it allows stable coating wear resistance to be achieved on ships, underwater structures, and the like.

[0016] The dissolving resin is as follows: Metal salt bond-containing copolymer (d1) (hereinafter also referred to as "copolymer (d1)"), Metal salt bond-containing copolymer (d2) (hereinafter also referred to as "copolymer (d2)"), and Silyl ester copolymer (d3) (hereinafter also referred to as "copolymer (d3)") It is preferable that the resin contains one or more soluble resins selected from the group consisting of: The soluble resin may be a copolymer that satisfies the requirements of both copolymers (d1) and (d2), containing both the side chain terminal type metal salt bond structure found in copolymer (d1) and the cross-linked type metal salt bond structure found in copolymer (d2). The soluble resins may be used alone or in combination of two or more.

[0017] [Metal salt bond-containing copolymer (d1)] The metal salt bond-containing copolymer (d1) is an acrylic resin or polyester resin, and is a metal salt bond-containing copolymer having a side chain terminal group represented by general formula (DI). In this specification, the above structure may be referred to as a "side chain terminal type metal salt bond." -COO-MO-COR 1 (DI) (In formula (DI), M is zinc or copper, and R 1 is an organic group. When the copolymer (d1) has a plurality of side chain terminal groups represented by formula (DI), each R 1 and M may be the same or different.

[0018] Organic group R in copolymer (d1) 1 (and the organic group R in formula (D-IV) described later) 1 ) is an organic acid residue formed from a monobasic acid, and is preferably a saturated or unsaturated aliphatic hydrocarbon group having from 2 to 30 carbon atoms, a saturated or unsaturated alicyclic hydrocarbon group having from 3 to 20 carbon atoms, or an aromatic hydrocarbon group having from 6 to 18 carbon atoms, or a substituted product thereof. Examples of the substituted product include a hydroxyl group-substituted product.

[0019] Among the copolymers (d1), acrylic resin-type polymers are preferred. Such acrylic resin-type polymers can be prepared, for example, by a polymerization reaction using a monomer having a metal salt bond represented by general formula (D-IV), i.e., a monobasic acid metal (meth)acrylate (hereinafter also referred to as "monomer (d11)"). CH2=C(R 2 )-COO-MO-COR 1 (D-IV) (In formula (D-IV), M is zinc or copper, and R 1 is an organic group, and R 2 is a hydrogen atom or a methyl group. 1 and preferred types thereof include the organic group R 1 However, in order to distinguish it from the monomer (d21) represented by formula (D-II) which can form a crosslinked metal salt bond described later, R 1 excludes the vinyl group [-CH=CH2] and the isopropenyl group [-C(CH3)=CH2].

[0020] The copolymer (d1) may be a polymer obtained by copolymerization of two or more monomers (d11). Alternatively, the copolymer (d1) may be a polymer obtained by copolymerization of one or more monomers (d11) with one or more other unsaturated monomers copolymerizable with the monomer (d11) (hereinafter also referred to as "monomer (d12)"), i.e., a copolymer having constituent units derived from the monomer (d11) and constituent units derived from the monomer (d12).

[0021] The monomer (d12) can be appropriately selected from various compounds used as polymerizable unsaturated monomers for acrylic resins. For example, monomers that do not contain a metal salt bond, such as alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, and hydroxyalkyl (meth)acrylate, are preferred. Among these, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate are more preferred.

[0022] The acrylic resin type copolymer (d1) can be prepared by, for example, preparing an acrylic resin using (meth)acrylic acid, alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, or the like, and then attaching an organic group (R 1 The compound can also be prepared by a method in which a reaction is carried out to introduce a structure having a bonded group (D) to form a side chain terminal group represented by the formula (DI).

[0023] Even when a predetermined side chain terminal group is introduced into the acrylic resin by the above-mentioned preparation method, R 1 In the preparation method, the monobasic acid is converted into an organic group R 1 can be used in a reaction to introduce

[0024] In copolymer (d1), the content of zinc and / or copper resulting from the structure of formula (DI) is preferably 0.5% by mass or more and 20% by mass or less of the copolymer. By using copolymer (d1) that satisfies these conditions, it becomes possible to form an antifouling coating film that is even more excellent in both antifouling properties and wear resistance. Here, the "content of zinc and / or copper" means the total content of zinc and copper when both zinc and copper are contained.

[0025] The content of zinc and / or copper can be adjusted to fall within the above range by adjusting the blending ratio of the monomer (d11) containing these metals and the other monomer (d12) used in preparing the copolymer (d1), or by adjusting the amount of the compound containing zinc and / or copper (e.g., the monobasic acid) added to be subsequently reacted with the acrylic resin.

[0026] [Metal salt bond-containing copolymer (d2)] The metal salt bond-containing copolymer (d2) is a copolymer having a component unit derived from a monomer (d21) represented by general formula (D-II) and a component unit derived from another unsaturated monomer (d22) copolymerizable with the monomer (d21).

[0027] CH2=C(R 2 )-COO-MO-CO-C(R 2 )=CH2(D-II) (In formula (D-II), M is zinc or copper, and R 2 is a hydrogen atom or a methyl group. When the copolymer (d2) contains a plurality of component units derived from the monomer (d21) represented by formula (D-II), each R 2 and M may be the same or different.)

[0028] Examples of the monomer (d21) include zinc diacrylate, zinc dimethacrylate, copper diacrylate, and copper dimethacrylate. The monomer (d21) may be used alone or in combination of two or more.

[0029] Monomer (d21) can be prepared by a known method, for example, by heating and stirring an inorganic metal compound (such as an oxide, hydroxide, or chloride of zinc or copper) and (meth)acrylic acid or an ester compound thereof in the presence of an alcohol-based organic solvent and water at a temperature equal to or lower than the decomposition temperature of the metal salt.

[0030] The component unit derived from the monomer (d21) has a structure represented by the following general formula, and in this specification, the structure may be referred to as a "bridged metal salt bond."

[0031] [ka]

[0032] The other unsaturated monomer (d22) copolymerizable with the monomer (d21) can be appropriately selected from various compounds used as polymerizable unsaturated monomers for acrylic resins, similar to the monomer (d12) for the copolymer (d1) described above. That is, as the unsaturated monomer (d22), alkyl (meth)acrylate, alkoxyalkyl (meth)acrylate, hydroxyalkyl (meth)acrylate, etc. are preferred, and among these, methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, 2-methoxyethyl (meth)acrylate, 3-methoxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, etc. are more preferred.

[0033] The monomer (d11) for the copolymer (d1), i.e., the monobasic metal (meth)acrylate represented by the formula (D-IV), is also a monomer copolymerizable with the monomer (d21), and corresponds to the unsaturated monomer (d22) that can be used to prepare the metal salt bond-containing copolymer (d2). 1 and a preferred embodiment thereof is an organic group R 1 is the same as: The unsaturated monomer (d22) may be used alone or in combination of two or more kinds.

[0034] It is also preferable that the unsaturated monomer (d22) contains a monobasic metal (meth)acrylate represented by the formula (D-IV) and one or more unsaturated monomers selected from the group consisting of alkyl (meth)acrylates, alkoxyalkyl (meth)acrylates, and hydroxyalkyl (meth)acrylates.

[0035] Other examples of the unsaturated monomer (d22) include styrene and styrene derivatives; vinyl esters such as vinyl acetate and vinyl propionate; (meth)acrylamide and its derivatives; and (meth)acrylonitrile.

[0036] In copolymer (d2), from the same viewpoint as in copolymer (d1), the content of zinc and / or copper resulting from the structure of formula (D-II) is preferably 0.5% by mass or more and 20% by mass or less, more preferably 1% by mass or more and 19% by mass or less, of the copolymer. Here, the "content of zinc and / or copper" means the total content of zinc and copper when both zinc and copper are contained.

[0037] The content of zinc and / or copper can be adjusted by the blending ratio of the monomers used in preparing copolymer (d2). When copolymer (d2) has both a cross-linked metal salt bond structure and a side chain terminal metal salt bond structure, it is preferable that the total content of zinc and / or copper resulting from each structure be within the above range.

[0038] The number-average molecular weight and weight-average molecular weight of copolymer (d1) and copolymer (d2) can be appropriately adjusted taking into consideration the viscosity and storage stability of the antifouling coating composition, the dissolution rate of the antifouling coating film, etc., but the number-average molecular weight is preferably from 1,000 to 100,000, more preferably from 1,000 to 50,000, and the weight-average molecular weight is preferably from 1,000 to 200,000, more preferably from 1,000 to 100,000. The number average molecular weight and weight average molecular weight in this specification are values ​​determined by gel permeation chromatography using polystyrene as a standard substance.

[0039] [Silyl ester copolymer (d3)] The silyl ester copolymer (d3) is a copolymer having a component unit (hereinafter also referred to as a "silyl ester component unit") derived from a monomer (d31) represented by general formula (D-III) (hereinafter also referred to as a "silyl ester monomer"), and optionally having a component unit derived from another unsaturated monomer (d32) copolymerizable with the monomer (d31).

[0040] R 7 -CH=C(R 3 )-COO-SiR4 R 5 R 6 (D-III) (In formula (D-III), R 3 is a hydrogen atom or a methyl group, and R 4 , R 5 and R 6 are each independently a hydrocarbon group, and R 7 is a hydrogen atom or R 8 -O-CO-(However, R 8 is an organic group or SiR 9 R 10 R 11 is a silyl group represented by R 9 , R 10 and R 11 are each independently a hydrocarbon group.

[0041] Among the silyl ester monomers (d31), R 7 When is a hydrogen atom, the monomer is represented by general formula (D-IIIa). CH2=C(R 3 )-COO-SiR 4 R 5 R 6 (D-IIIa) (In formula (D-IIIa), R 3 , R 4 , R 5 and R 6 are R in formula (D-III), respectively. 3 , R 4 , R 5 and R 6 The same as the above R 4 , R 5 and R 6 The hydrocarbon group in is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group such as methyl, ethyl, propyl, or isopropyl.

[0042] Among the silyl ester monomers (d31), R 7 "R 8 When the formula is —O—CO—, the monomer is represented by general formula (D-IIIb). R 8-O-CO-CH=C(R 3 )-COO-SiR 4 R 5 R 6 (D-IIIb) (In formula (D-IIIb), R 3 , R 4 , R 5 , R 6 and R 8 represents R in formula (D-III) or formula (D-IIIa), respectively. 3 , R 4 , R 5 , R 6 and R 8 The same as the above R 8 The organic group in R is preferably an alkyl group having 1 to 10 carbon atoms, and more preferably an alkyl group such as methyl, ethyl, propyl, or isopropyl. 9 , R 10 and R 11 The hydrocarbon group in is preferably an alkyl group having 1 to 10 carbon atoms, more preferably an alkyl group such as methyl, ethyl, propyl, or isopropyl.

[0043] Examples of the silyl ester monomer (d34) represented by the formula (D-IIIb) include maleic acid esters (R 3 = hydrogen atoms).

[0044] Examples of the other unsaturated monomer (d32) copolymerizable with the monomer (d31) (or the monomers (d33) and / or (d34)) include the "other unsaturated monomers (d12) and (d22)" exemplified as raw material compounds for the copolymers (d1) and (d2).

[0045] The silyl ester monomer (d31) may be used alone or in combination of two or more kinds, and the other unsaturated monomer (d32) may be used alone or in combination of two or more kinds.

[0046] In the silyl ester copolymer (d3), the component units derived from the silyl ester monomer (d31) are preferably contained in the copolymer (total constituent units 100 mol%) in an amount of 10 mol% to 100 mol%, and the component units derived from other unsaturated monomers (d32) are contained in the remaining amount, i.e., preferably in an amount of 0 mol% to 90 mol%. A content of the component units within the above range is preferable in terms of excellent resin viscosity in the coating film (e.g., crack resistance), storage stability of the coating, and elution of the resin in the coating film.

[0047] The number average molecular weight of the silyl ester copolymer (d3) is preferably from 1,000 to 200,000 (two hundred thousand). A number average molecular weight within this range is preferred in that it provides excellent resin viscosity in the coating film (e.g., crack resistance), storage stability of the coating material, and elution of the resin in the coating film.

[0048] <Film containing component (A) and component (B)> The film containing component (A) and component (B) has synovial properties, and therefore can impart synovial properties to the laminate. Such a film can be formed, for example, by drying the emulsion composition described below.

[0049] The thickness of the film is preferably 0.1 μm or more, more preferably 1 μm or more, and even more preferably 10 μm or more from the viewpoint of easy removal of deposits, and is preferably 10 mm or less, more preferably 1 mm or less, and even more preferably 100 μm or less from the viewpoint of improving productivity. The film thickness can be adjusted to a desired value by adjusting the coating film thickness during spraying and the ratio of the medium. The film thickness can be measured according to the method described in the Examples below.

[0050] [Component (A)] Component (A) is a cellulose fiber having a modified group. A preferred example of a cellulose fiber having a modifying group is a modified cellulose fiber in which a modifying group is bonded to one or more groups selected from the group consisting of anionic groups and hydroxy groups of an anion-modified cellulose fiber having a type I crystal structure.

[0051] [Anion-modified cellulose fiber] Anion-modified cellulose fibers are cellulose fibers that have been modified to contain anionic groups. Anion-modified cellulose fibers have a cellulose type I crystal structure derived from the raw cellulose fibers. From the viewpoint of strength development during film formation, the crystallinity of the anion-modified cellulose fibers is preferably 10% or more, more preferably 15% or more, and even more preferably 20% or more. Furthermore, from the viewpoint of raw material availability, the crystallinity is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less.

[0052] In this specification, the crystallinity of various cellulose fibers refers to the cellulose type I crystallinity calculated from the diffraction intensity value obtained by X-ray diffraction, and can be measured according to the method described in the Examples below. Cellulose type I refers to the crystalline form of natural cellulose, and cellulose type I crystallinity refers to the proportion of crystalline regions in the entire cellulose fiber. The presence or absence of a cellulose type I crystalline structure can be determined by the presence of a peak at 2θ = 22.6° in X-ray diffraction measurement.

[0053] Examples of the anionic group contained in the anion-modified cellulose fiber include a carboxy group, a sulfonic acid group, and a phosphate group. From the viewpoint of the efficiency of introducing the modifying group into the cellulose fiber, the anionic group is preferably a carboxy group. Examples of the ion (counter ion) that forms a pair with the anionic group in the anion-modified cellulose fiber include metal ions such as sodium ions, potassium ions, calcium ions, and aluminum ions that are generated in the presence of alkali during production, and protons that are generated by substituting these metal ions with an acid. As the anion-modified cellulose fiber, a carboxy group-containing cellulose fiber in which the anionic group is a carboxy group is more preferred from the viewpoints of ease of preparation and mild reaction conditions.

[0054] The anionic group content in the anion-modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.4 mmol / g or more, even more preferably 0.6 mmol / g or more, and even more preferably 0.8 mmol / g or more, from the viewpoint of introducing modifying groups. Furthermore, from the viewpoint of improving handleability, it is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and even more preferably 1.8 mmol / g or less. The "anionic group content" refers to the total amount of anionic groups in the cellulose constituting the cellulose fiber, and is specifically measured by the method described in the Examples below.

[0055] The average fiber diameter of the anion-modified cellulose fiber is preferably 0.1 nm or more, more preferably 1.0 nm or more, and even more preferably 2.0 nm or more from the viewpoint of handleability, and is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less from the viewpoint of strength when formed into a film. The average fiber diameter of the anion-modified cellulose fiber is measured by the method described in the examples below.

[0056] [Modified cellulose fiber] Cellulose fibers having a modifying group are also referred to herein as modified cellulose fibers. From the viewpoint of easily removing deposits from the membrane, the modified cellulose fibers are preferably anion-modified cellulose fibers in which the modifying group is bonded to an anionic group or a hydroxyl group. The modifying group is introduced by reacting the anion-modified cellulose fiber with a compound for introducing the modifying group (referred to herein as a "modifying compound"). That is, the structure of the modifying group depends on the structure of the modifying compound used.

[0057] When the bonding site is a hydroxy group, the bonding mode between the modifying group and the anion-modified cellulose fiber is a covalent bond, for example, an ether bond, an ester bond, or a carbonate bond.

[0058] When the bonding site is an anionic group, the bonding mode between the modifying group and the anion-modified cellulose fiber is an ionic bond or a covalent bond. Here, when the bonding mode is an ionic bond, the modifying compound having a cationic group bonds to the anionic group via electrostatic interaction. Here, when the bonding mode is a covalent bond, the two are bonded via an ester bond, an amide bond, or the like. In particular, when the anionic group is a carboxy group, the bonding mode is via an ester bond, an amide bond, a carbonate bond, a urethane bond, or the like.

[0059] [Modifying group] The modifying group may be (a) a polymer group or (b) a hydrocarbon group, from the viewpoint of facilitating removal of deposits from the membrane. One type of these modifying groups may be bonded to the anion-modified cellulose fiber alone, or two or more types may be bonded in combination.

[0060] (a) polymer group Polymer group is a functional group containing a polymer structure.In order to easily remove deposits from the film, the functional group equivalent of polymer group is preferably 100g / mol or more, more preferably 200g / mol or more, more preferably 300g / mol or more, more preferably 400g / mol or more, more preferably 600g / mol or more, more preferably 800g / mol or more, and more preferably 1,500g / mol or more.From the same viewpoint, it is preferably 16,000g / mol or less, more preferably 14,000g / mol or less, more preferably 12,000g / mol or less, more preferably 10,000g / mol or less, more preferably 7,000g / mol or less, more preferably 5,000g / mol or less, more preferably 4,000g / mol or less, more preferably 3,500g / mol or less, and more preferably 2,500g / mol or less. The functional group equivalent is the molecular weight per functional group, and is calculated by functional group equivalent (g / mol) = weight average molecular weight / number of functional groups per molecule.

[0061] The weight average molecular weight of the polymer group is preferably 2,000 or more, more preferably 5,000 or more, and even more preferably 8,000 or more, from the viewpoint of facilitating removal of deposits from the membrane, and from the same viewpoint, is preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0062] From the viewpoint of easily removing deposits from the film, the polymer group is preferably a functional group having a repeating structure linked by a structure having an oxygen atom, more preferably a functional group having a repeating structure linked by an oxygen atom, such as a polyoxyalkylene structure or a polysiloxane structure, more preferably a functional group having a polysiloxane structure.

[0063] The polysiloxane structure is a structure having a siloxane bond as the main chain, and may further include an alkylene group. The polysiloxane structure may have a substituent, which will be described later.

[0064] (b) Hydrocarbon group The hydrocarbon group includes monovalent hydrocarbon groups, such as chain saturated hydrocarbon groups, chain unsaturated hydrocarbon groups, cyclic saturated hydrocarbon groups, and (heterocyclic) aromatic hydrocarbon groups.

[0065] From the viewpoint of improving the durability of the synovial fluid performance of the membrane, the number of carbon atoms in the hydrocarbon group is preferably 1 or more, more preferably 2 or more, even more preferably 3 or more, even more preferably 4 or more, even more preferably 8 or more, even more preferably 12 or more, even more preferably 16 or more, even more preferably 18 or more, and from the same viewpoint, it is preferably 40 or less, more preferably 30 or less, even more preferably 24 or less, even more preferably 22 or less. The hydrocarbon group may have a substituent as described below, and a portion of the hydrocarbon group may be substituted with a hydrogen nitride group. The aromatic hydrocarbon group is, for example, selected from the group consisting of an aryl group and an aralkyl group.

[0066] (c) Further Substituents The modifying groups such as (a) polymer groups and (b) hydrocarbon groups may further have a substituent. Examples of the substituent include alkoxy groups having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, and hexyloxy; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, and sec-butoxycarbonyl; alkoxycarbonyl groups having 1 to 6 carbon atoms, such as a tert-butoxycarbonyl group, a pentyloxycarbonyl group, or an isopentyloxycarbonyl group; halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom; acyl groups having 1 to 6 carbon atoms, such as an acetyl group or a propionyl group; aralkyl groups; aralkyloxy groups; alkylamino groups having 1 to 6 carbon atoms; dialkylamino groups having an alkyl group with 1 to 6 carbon atoms; and a hydroxy group.

[0067] The bond amount (mmol / g) and introduction rate (mol%) of the modifying group in the modified cellulose fiber refer to the amount and ratio of the modifying group introduced into the modified cellulose fiber. The bond amount and introduction rate of the modifying group can be adjusted by the amount and type of modifying compound added, the reaction temperature, the reaction time, the solvent, etc.

[0068] The amount of the modifying group bonded to the modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, and even more preferably 0.5 mmol / g or more, from the viewpoint of easy removal of deposits from the membrane, and is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, and even more preferably 2 mmol / g or less, from the viewpoint of reactivity.

[0069] Furthermore, the introduction rate of the modifying group in the modified cellulose fiber is preferably 10 mol% or more, more preferably 20 mol% or more, even more preferably 40 mol% or more, and even more preferably 50 mol% or more, from the viewpoint of easily removing deposits from the membrane, and from the viewpoint of reactivity, it is preferably 99 mol% or less, more preferably 97 mol% or less, even more preferably 95 mol% or less, and even more preferably 90 mol% or less.

[0070] [Method for manufacturing modified cellulose fibers] The modified cellulose fiber can be produced, for example, by a method comprising the steps of: (1) introducing anionic groups into raw cellulose fiber to obtain anionically modified cellulose fiber; and (2) binding a modifying compound to the anionically modified cellulose fiber obtained by the method comprising step (1) to obtain the modified cellulose fiber.

[0071] (1) A process for obtaining anion-modified cellulose fibers The anionically modified cellulose fiber used in the present invention can be obtained by subjecting raw cellulose fiber to an oxidation treatment or an anionic group addition treatment to introduce one or more anionic groups and thereby anionically modifying the fiber.

[0072] Cellulose fibers to be anionically modified, i.e., cellulose fibers used as raw materials for modified cellulose fibers and anionically modified cellulose fibers, are preferably natural cellulose fibers from an environmental perspective, and examples include wood pulp such as softwood pulp and hardwood pulp; cotton pulp such as cotton linter and cotton lint; non-wood pulp such as straw pulp and bagasse pulp; and bacterial cellulose, and these can be used alone or in combination of two or more.

[0073] The average fiber diameter of the raw material cellulose fibers is preferably 1 μm or more, and preferably 300 μm or less, from the viewpoints of handling and cost.

[0074] Furthermore, from the viewpoints of availability and cost, the average fiber length of the raw cellulose fibers is preferably 100 μm or more and preferably 5,000 μm or less. The average fiber diameter and average fiber length of the raw cellulose fibers can be measured according to the method described in the Examples below. From the viewpoint of dispersibility, it is preferable to use cellulose fibers that have been subjected to a fiber shortening treatment such as alkaline hydrolysis or acid hydrolysis, and have an average fiber length of 1 μm or more and 1,000 μm or less.

[0075] The anionic group to be introduced includes a carboxy group, a sulfonic acid group, or a phosphoric acid group.

[0076] (i) When carboxyl groups are introduced as anionic groups into cellulose fibers Methods for introducing carboxy groups into cellulose fibers include, for example, a method of converting hydroxy groups of cellulose into carboxy groups by oxidation, and a method of reacting the hydroxy groups of cellulose with one or more compounds selected from the group consisting of compounds having carboxy groups, acid anhydrides of compounds having carboxy groups, and derivatives thereof.

[0077] The hydroxyl groups of the cellulose can be oxidized, for example, by reacting an oxidizing agent such as sodium hypochlorite with a bromide such as sodium bromide using 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) as a catalyst. For more details, known methods, such as those described in JP 2011-140632 A, can be used.

[0078] By subjecting cellulose fibers to oxidation using TEMPO as a catalyst, hydroxymethyl groups (—CHOH) at the C6 position of cellulose structural units are selectively converted to carboxy groups. This method is particularly advantageous in that it exhibits excellent selectivity for the hydroxy group at the C6 position, which is the target of oxidation on the surface of the raw cellulose fibers, and the reaction conditions are mild. Therefore, a preferred embodiment of the anion-modified cellulose fiber of the present invention is a cellulose fiber in which the C6 position of the cellulose structural unit is a carboxy group. In this specification, cellulose fibers obtained by oxidizing hydroxyl groups in cellulose structural units are sometimes referred to as “oxidized cellulose fibers,” and cellulose fibers in which the C6 position of the cellulose structural unit is a carboxy group are sometimes referred to as “TEMPO-oxidized cellulose fibers.” Oxidized cellulose fibers are preferred because they are easier to prepare than other anion-modified cellulose fibers. Therefore, one preferred embodiment of the modified cellulose fiber of the present invention is a modified cellulose fiber in which an amino-modified silicone is bonded to an oxidized cellulose fiber, and one more preferred embodiment is a modified cellulose fiber in which an amino-modified silicone is bonded to a TEMPO-oxidized cellulose fiber.

[0079] By further subjecting the oxidized cellulose fibers to a further oxidation treatment or reduction treatment, it is possible to prepare oxidized cellulose fibers from which the remaining aldehyde groups have been removed.

[0080] (ii) When sulfonic acid groups or phosphate groups are introduced as anionic groups into cellulose fibers As a method for introducing sulfonic acid groups as anionic groups into cellulose fibers, a method of adding sulfuric acid to cellulose fibers and heating the fibers can be given. Methods for introducing phosphate groups as anionic groups into cellulose fibers include mixing a powder or aqueous solution of phosphoric acid or a phosphoric acid derivative with dry or wet cellulose fibers, adding an aqueous solution of phosphoric acid or a phosphoric acid derivative to a dispersion of cellulose fibers, etc. When these methods are employed, dehydration treatment, heat treatment, etc. are generally carried out after mixing or adding a powder or aqueous solution of phosphoric acid or a phosphoric acid derivative.

[0081] (2) A process for obtaining modified cellulose fibers The modified cellulose fiber can be produced by bonding the anion-modified cellulose fiber with one or more compounds selected from the group consisting of a compound having a modifying group, preferably an amino-modified silicone, and a hydrocarbon compound having a cationic group, from the viewpoint of easily removing deposits from the membrane. Such a production method can be a known method, such as the method described in JP 2015-143336 A.

[0082] (Modification compound) From the viewpoint of improving the durability of the synovial fluid performance of the membrane, the modifying compound is a compound that has a modifying group and can bond with anion-modified cellulose fibers, preferably a compound that has a modifying group and can bond with anionic groups or hydroxy groups of anion-modified cellulose fibers, more preferably a compound that has a modifying group and a cationic group, even more preferably a compound that has a modifying group and an amino group or a quaternary ammonium group, and even more preferably a primary amine, secondary amine, tertiary amine or quaternary ammonium compound that has a modifying group. Preferred examples of the modifying compound include polymer compounds having an amino group and hydrocarbon compounds having a cationic group, from the viewpoint of easily removing deposits from the membrane.

[0083] (i) Polymer compounds having amino groups Polymer compounds having an amino group that are suitable as modifying compounds for the present invention are commercially available or can be prepared according to known methods. Only one type of polymer compound having an amino group may be used, or two or more types may be used.

[0084] Examples of the polymer compound having an amino group in the present invention include resins such as amino-modified silicone, polyoxyalkyleneamine, amino-modified poly(meth)acrylate polymer, amino-modified vinyl polymer, amino-modified polyester, amino-modified polycarbonate, polyallylamine, polyethyleneimine, etc.; chain aliphatic polyamine, cyclic aliphatic polyamine, alicyclic aromatic polyamine, etc., and the position of the reactive group may be any of the main chain, side chain, or terminal of the polymer compound. Among these, amino-modified silicone is preferred from the viewpoint of improving the durability of the synovial fluid performance of the membrane.

[0085] Amino-modified silicone is a silicone compound containing an amino group. Amino-modified silicone has a kinematic viscosity of 10 mm at 25°C. 2 / s or more 20,000mm 2 Further, amino-modified silicones having an amino equivalent of 400 g / mol or more and 16,000 g / mol or less are preferred.

[0086] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer. From the viewpoint of easily removing deposits from the film, a kinematic viscosity of 20 mm is more preferable. 2 / s or more, more preferably 50 mm 2 / s or more, and from the viewpoint of handling, 10,000 mm 2 / s or less, more preferably 5,000 mm 2 / s or less.

[0087] The amino equivalent is preferably 400 g / mol or more, more preferably 600 g / mol or more, and even more preferably 800 g / mol or more, from the viewpoint of easy removal of deposits from the membrane, and is preferably 16,000 g / mol or less, more preferably 14,000 g / mol or less, and even more preferably 12,000 g / mol or less, from the viewpoint of ease of bonding to anion-modified cellulose fibers. The amino equivalent is the molecular weight per nitrogen atom and is calculated by amino equivalent (g / mol) = weight average molecular weight / number of nitrogen atoms per molecule. Here, the number of nitrogen atoms can be determined by elemental analysis.

[0088] Specific examples of amino-modified silicones include compounds represented by general formula (a1).

[0089] [ka]

[0090] [In the formula, R 1a R represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, and is preferably a methyl group or a hydroxy group from the viewpoint of easily removing deposits from the film. 2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, or a hydrogen atom, and from the same viewpoint, is preferably a methyl group or a hydroxy group. B represents a side chain having at least one amino group, and R 3a represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. x and y each represent an average degree of polymerization, and are selected so that the kinematic viscosity at 25°C and amino equivalent of the compound fall within the above ranges. 1a , R 2a , R 3a may be the same or different, and multiple R 2a may be the same or different.

[0091] In the compound of general formula (a1), from the viewpoint of easily removing deposits from the membrane, x is preferably a number of 10 or more and 10,000 or less, more preferably a number of 20 or more and 5,000 or less, and even more preferably a number of 30 or more and 3,000 or less. y is preferably a number of 1 or more and 1,000 or less, more preferably a number of 1 or more and 500 or less, and even more preferably a number of 1 or more and 200 or less. From the viewpoint of improving the durability of the synovial fluid performance of the membrane, the weight-average molecular weight of the compound of general formula (a1) is preferably 2,000 or more, more preferably 5,000 or more, and even more preferably 8,000 or more, and from the same viewpoint, it is preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0092] In the general formula (a1), examples of the side chain B having an amino group include the following. -C3H6-NH2 -C3H6-NH-C2H4-NH2 -C3H6-NH-[C2H4-NH] e -C2H4-NH2 -C3H6-NH(CH3) -C3H6-NH-C2H4-NH(CH3) -C3H6-NH-[C2H4-NH] f -C2H4-NH(CH3) -C3H6-N(CH3)2 -C3H6-N(CH3)-C2H4-N(CH3)2 -C3H6-N(CH3)-[C2H4-N(CH3)] g -C2H4-N(CH3)2 -C3H6-NH-cyclo-C5H 11 (where e, f, and g are numbers from 1 to 30.)

[0093] (ii) Hydrocarbon compounds having cationic groups In the present invention, the hydrocarbon compound having a cationic group is one in which one or more hydrocarbon groups are bonded to one cationic group. The total carbon number of the hydrocarbon compound having a cationic group is preferably 4 or more, more preferably 8 or more, even more preferably 12 or more, even more preferably 16 or more, and even more preferably 18 or more, from the viewpoint of easy removal of deposits from the membrane, and is preferably 40 or less, more preferably 30 or less, even more preferably 26 or less, and even more preferably 22 or less, from the viewpoint of handleability.

[0094] A hydrocarbon compound having a cationic group is a compound in which the hydrocarbon group is directly bonded to a nitrogen atom or a phosphorus atom via a covalent bond when the cationic group is a primary amine, secondary amine, tertiary amine, quaternary ammonium, phosphonium, etc.; when the cationic group is an amidine, guanidine, etc., the compound is a compound in which the hydrocarbon group is bonded to at least one of the nitrogen atom or carbon atom of the functional group via a covalent bond; when the cationic group is an imidazolium, pyridinium, imidazoline, etc., the compound is a compound in which at least one hydrocarbon group is bonded to any position of the ring structure via a covalent bond. The hydrocarbon compound having a cationic group is more preferably one that does not contain an oxyalkylene group.

[0095] The hydrocarbon compounds may further have some hydrogen atoms substituted with, for example, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, a methoxy group, an ethoxy group, a carboxy group, an aldehyde group, a ketone group, or a thiol group.

[0096] (3) Micro-processing process By micronizing the cellulose at any stage in the manufacturing process of the modified cellulose fiber, it is possible to reduce the micrometer-scale cellulose to the nanometer-scale. By reducing the average fiber diameter to nanometer size, the strength of the film when formed is improved, so it is preferable to carry out an additional micronization treatment step.

[0097] [Component (B)] Component (B) in the present invention is an organic compound that is nonvolatile at 25°C and 1 atmosphere. Component (B) may be a solvent used in preparing component (A). In this specification, an organic compound that is nonvolatile at 25°C and 1 atmosphere means an organic compound that has a vapor pressure of less than 10 Pa under these conditions.

[0098] The solubility of component (B) in water is preferably 10 g or less, and more preferably 1 g or less, per 100 g of water at 25°C. From the viewpoint of easily removing deposits from the membrane, the molecular weight of component (B) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less, and from the same viewpoint, it is preferably 100 or more, more preferably 200 or more.

[0099] Specific examples of component (B) in the present invention include oils, organic solvents, polymerizable monomers, prepolymers, etc. Component (B) in the present invention is preferably an oil, and examples of the oil, from the viewpoint of easily removing deposits from the film, include one or more selected from the group consisting of alcohols, ester oils, hydrocarbon oils, silicone oils, ether oils, fats and oils, fluorine-based inert liquids, and fatty acids, preferably one or more selected from the group consisting of ester oils, silicone oils, ether oils, fats and oils, and fluorine-based inert liquids, more preferably one or more selected from the group consisting of silicone oils, ester oils, and ether oils, and even more preferably silicone oils and / or ester oils.

[0100] Examples of ester oils include monoester oils, diester oils, and triester oils, and specific examples include aliphatic or aromatic monocarboxylic or dicarboxylic acid esters having 2 to 18 carbon atoms, such as isopropyl myristate, octyldodecyl myristate, myristyl myristate, 2-hexyldecyl myristate, isopropyl palmitate, glycerin tri-2-ethylhexanoate, and glycerin triisostearate.

[0101] Examples of silicone oils include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.

[0102] Examples of fats and oils include vegetable oils such as soybean oil, coconut oil, linseed oil, cottonseed oil, rapeseed oil, and castor oil, as well as animal oils.

[0103] From the viewpoint of easily removing deposits from the film, component (B) preferably has an SP value of 10 or less, more preferably 9.5 or less, even more preferably 9.0 or less, and even more preferably 8.5 or less, and from the same viewpoint, preferably 6.0 or more, more preferably 6.5 or more. For example, an oil agent having an SP value of 10 or less, as described below, can be exemplified as a preferred example.

[0104] The SP value in this specification refers to the solubility parameter calculated by the Fedors method (unit: (cal / cm 3 ) 1 / 2 ) and are described in, for example, references such as "SP Value Basics, Applications and Calculation Methods" (Johokikansha, 2005) and Polymer Handbook Third Edition (A Wiley-Interscience publication, 1989).

[0105] Examples of oils having an SP value of 10 or less that can be suitably used in the present invention include oleic acid (SP value: 9.2), PEG400 (SP value: 9.4), dimethyl succinate (SP value: 9.9), neopentyl glycol dicaprate (SP value: 8.9), hexyl laurate (SP value: 8.6), isopropyl laurate (SP value: 8.5), isopropyl myristate (SP value: 8.5), isopropyl palmitate (SP value: 8.5), isopropyl oleate (SP value: 8.6), hexadecane (SP value: 8.0), olive oil (SP value: 9.3), jojoba oil (SP value: 8.6), squalane (SP value: 7.9), liquid paraffin (SP value: 7.9), and fluorine-based inert liquids. (For example, Fluorinert FC-40 (manufactured by 3M, SP value: 6.1), Fluorinert FC-43 (manufactured by 3M, SP value: 6.1), Fluorinert FC-72 (manufactured by 3M, SP value: 6.1), Fluorinert FC-770 (manufactured by 3M, SP value: 6.1)), silicone oil (for example, KF96-1cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3) , KF-96-10cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-50cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96-1000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), KF-96H-10,000cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), etc.

[0106] [Component (C)] The membrane of the present invention may further contain a polyether-modified silicone compound as component (C). By incorporating such component (C) into the emulsion composition, the membrane is preferably improved in its ability to easily remove deposits. An example of component (C) is a compound having a methylsilicone chain as the main chain and a polyoxyethylene group as the side chain, and specifically, a compound represented by the following general formula:

[0107] [ka]

[0108] In the formula, R 1is a methylene group, an ethylene group, or a trimethylene group, and R 2 represents an alkyl group having 1 to 4 carbon atoms, m represents an integer of 0 to 50, n represents an integer of 1 to 10, p represents an integer of 1 to 50, and q represents an integer of 0 to 50. 1 (C2H4O) p (C3H6O) q R 2 In the group represented by (C2H4O) p and (C3H6O) q can be random or block.

[0109] From the viewpoint of the durability of the film obtained by drying the emulsion composition, the HLB value of component (C) is preferably within a specific range, specifically, preferably 1 or more, more preferably 5 or more, even more preferably 10 or more, and preferably 18 or less, more preferably 16 or less.

[0110] When two or more polyether-modified silicones with different HLB values ​​are used, the HLB value of component (C) should be such that their weighted average falls within the above range. The HLB value is an index that represents the balance between hydrophilicity and lipophilicity, and in the present invention refers to the value calculated using the following Griffin formula: HLB value = 20 × total molecular weight of hydrophilic groups / molecular weight

[0111] The kinematic viscosity of component (C) at 25°C is preferably within a specific range from the viewpoint of the durability of the film obtained by drying the emulsion composition, and specifically, is preferably within a range of 1 mm 2 / s or more, preferably 5 mm 2 / s or more, preferably 1000 mm 2 / s or less, preferably 500 mm 2 / s or less, more preferably 200 mm 2 / s or less.

[0112] Polyether-modified silicone compounds that can be preferably used as component (C) are commercially available, and examples of commercially available products include KF-615A, KF-640, KF-642, KF-643, KF-644, KF-351A, KF-354L, KF-355A, KF-6011, KF-6012, KF-6015, KF-6016, KF-6017, KF-6020, and KF-6043 manufactured by Shin-Etsu Chemical Co., Ltd., and from the viewpoint of the durability of the film obtained by drying the emulsion composition, KF-640, KF-642, KF-643, KF-351A, KF-354L, and KF-355A can be preferably used. Commercially available products having a structure that does not fall within the general formula above (for example, KF-6028 and KF-6038 manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as component (C).

[0113] [Component (D)] The membrane of the present invention may further contain a polymer compound as component (D). Component (D) does not include components (A), (B), or (C). By incorporating component (D) into the emulsion composition, the membrane can be improved in its ability to easily remove deposits, which is preferable.

[0114] The weight average molecular weight of component (D) is preferably 1,000 or more from the viewpoint of facilitating removal of deposits from the membrane, and from the same viewpoint, is preferably 500,000 or less. As the component (D), one or more compounds selected from the group consisting of the following polymer compounds (X) and (Y) are preferred. Polymer compound (X): a polymer compound having an ester group, an amide group, a urethane group, an amino group, an ether group, or a carbonate group in the main chain Polymer compound (Y): a methacrylic or acrylic polymer having an ester group or an amide group in the side chain Specific preferred examples of component (D) include polyalkyl(meth)acrylates such as polymethyl(meth)acrylate, polyethyl(meth)acrylate, and polybutyl(meth)acrylate; copolymers with acrylic such as styrene-acrylic and urethane-acrylic; and poly(meth)acrylamides such as poly(meth)acrylamide, poly-N-methyl(meth)acrylamide, poly-N,N-dimethyl(meth)acrylamide, and poly-N-phenyl(meth)acrylamide.

[0115] [Volatile organic compounds] The film of the present invention may further contain an organic compound that is volatile at 25°C and 1 atmosphere. By incorporating such a component into the emulsion composition, it is possible to improve the property of easily removing deposits from the film, which is preferable. In this specification, an organic compound that is volatile at 25°C and 1 atmosphere means an organic compound whose vapor pressure under such conditions is 10 Pa or more.

[0116] Such components include, for example, N-methylpyrrolidone, 2-propanol, 1-propanol, ethanol, methanol, t-butanol, 1-butanol, 2-butanol, toluene, xylene, methyl ethyl ketone, acetone, ethyl acetate, dimethylformamide, methyl isobutyl ketone, acetonitrile, dimethyl sulfoxide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, hexane, cyclohexane, cyclohexanone, 1,4-dioxane, chloroform, dichloromethane, diethyl ether, and mixtures thereof.

[0117] [Other ingredients] In addition to the above components, the film of the present invention can contain plasticizers, nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, lubricants such as hydrocarbon waxes and anionic surfactants, UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, mildew inhibitors, antibacterial agents, foaming agents, surfactants; starches, polysaccharides such as alginic acid; natural proteins such as gelatin, glue, and casein; inorganic compounds such as tannins, zeolites, ceramics, and metal powders; fragrances; flow adjusters; leveling agents; conductive agents; UV dispersants; deodorizers, etc., within a range that does not impair the effects of the present invention. Similarly, other polymeric materials and other compositions can also be added within a range that does not impair the effects of the present invention.

[0118] [Content of each component in the film] The content of component (A) in the film is preferably 5% by mass or more, more preferably 10% by mass or more, and even more preferably 20% by mass or more from the viewpoint of improving the durability of the film, while from the viewpoint of handleability, it is preferably 80% by mass or less, more preferably 50% by mass or less, and even more preferably 30% by mass or less.

[0119] The content of component (B) in the film is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more, from the viewpoint of easy removal of deposits from the film, while from the viewpoint of film durability, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0120] From the viewpoint of durability of the film, the content of component (C) in the film is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, while from the same viewpoint, it is preferably 4% by mass or less, more preferably 3% by mass or less, and even more preferably 2% by mass or less.

[0121] The content of component (D) in the film is preferably 10% by mass or more, more preferably 20% by mass or more, and even more preferably 30% by mass or more from the viewpoint of film durability, while it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less from the viewpoint of easy removal of deposits from the film.

[0122] 2. Base material The substrate is a material that ensures the mechanical strength of various members, and examples thereof include various metals such as steel, stainless steel, copper alloys, and aluminum, as well as plastics, glass, and concrete.

[0123] The thickness of the substrate is preferably 0.01 mm or more, more preferably 0.1 mm or more, and even more preferably 1 mm or more from the viewpoint of mechanical strength, and is preferably 100 mm or less, more preferably 10 mm or less, and even more preferably 5 mm or less from the viewpoint of productivity.

[0124] 3. Method for forming laminate The laminate can be formed, for example, by a method including the following steps 1 and 2. Step 1: A step of applying an emulsion composition containing the following components (A), (B), and water onto a resin surface. (A) Cellulose fibers with modified groups (B) Non-volatile organic compounds at 25°C and 1 atmosphere Step 2: After Step 1, drying the emulsion composition

[0125] <Process 1> Step 1 is a step of applying an emulsion composition onto the surface of a resin. Examples of application methods include spraying the emulsion composition using an air spray, airless spray, trigger spray, or the like, spraying using an aerosol can, application using a brush, roller, cloth, or the like, dip application, etc. These application methods can be said to be very simple and convenient. The thickness of the coating film on the resin surface is preferably 0.001 mm or more, more preferably 0.01 mm or more, and even more preferably 0.1 mm or more, from the viewpoint of easy removal of deposits from the film, and is preferably 10 mm or less, more preferably 1 mm or less, and even more preferably 0.5 mm or less, from the viewpoint of productivity.

[0126] <Process 2> Step 2 is a step of drying the emulsion composition after step 1. By drying the emulsion composition, a film is formed on the resin surface.

[0127] The method for drying the emulsion composition may be air drying at room temperature and normal pressure, or the drying may be accelerated by heating or reducing the pressure.

[0128] <Emulsified composition> The emulsion composition contains the above-mentioned components (A), (B), and water, and may optionally contain components (C), (D), and a volatile organic compound.

[0129] The content of component (A) in the emulsion composition is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of emulsifying power, while it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of handleability.

[0130] The content of component (B) in the emulsion composition is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more, from the viewpoint of maintaining the emulsified state, while from the viewpoint of viscosity and handleability, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0131] The content of component (C) in the emulsion composition is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, from the viewpoint of improving the durability of the film, and from the same viewpoint, is preferably 10% by mass or less, more preferably 1% by mass or less, and even more preferably 0.3% by mass or less.

[0132] The content of component (D) in the emulsion composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of improving the durability of the film, and from the same viewpoint, is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 7% by mass or less.

[0133] The content of the volatile organic compounds in the emulsion composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of facilitating film formation on a substrate, and from the same viewpoint, is preferably 50% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0134] The water content in the emulsion composition is preferably 10% by mass or more, more preferably 30% by mass or more, even more preferably 50% by mass or more, and even more preferably 70% by mass or more, from the viewpoint of maintaining the emulsified state, while from the viewpoint of viscosity and handleability, it is preferably 98% by mass or less, more preferably 90% by mass or less, and even more preferably 80% by mass or less.

[0135] The mass ratio of component (B) to component (A) in the emulsion composition ((B) / (A)) is preferably 0.1 or more, more preferably 1 or more, and even more preferably 1.5 or more, from the viewpoint of easily removing deposits from the film, and from the same viewpoint, is preferably 10 or less, more preferably 5 or less, and even more preferably 2 or less.

[0136] From the viewpoint of ease of handling, the viscosity of the emulsion composition at 25°C is preferably 0.5 mPa·s or more, more preferably 0.8 mPa·s or more, even more preferably 1 mPa·s or more, and even more preferably 5 mPa·s or more, and from the same viewpoint, is preferably 30 Pa·s or less, more preferably 10 Pa·s or less, even more preferably 1 Pa·s or less, even more preferably 100 mPa·s or less, and even more preferably 20 mPa·s or less. Here, the viscosity can be measured according to the method described in the Examples below.

[0137] The median particle size of the emulsified droplets in the emulsion composition, as measured by the laser diffraction method described below, is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more, from the viewpoint of improving water resistance, synovial fluid resistance, and durability thereof; and from the same viewpoint, is preferably 2000 nm or less, more preferably 1000 nm or less, even more preferably 700 nm or less, and even more preferably 500 nm or less.

[0138] <Method for preparing emulsion composition> The method for preparing the emulsion composition of the present invention includes a step of mixing the aforementioned component (A), component (B), water, etc., or a step of mixing anion-modified cellulose fiber, a modifying compound, component (B), water, etc.

[0139] Mixing the components causes emulsification, resulting in an emulsion composition. For this mixing process, a magnetic stirrer, mechanical stirrer, homomixer, vacuum emulsifier, low-pressure homogenizer, high-pressure homogenizer, grinder, cutter mill, ball mill, jet mill, single-screw extruder, twin-screw extruder, ultrasonic agitator, household juicer mixer, etc. can be used. The mixing process may be performed by combining two or more operations.

[0140] The temperature and time for mixing the components are preferably within the range of 5 to 50°C and 1 minute to 3 hours, for example.

[0141] The preferred range of the content of each component when mixed is the same as the preferred range of the content of each component in the emulsion composition of the present invention described above.

[0142] 4. Method of removing the membrane-containing layer from the laminate using a water jet The film containing component (A) and component (B), or the resin layer together with the film, can be removed from the laminate of the present invention with a water stream. A specific method for removing the membrane using a water flow is to spray a water flow at a certain pressure onto the laminate, or in the case of a ship of the present invention equipped with the laminate, since it contains a soluble resin, the layer including the membrane can be gradually removed by sailing on fresh water or seawater. [Example]

[0143] The present invention will be specifically described below by showing examples etc. Note that the following examples are merely illustrative of the present invention and are not intended to limit the present invention in any way.

[0144] [Average fiber diameter, average fiber length, and average aspect ratio of anion-modified cellulose fibers and modified cellulose fibers] Water is added to the cellulose fibers to be measured to prepare a dispersion with a cellulose content of 0.0001% by mass. The dispersion is dropped onto mica and dried to serve as an observation sample. An atomic force microscope (AFM) (Digital Instruments, Nanoscope II Tapping mode AFM; Nanosensors, Point Probe (NCH) probe) is used to measure the fiber height (height difference between fiber-containing and fiber-free areas) of the cellulose fibers in the observation sample. At this time, 100 or more cellulose fibers are extracted from a microscopic image in which the cellulose fibers can be seen, and the average fiber diameter is calculated from their fiber height. The average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated by dividing the average fiber length by the average fiber diameter. The height analyzed in the AFM image can be considered the fiber diameter.

[0145] [Average fiber diameter and average fiber length of raw cellulose fibers] Deionized water is added to the cellulose fibers to be measured to prepare a dispersion containing 0.01% by mass of cellulose. The dispersion is measured using a wet dispersion image analysis particle size distribution analyzer (IF-3200, manufactured by Jusco International) under the following conditions: front lens: 2x, telecentric zoom lens: 1x, image resolution: 0.835 μm / pixel, syringe inner diameter: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghost, threshold: 8, analysis sample volume: 1 mL, and sampling: 15%. At least 100 cellulose fibers are measured, and the average ISO fiber diameter and average ISO fiber length are calculated as the average fiber diameter and average fiber length, respectively.

[0146] [Anionic Group Content of Anion-Modified Cellulose Fibers and Modified Cellulose Fibers] A 100 mL beaker is filled with 0.5 g of dry cellulose fiber to be measured, and deionized water or a 2:1 methanol / water mixture is added to make a total volume of 55 mL. 5 mL of 0.01 M sodium chloride aqueous solution is then added to prepare a dispersion. The dispersion is stirred until the cellulose fiber to be measured is fully dispersed. 0.1 M hydrochloric acid is added to the dispersion to adjust the pH to 2.5-3. Using an automatic titrator (DKK-TOA Corporation, AUT-701), 0.05 M sodium hydroxide aqueous solution is added dropwise to the dispersion with a waiting time of 60 seconds, and the conductivity and pH values ​​are measured every minute. Measurements are continued until the pH reaches approximately 11, and a conductivity curve is obtained. The sodium hydroxide titration amount is determined from this conductivity curve, and the anionic group content of the cellulose fiber to be measured is calculated using the following formula: Anionic group content (mmol / g) = [sodium hydroxide titration amount × sodium hydroxide aqueous solution concentration (0.05 M)] / [mass of cellulose fiber to be measured (0.5 g)]

[0147] [Aldehyde group content of oxidized cellulose fiber] The carboxy group content of the oxidized cellulose fiber to be measured is measured by the above-mentioned method for measuring the anionic group content. Separately, 100 g of the aqueous dispersion of the oxidized cellulose fiber to be measured (solids content: 1.0% by mass), 100 g of acetate buffer (pH 4.8), 0.33 g of 2-methyl-2-butene, and 0.45 g of sodium chlorite were added to a beaker and stirred at 25°C for 16 hours to oxidize any remaining aldehyde groups in the oxidized cellulose fiber. After the reaction was complete, the fiber was washed with deionized water to obtain cellulose fiber with the aldehyde groups oxidized. The reaction solution was freeze-dried, and the carboxyl group content of the resulting dried product was measured using the anionic group content measurement method described above to calculate the "carboxyl group content of the oxidized oxidized cellulose fiber." The aldehyde group content of the oxidized cellulose fiber to be measured was then calculated using Equation 1. Aldehyde group content (mmol / g) = (carboxyl group content of oxidized cellulose fiber after oxidation treatment) - (carboxyl group content of oxidized cellulose fiber to be measured) Equation 1

[0148] [Solid content in dispersion] Measurements are taken using a halogen moisture meter (Shimadzu Corporation, MOC-120H). Measurements are taken every 30 seconds for 1 g of sample at a constant temperature of 150°C, and the value when the mass loss is 0.1% or less of the initial amount of the sample is taken as the solid content.

[0149] [Confirmation of crystalline structure in modified cellulose fibers] The crystalline structure of the modified cellulose fiber is confirmed by measurement under the following conditions using an X-ray diffractometer (MiniFlexII, manufactured by Rigaku Corporation). The measurement conditions were as follows: X-ray source: Cu / Kα-radiation, tube voltage: 30 kV, tube current: 15 mA, measurement range: diffraction angle 2θ = 5 to 45°, X-ray scan speed: 10° / min. The measurement sample had an area of ​​320 mm 2 The cellulose is compressed into a pellet with a thickness of 1 mm. The degree of crystallinity of the cellulose type I crystal structure is calculated from the obtained X-ray diffraction intensity according to the following formula A.

[0150] <Formula A> Cellulose type I crystallinity (%) = [(I 22.6 -I 18.5 ) / I22.6 ] x 100 [In the formula, I 22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6°) in X-ray diffraction, I 18.5 indicates the diffraction intensity of the amorphous part (diffraction angle 2θ = 18.5°).

[0151] On the other hand, if the crystallinity obtained by the above formula A is 35% or less, it is preferable to calculate it based on the following formula B in accordance with the description on pages 199-200 of the "Wood Science Experiment Manual" (edited by the Japan Wood Research Society; published in April 2000) in order to improve calculation accuracy. Therefore, when the crystallinity obtained by the above formula A is 35% or less, the value calculated based on the following formula B can be used as the crystallinity.

[0152] <Formula B> Cellulose type I crystallinity (%) = [A c / (A c +A a )] × 100 [In the ceremony, A c is the sum of the peak areas of the lattice planes (002 plane) (diffraction angle 2θ = 22.6°), (011 plane) (diffraction angle 2θ = 15.1°), and (0-11 plane) (diffraction angle 2θ = 16.2°) in X-ray diffraction, A a indicates the peak area of ​​the amorphous portion (diffraction angle 2θ = 18.5°), and each peak area is determined by fitting the obtained X-ray diffraction chart with a Gaussian function.

[0153] [Measurement of Viscosity of Emulsion Composition] Using a B-type viscometer (Toki Sangyo TVB-10) with a No. 1 rotor, measure the viscosity after 1 minute at 25°C and a rotation speed of 60 RPM.

[0154] [Measurement of particle size of emulsion droplets by laser diffraction method] The particle size of the emulsified droplets is measured by laser diffraction using an LA-960 manufactured by Horiba Ltd. Measurement conditions: Add water to the measurement cell and measure the volume particle size distribution and median (volume cumulative median particle size (D50)) at a concentration that brings the absorbance into the appropriate range. The relative refractive index is 1.20, the temperature is 25°C, the circulation pump is on, the circulation speed is 5, and the stirring speed is 5.

[0155] [Measurement of film thickness] The thickness of the dried film was measured using a laser microscope (Keyence VK-9710) under the following conditions: objective lens: 10x, light intensity: 3%, brightness: 1548, Z pitch: 0.5 μm. A portion of the film was scraped off with a metal spatula, and the sample with the exposed base was measured. The height of the base and the height of the film were measured using the built-in image processing software, and the difference between these values ​​was used to determine the film thickness.

[0156] [Composition of the upper layer] After the emulsion composition is spread on the base body Drying Assuming that all of the volatile organic compounds and water in the emulsion composition had evaporated, the composition of the upper layer was calculated from the concentration of the active ingredients of each component in the emulsion composition shown in Table 3.

[0157] [Anion-modified cellulose fiber] Anion-modified cellulose fibers having the physical properties shown in Table 1 were used as raw materials.

[0158] [Table 1]

[0159] Such anionically modified cellulose fibers can be prepared, for example, by the TEMPO oxidation treatment described below.

[0160] [TEMPO oxidation treatment] 10 g of bleached softwood kraft pulp fiber (natural cellulose fiber) and 990 g of deionized water were weighed into a 2 L polypropylene beaker equipped with a mechanical stirrer and impeller and stirred at 25°C and 100 rpm for 30 minutes. Next, 0.13 g of TEMPO, 1.3 g of sodium bromide, and 35.5 g of a 10.5% by mass sodium hypochlorite solution were added to the 10 g of pulp fiber in this order. Next, pH stat titration was performed using an automatic titrator, and 0.5 M sodium hydroxide solution was added dropwise to maintain the pH at 10.5. The reaction was carried out at 25°C for 120 minutes with stirring at 100 rpm.

[0161] Next, 0.01 M hydrochloric acid is added to the suspension while stirring to adjust the pH of the suspension to 2. The solids are then separated by suction filtration. The solids are dispersed in deionized water and the filtrate is separated by suction filtration. This procedure is repeated until the conductivity of the filtrate reaches 200 μs / cm or less. The resulting solids are then dehydrated to obtain anionically modified cellulose fibers.

[0162] [Preparation of reduction-treated, finely divided anion-modified cellulose fibers] The anion-modified cellulose fibers were subjected to a micronization treatment and then a reduction treatment to prepare micronized anion-modified cellulose fibers having the physical properties shown in Table 2.

[0163] [Table 2]

[0164] Such finely divided anionically modified cellulose fibers can be prepared, for example, by the following fine division treatment and reduction treatment.

[0165] [Fine processing] Deionized water was added to the anion-modified cellulose fiber to prepare 100 g of a suspension (solid content 2.0% by mass), to which 0.5 M aqueous sodium hydroxide was added to adjust the pH to 8. Deionized water was then added to make a total of 200 g. This suspension was subjected to a micronization treatment three times at 150 MPa using a high-pressure homogenizer to obtain a micronized anion-modified cellulose fiber dispersion (solid content 1.0% by mass).

[0166] [Reduction process] 182 g of a finely divided anion-modified cellulose fiber dispersion (solid content 1.0% by mass) was weighed out and added with deionized water to a total of 400 g. 1.2 mL of 0.1 M aqueous sodium hydroxide and 120 mg of sodium borohydride were added and stirred at 25°C for 4 hours. 9 mL of 1 M hydrochloric acid was then added and stirring continued. After stirring was completed, the solids obtained by suction filtration were dispersed in deionized water, and the solids were separated by suction filtration. This procedure was repeated six times. In this way, a finely divided anion-modified cellulose fiber dispersion (solid content 0.9% by mass) in which the aldehyde groups present in the finely divided anion-modified cellulose fiber had been reduced was obtained.

[0167] [Preparation of emulsified mixture] In a beaker, 66.7 g of the dispersion of the micronized anion-modified cellulose fiber (solids content 0.9% by mass) having the physical properties listed in Table 2, 6.0 g of silicone oil, and 2.67 g of amino-modified silicone as a modifying compound (corresponding to 1.75 equivalents relative to the carboxy groups of the anion-modified cellulose fiber) were mixed, and deionized water was added to make a total of 100 g. This dispersion was stirred with a mechanical stirrer at room temperature for 5 minutes and then subjected to 10 passes at 150 MPa in a high-pressure homogenizer (Yoshida Kikai Co., Ltd., Nanovaita L-ES) to obtain an emulsified mixture containing modified cellulose fiber in which the amino-modified silicone was ionic-bonded to the anion-modified cellulose fiber. The resulting mixture was a cloudy white liquid, and oil droplets dispersed in water were observed under an optical microscope, indicating that it was an emulsion. The median particle size of the emulsified droplets was 300 nm.

[0168] Examples 1 and 2 The emulsified mixture and the raw materials shown in the table were weighed into a beaker so as to achieve the active ingredient concentrations shown in the table, and stirred at 25°C for 30 minutes to obtain an emulsified composition for forming a laminate.

[0169] Details of representative components used in the examples are summarized below. [Modification compound] Amino-modified silicone: Dow Toray, DOWSIL TM SS-3551, kinematic viscosity: 1,000, amino equivalent: 1,700 [Component (B)] Silicone oil: Shin-Etsu Chemical Co., Ltd., KF-96-100cs, SP value: 7.3 [Volatile organic compounds at 25°C and 1 atmosphere] N-methylpyrrolidone: Fujifilm Wako Pure Chemical Industries, Ltd. 2-Propanol: Fujifilm Wako Pure Chemical Industries, Ltd. [Component (C)] Polyether-modified silicone: Shin-Etsu Chemical Co., Ltd., KF-642, HLB: 14 [Component (D)] Styrene acrylic: NeoCryl XK-188 (solid content 44.5% by mass) manufactured by DSM

[0170] [Coating of lower layer body] An acrylic resin paint (SEAFLO NEO CF Z, manufactured by Chugoku Paint Co., Ltd.) was applied to a SUS329J4L substrate (100 mm x 300 mm x 3 mm thick) to form a lower layer using an applicator (manufactured by Tester Sangyo Co., Ltd.) to a thickness of 200 μm. The solvent was evaporated by drying at room temperature for 12 hours, resulting in a laminated structure of the substrate and lower layer with a film thickness of approximately 100 μm. The acrylic resin paint used here is a soluble resin.

[0171] [Creating an upper layer on a lower layer] Each of the emulsion compositions prepared in Examples 1 and 2 was spread over the entire surface of the lower layer of the laminated structure to give a coating thickness shown in the table. The solvent was then evaporated by drying at room temperature for 24 hours, yielding a structure comprising a laminate of the lower layer and upper layer shown in the table.

[0172] Comparative Example 1 A structure having only the lower layer body without the upper layer body was used as Comparative Example 1.

[0173] [Evaluation of synovial fluid] Test Example 1 The structures of Examples 1 and 2 and Comparative Example 1 prepared as described above were placed horizontally with the upper layer facing upward. An 8 μL water droplet (23°C) was dropped onto each film at 23°C using a fully automatic contact angle meter (Kyowa Interface Science Co., Ltd., FAMAS) and allowed to stand for 1 second. The film surface was then tilted to 85° at a rate of 1° / s, and the angle at which the water droplet began to slide was measured. The smaller the water droplet sliding angle, the higher the film's synovial properties. The composition of each component (mass parts in the dry film) and the evaluation results are shown in the table below. However, if the water droplet did not slide even when tilted to 85°, the water droplet sliding angle was recorded as "greater than 85°."

[0174] [Field aquatic organism adhesion test] Test Example 2 The substrates equipped with the laminate of the upper and lower layers of Examples 1 and 2 and the substrate of Comparative Example 1 were connected with chains and placed in seawater near Shimotsu Port in Wakayama Prefecture so that they were 2 m deep from the water surface at low tide, and an immersion test in seawater was conducted for 7 months. After 1 month, 3 months, and 7 months of immersion, the degree of adhesion of crustaceans and algae to the substrates was visually evaluated. The evaluation criteria were as follows: The smaller the value, the greater the effect of inhibiting adhesion of aquatic organisms.

[0175] 1: A state in which aquatic organisms adhere to the substrate surface at 2% or less of its area. 2: A state in which aquatic organisms are attached to more than 2% and less than 10% of the area of ​​the substrate surface. 3: A state in which aquatic organisms are attached to more than 10% but less than 20% of the surface area of ​​the substrate. 4: A state in which aquatic organisms are attached to more than 20% but less than 30% of the area of ​​the substrate surface. 5: A state in which aquatic organisms are attached to more than 30% but less than 50% of the area of ​​the substrate surface. 6: A state in which aquatic organisms are attached to more than 50% but less than 80% of the area of ​​the substrate surface. 7: A state in which aquatic organisms are attached to more than 80% of the surface area of ​​the substrate.

[0176] [Deposit removal test] Test Example 3 In the above Test Example 1, the removability of aquatic organisms attached to the substrate was evaluated after 1 month, 3 months, and 7 months according to the following criteria. The water flow here was evaluated by flowing water at a speed of 13.3 L / min horizontally to the substrate. The smaller the value, the easier it was to remove the attached organisms. In Example 2, the upper layer peeled off from the lower layer after 3 months, and the evaluation was terminated at that point.

[0177] 1: Only the adhesions can be removed with a water flow. 2: The upper layer can be removed by using a water flow to peel off the attached material. 3: Only the adhesions can be removed by using a water jet and scrubbing. 4: Tools are required to remove adhesions.

[0178] Furthermore, the surface condition after removal of the deposits was visually inspected and evaluated for the presence or absence of surface damage due to the removal work. In cases where the removability score was 2 or 3 (the upper layer was also peeled off), the surface condition of the lower layer after the upper layer was peeled off was evaluated.

[0179] [Table 3]

[0180] From Table 1, it can be seen that the structure of the example in which the upper layer body is laminated on the lower layer body has the effect of suppressing the adhesion of aquatic organisms itself compared to the lower layer body alone, and is also excellent in removing attached aquatic organisms. It was confirmed that it was particularly excellent in suppressing the adhesion of crustaceans. Furthermore, it was found that the structure of the example in which the upper layer body was laminated on the lower layer body could be easily peeled off together with the attached matter using only a water flow after immersion for a certain period of time, and a clean lower layer body without any defects could be exposed. Therefore, it is possible to form an upper layer body again on the lower layer body with a simple operation using the emulsion composition of the present invention.

[0181] A comparison of Examples 1 and 2 revealed that the durability period until the upper layer peeled off from the lower layer was longer when N-methylpyrrolidone was used as the volatile organic compound than when 2-propanol was used. While the reason for this is unclear, it is believed that, despite being organic media with similar SP values, N-methylpyrrolidone has a higher boiling point than 2-propanol, and therefore takes longer to volatilize, allowing it to slowly interdiffuse with the lower layer. On the other hand, when crustaceans adhered to Comparative Example 1, tools were required to remove the deposits, and defects were observed on the surface after removal. From these results, it can be expected that a ship equipped with a resin layer containing a soluble resin and a laminate including a film containing component (A) and component (B) will also be able to suppress the attachment of aquatic organisms themselves, and will also have excellent effects in removing attached aquatic organisms. [Explanation of symbols]

[0182] 1 Base material 2 Resin layer 3 membrane

Claims

1. A laminate comprising a resin layer containing a soluble resin and a film containing the following components (A) and (B), wherein the soluble resin is a resin that exhibits solubility under conditions in which it comes into contact with flowing water. (A) Anion-modified cellulose fibers into which modifying groups have been introduced using amino-modified silicone (B) Oil with an SP value of 10 or less

2. The laminate according to claim 1 , wherein the film further contains the following component (C): (C) Polyether-modified silicone

3. The laminate according to claim 1 or 2, wherein the film further contains the following component (D): (D) Polymer compounds (excluding those falling under component (A), component (B), or component (C))

4. A method for removing the layer containing the film from the laminate according to any one of claims 1 to 3 using a water jet.

5. A ship equipped with a laminate including a resin layer containing a soluble resin and a membrane containing the following components (A) and (B), wherein the soluble resin is a resin that exhibits solubility under conditions in which it comes into contact with flowing water. (A) Anion-modified cellulose fibers into which modifying groups have been introduced using amino-modified silicone (B) Oil with an SP value of 10 or less

6. A method for removing a layer including the membrane from a vessel equipped with the laminate according to claim 5 using a water flow.

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