Method for restoring the surface properties of synovial fluid surface films

Abstract

To provide a method for restoring the synovial surface properties of a synovial surface film that has been damaged and whose synovial surface properties have deteriorated. [Solution] A method for restoring the synovial surface properties of a synovial surface film, comprising a standing step of allowing the damaged synovial surface film, whose synovial surface properties have deteriorated, to stand for more than 5 minutes, wherein the synovial surface film is a synovial surface film containing a liquid organic compound at 25°C and 1 atm.

Description

[Technical Field]

[0001] The present invention relates to a method for restoring the synovial surface properties of a synovial surface film having synovial surface properties. [Background technology]

[0002] Conventionally, surface films have been developed to prevent the adhesion of dirt, marine organisms, and other materials. Recently, a synovial film containing hydrophobic modified cellulose fibers and oil has become known as such a surface film. Patent Document 1 discloses that a synovial film can be obtained by applying an emulsified composition containing anionic modified cellulose fibers, amino-modified silicone, and an organic compound that is liquid at 25°C and 1 atm to a solid surface.

[0003] Such a lubricating film can also be used outdoors. By forming the film on outdoor structures, such as traffic lights, it is possible to prevent dirt and snow from accumulating, which can lead to a reduction in maintenance costs.

[0004] A film having such a synovial surface film is formed on one surface of a base film, and an adhesive layer is provided on the other surface of the base film. This film can be easily applied by anyone and is used as an anti-fouling film that prevents the adhesion of bird droppings, snow, rainwater, etc. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2021-095557 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, when such an antifouling film is used outdoors, there are specific circumstances. Specifically, outdoors, there are external factors that can damage the lubricant surface film itself, such as dust, sand, wind, rain, bird claws, flying stones, and when placed in the sea, waves and floating objects, etc. When damaged by such external factors, the lubricant surface property is impaired at the damaged location, so the sliding off of dirt, etc. stops at that part, and the function as an antifouling film is greatly impaired.

[0007] Therefore, the present invention relates to providing a method for restoring the lubricant surface property of a lubricant surface film whose lubricant surface property has decreased due to damage.

Means for Solving the Problems

[0008] The present invention relates to the following [1] to

[12] . [1] A method for restoring the lubricant surface property of a lubricant surface film, including a standing step of allowing a lubricant surface film whose lubricant surface property has decreased due to damage to stand for more than 5 minutes, wherein the lubricant surface film is a lubricant surface film containing the following component (A), A method for restoring the lubricant surface property of a lubricant surface film. (A) An organic compound that is liquid at 25°C and 1 atm [2] The method for restoring the lubricant surface property according to [1] above, wherein the lubricant surface film contains the following component (B). (B) Anionic modified cellulose fiber [3] The method for restoring the lubricant surface property according to [1] or [2] above, wherein the lubricant surface film contains the following component (C). (C) A hydrophobic compound having a cationic functional group (excluding those corresponding to the above component (A)). [4] The method for restoring the lubricant surface property according to any one of [1] to [3] above, wherein the relative humidity in the standing step is 40%RH or more. [5] A film having a resin layer and a lubricant surface film on one surface of the resin layer, wherein the lubricant surface film is a lubricant surface film having a lubricant surface property and containing the following component (A). (A) An organic compound that is liquid at 25°C and 1 atm [6] The film according to [5], which has the ability to restore the synovial surface properties when damaged and the synovial surface properties are reduced. [7] The film according to [5] or [6], wherein the synovial surface film contains the following component (B). (B) Anionic modified cellulose fibers [8] The film according to any one of items [5] to [7] above, wherein the synovial fluid surface film contains the following component (C). (C) Hydrophobic compounds having cationic functional groups (excluding those corresponding to component (A) above). [9] A film as described in any one of items [5] to [8] above, which is for stain prevention, snow prevention and / or antibacterial purposes.

[10] The film according to any one of the above [5] to [9], further having an adhesive layer on the surface opposite to the surface having a synovial surface film of the resin layer.

[11] A film repair agent containing the following ingredient (A). (A) Organic compounds that are liquid at 25°C and 1 atm

[12] The film repair agent according to

[11] , further comprising the following component (B) and / or component (C). (B) Anionic modified cellulose fibers (C) Hydrophobic compounds having cationic functional groups (excluding those corresponding to component (A) above). [Effects of the Invention]

[0009] According to the present invention, a method can be provided for restoring the synovial surface properties of a synovial surface film that has been damaged and whose synovial surface properties have deteriorated. [Brief explanation of the drawing]

[0010] [Figure 1] Figure 1 is a schematic diagram showing how damaged area 1 recovers through rest, and the numerical values ​​in the graph are relative values. [Figure 2] Figure 2 is a schematic diagram illustrating the general procedure for the film slippage test. [Modes for carrying out the invention]

[0011] As a result of our investigations, we discovered that the synovial surface properties of a synovial fluid surface film containing a specific component, namely a liquid organic compound at 25°C and 1 atm, can be unexpectedly restored by allowing it to stand for a certain period of time, preferably under a constant relative humidity, thus completing the present invention.

[0012] <Method for restoring the surface properties of the synovial fluid surface film> The present invention provides a method for restoring the synovial surface properties of a synovial surface film, which includes a settling step of allowing a damaged synovial surface film, whose synovial surface properties have deteriorated, to stand for more than 5 minutes, wherein the synovial surface film is a synovial surface film containing the following component (A). (A) Organic compounds that are liquid at 25°C and 1 atm.

[0013] In the settling process, the damaged synovial fluid surface film is left to stand for more than 5 minutes. It is presumed that by standing, component (A) gradually moves (bleeds) from the surrounding area to fill the damage, thereby restoring the synovial fluid surface properties. Figure 1 is a schematic diagram showing how the damaged area 1 recovers through standing, and the numerical values ​​in the graph are relative values.

[0014] Causes of damage include dust and sand in the air, snow, rainwater, freezing of condensed water droplets, flying objects such as stones, and physical damage caused by the activity of plants and animals. The restoration method of the present invention is applicable regardless of the cause of the damage.

[0015] The standing time in the standing process is more than 5 minutes, preferably 10 minutes or more, and more preferably 24 hours or more, from the viewpoint of ensuring time for component (A) to bleed and restore the synovial surface properties. On the other hand, there is no particular upper limit to the standing time, but for example, 1 year or less is preferred.

[0016] From the viewpoint of promoting the bleeding of component (A), a higher relative humidity during the standing process is preferable. Specifically, the relative humidity during the standing process is preferably 40%RH or higher, more preferably 60%RH or higher, and even more preferably 80%RH or higher. There is no particular upper limit to the relative humidity during the standing process, but for example, 100%RH or lower is preferable.

[0017] From the viewpoint of promoting the bleeding of component (A), a higher temperature during the standing process is preferable. However, even when the temperature is below freezing, such as outdoors in winter, the lubricant surface properties can be restored according to the recovery method of the present invention. Specifically, the temperature during the standing process is preferably -20°C or higher, more preferably -10°C or higher, even more preferably 0°C or higher, and even more preferably 5°C or higher. The upper limit of the temperature during the standing process is preferably 250°C or lower, more preferably 150°C or lower, and even more preferably 100°C or lower, from the viewpoint of preventing thermal decomposition of component (B).

[0018] <Synovial surface film with synovial surface properties> The synovial surface film in the present invention exhibits the synovial surface properties described in the literature (Technology of Superhydrophobic, Superoleophobic, and Synovial Surfaces / Publisher: Hiroshi Motoki / Distributor: Science & Technology Co., Ltd. / Published January 28, 2016). In this specification, such synovial surface properties are also simply referred to as "synovial properties." Whether a film has synovial surface properties can be evaluated by the method described in the examples below.

[0019] There are no particular limitations on the thickness of the synovial surface film having synovial surface properties. From the viewpoint of film durability, it is preferably 1 μm or more, more preferably 3 μm or more, and even more preferably 5 μm or more. From the viewpoint of economic efficiency, it is preferably 2,000 μm or less, more preferably 1,200 μm or less, even more preferably 500 μm or less, and even more preferably 100 μm or less. The film thickness can be set to a desired value by adjusting the film thickness using an applicator or other coating tool, or by adjusting the solvent ratio.

[0020] A synovial surface film having synovial properties can be manufactured, for example, by forming a film using the film preparation composition detailed below. By applying the film preparation composition to a hard surface (for example, a metal surface, resin surface, glass surface, ceramic surface, etc.) and drying the composition at room temperature and pressure, or by heating or reducing pressure as necessary, a synovial surface film having synovial properties can be formed on the hard surface.

[0021] A synovial surface film having synovial surface properties requires component (A) and preferably contains one or more selected from the group consisting of components (B) and (C). In a film containing components (A), (B), and (C), the anionically modified cellulose fibers of component (B) and the hydrophobic compound having a cationic functional group of component (C) form a salt.

[0022] [Membrane preparation composition] The following describes the membrane preparation composition. The membrane preparation composition in the present invention is essential for component (A), and preferably contains one or more selected from the group consisting of component (B), component (C), and water. In the membrane, the anionically modified cellulose fibers of component (B) and the hydrophobic compound having a cationic functional group of component (C) form a salt.

[0023] [Ingredients (A)] Component (A) in this invention is an organic compound that is liquid at 25°C and 1 atm.

[0024] The solubility of component (A) in water is preferably 10 g or less per 100 g of water at 25°C, and more preferably 1 g or less.

[0025] The weight-average molecular weight of component (A) is preferably 100,000 or less, more preferably 50,000 or less, and even more preferably 10,000 or less, from the viewpoint of the stability of the film preparation composition, and preferably 100 or more, and more preferably 200 or more, from the same viewpoint.

[0026] Component (A) in the present invention specifically includes oils, organic solvents, polymerizable monomers, prepolymers, etc. Component (A) in the present invention is preferably an oil, and from the viewpoint of the stability of the film-preparing composition, examples of oils include one or more selected from the group consisting of higher alcohols, ester oils, hydrocarbon oils, silicone oils, ether oils, fats and oils, fluorinated inert liquids, and fatty acids. One or more selected from the group consisting of ester oils, silicone oils, ether oils, fats and oils, and fluorinated inert liquids are preferred, one or more selected from the group consisting of silicone oils, ester oils, and ether oils are more preferred, and silicone oil and / or ester oil are even more preferred.

[0027] Examples of higher alcohols include 1-octanol, 2-octanol, 1-decanol, 2-decanol, oleyl alcohol, isostearyl alcohol, and behenyl alcohol, which are saturated or unsaturated linear or branched alkyl chains having 8 to 22 carbon atoms.

[0028] Examples of ester oils include monoester oils, diester oils, and triester oils. 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, glyceryl tri-2-ethylhexanoate, and glyceryl triisostearate.

[0029] Examples of silicone oils include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, phenyl-modified silicone, alkyl-modified silicone, polyether-modified silicone, fluorine-modified silicone, and other modified silicones.

[0030] Examples of oils and fats include vegetable oils such as soybean oil, coconut oil, linseed oil, cottonseed oil, rapeseed oil, and castor oil, as well as animal oils.

[0031] From the viewpoint of the stability of the film-preparing composition, component (A) 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 with an SP value of 10 or less, as described later, can be cited as a preferred example.

[0032] In this specification, SP value refers to the solubility parameter calculated by the Fedors method (unit: (cal / cm³) 3 ) 1 / 2 This is shown in references such as "SP Value Basics, Applications, and Calculation Methods" (Information Organization Co., Ltd., 2005) and "Polymer Handbook Third Edition" (A Wiley-Interscience publication, 1989).

[0033] Examples of oils with an SP value of 10 or less that are preferably used in the present invention include oleic acid (SP value: 9.2), D-limonene (SP value: 9.4), 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 fluorinated inert liquids (e.g., fluorine-based inert liquids). Linart FC-40 (manufactured by 3M, SP value: 6.1), Florinart FC-43 (manufactured by 3M, SP value: 6.1), Florinart FC-72 (manufactured by 3M, SP value: 6.1), Florinart 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.) Examples include 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-96-3000cs (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. All of these oils are liquid at 25°C and 1 atm.

[0034] [Component (B)] Component (B) is anionic modified cellulose fiber. Anionically modified cellulose fibers are cellulose fibers that have been anionically modified to contain anionic groups. Component (B), alone or in combination with other components, functions as an emulsifier that emulsifies water with hydrophobic components (e.g., component (A)).

[0035] The anion-modified cellulose fibers are preferably those having a cellulose type I crystalline structure derived from the raw cellulose fibers. From the viewpoint of the stability of the film preparation composition, the degree of 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, it is preferably 90% or less, more preferably 85% or less, even more preferably 80% or less, and even more preferably 75% or less.

[0036] In this specification, the degree of crystallinity of various cellulose fibers is the degree of cellulose type I crystallinity calculated from the diffraction intensity value by X-ray diffraction, and can be measured, for example, according to the method described in Japanese Patent Application Publication No. 2024-067274. Cellulose type I refers to the crystalline form of natural cellulose, and the degree of cellulose type I crystallinity means the proportion of the crystalline region in the total 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.

[0037] Examples of anionic groups contained in anionic-modified cellulose fibers include carboxyl groups, sulfonic acid groups, and phosphate groups. From the viewpoint of bonding with component (C), the anionic group is preferably a carboxyl group. As anionically modified cellulose fibers, carboxyl-containing cellulose fibers, in which the anionic group is a carboxyl group, are more preferred from the viewpoint of ease of preparation and mild reaction conditions.

[0038] Examples of counterions that pair with the anionic groups in anionic-modified cellulose fibers include metal ions such as sodium ions, potassium ions, calcium ions, and aluminum ions, which are generated in the presence of alkali during manufacturing, as well as protons and ammonium ions, which are generated by substituting these metal ions with acid.

[0039] The anionic group content in anionically modified cellulose fibers 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 bonding with component (C). Furthermore, from the viewpoint of improving handling, 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. Note that "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.

[0040] From the viewpoint of ease of handling, the average fiber diameter of anion-modified cellulose fibers 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 strength when a film is formed, it is preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less. In this specification, anion-modified cellulose fibers with an average fiber diameter on the nm scale may be referred to as "finely milled anion-modified cellulose fibers." The average fiber diameter of anion-modified cellulose fibers and finely milled anion-modified cellulose fibers can be measured, for example, by the method described in Japanese Patent Application Publication No. 2024-067274.

[0041] [Method for producing anionically modified cellulose fibers] The anionically modified cellulose fibers used in the present invention can be obtained by subjecting raw material cellulose fibers to an oxidation treatment or an anionic group addition treatment, thereby introducing one or more anionic groups per glucose residue and causing anionic modification.

[0042] The cellulose fibers to be anion-modified, that is, the cellulose fibers used as raw materials for anion-modified cellulose fibers, are preferably natural cellulose fibers from an environmental standpoint. Examples include wood pulp such as coniferous pulp and hardwood pulp; cotton pulp such as cotton linters and cotton lint; non-wood pulp such as straw pulp and bagasse pulp; and bacterial cellulose. One of these can be used alone or in combination of two or more.

[0043] The average fiber diameter of the cellulose fibers used as raw materials is preferably 1 μm or more, and preferably 300 μm or less, from the viewpoint of handling ease and cost. Furthermore, the average fiber length of the cellulose fibers used as raw materials is preferably 100 μm or more, and preferably 5,000 μm or less, from the viewpoint of availability and cost. The average fiber diameter and average fiber length of the raw cellulose fibers can be measured, for example, according to the method described in Japanese Patent Publication No. 2024-067274. From the viewpoint of dispersibility, it is preferable to use cellulose fibers in which the raw cellulose fibers have been shortened by alkaline hydrolysis treatment, acid hydrolysis treatment, etc., and have an average fiber length of 1 μm or more and 1,000 μm or less.

[0044] Examples of anionic groups that can be introduced include carboxyl groups, sulfonic acid groups, or phosphate groups.

[0045] (i) When introducing a carboxyl group as an anionic group into cellulose fibers Methods for introducing carboxyl groups into cellulose fibers include, for example, oxidizing the hydroxyl groups of cellulose to convert them into carboxyl groups, or reacting the hydroxyl groups of cellulose with one or more compounds selected from the group consisting of compounds having carboxyl groups, acid anhydrides of compounds having carboxyl groups, and derivatives thereof.

[0046] As a method for oxidizing the hydroxyl groups of the cellulose, for example, a method can be applied in which 2,2,6,6-tetramethyl-1-piperidine-N-oxyl (TEMPO) is used as a catalyst to react with an oxidizing agent such as sodium hypochlorite and a bromide such as sodium bromide to perform the oxidation treatment. More specifically, known methods, such as the method described in Japanese Patent Application Publication No. 2011-140632, can be referred to.

[0047] By oxidizing cellulose fibers using TEMPO as a catalyst, the hydroxymethyl group (-CH2OH) at the C6 position of the cellulose constituent unit is selectively converted to a carboxyl group. This method is particularly advantageous because it exhibits excellent selectivity for the hydroxyl group at the C6 position on the surface of the raw material cellulose fibers, and the reaction conditions are mild. Therefore, a preferred embodiment of the anionically modified cellulose fiber in the present invention is a cellulose fiber in which the C6 position of the cellulose constituent unit is a carboxyl group. In this specification, cellulose fibers obtained by oxidation of hydroxyl groups in cellulose constituent units are sometimes referred to as "oxidized cellulose fibers," and cellulose fibers obtained by oxidizing cellulose fibers using TEMPO as a catalyst, in which the C6 position of the cellulose constituent unit is a carboxyl group, are sometimes referred to as "TEMPO-oxidized cellulose fibers." Oxidized cellulose fibers, particularly TEMPO-oxidized cellulose fibers, are preferred because they are easier to prepare than other anionically modified cellulose fibers.

[0048] By further oxidation or reduction treatment of oxidized cellulose fibers, oxidized cellulose fibers from which the remaining aldehyde groups have been removed can be prepared.

[0049] (ii) When introducing a sulfonic acid group or a phosphate group as an anionic group into cellulose fibers Methods for introducing sulfonic acid groups as anionic groups into cellulose fibers include adding sulfuric acid to the cellulose fibers and heating them. Methods for introducing phosphate groups as anionic groups into cellulose fibers include mixing cellulose fibers in a dry or wet state with powder or aqueous solution of phosphate or a phosphate derivative, or adding an aqueous solution of phosphate or a phosphate derivative to a dispersion of cellulose fibers. When these methods are employed, generally, after mixing or adding powder or aqueous solution of phosphate or a phosphate derivative, dehydration and heat treatment are performed. One method for introducing phosphate groups as anionic groups into cellulose fibers is described in Japanese Patent Publication No. 7196051, which involves impregnating raw cellulose fibers with a mixed aqueous solution of ammonium dihydrogen phosphate and urea to phosphate esterify the hydroxyl groups of the cellulose fibers.

[0050] [Component (C)] Component (C) is a hydrophobic compound having a cationic functional group. However, those corresponding to component (A) are excluded. Component (C) may be used alone or in combination of two or more types. From the viewpoint of synovial properties, component (C) is preferably one or more selected from the group consisting of polymer compounds having cationic functional groups and hydrocarbon compounds having cationic functional groups.

[0051] Examples of cationic functional groups in component (C) include amino groups, ammonium groups, and imidazolium groups, with amino groups being preferred from the viewpoint of availability. In this specification, an amino group means a monovalent functional group obtained by removing one hydrogen atom from ammonia, a primary amine, or a secondary amine.

[0052] (i) Polymer compounds having cationic functional groups The weight-average molecular weight of the polymer compound having a cationic functional 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 film formation strength, and similarly preferably 1,000,000 or less, more preferably 100,000 or less, and even more preferably 50,000 or less.

[0053] Examples of polymer compounds that are easy to modify include silicones having cationic functional groups, polyoxyalkylene oxides, poly(meth)acrylates, polyvinyl, polyesters, polyamides, and polycarbonates, and more preferably amino-modified silicones.

[0054] The silicone has a polysiloxane structure with siloxane bonds as the main chain, and may also contain alkylene groups. The polysiloxane structure may have substituents as described later.

[0055] [Substituent] Substituents include, for example, alkoxy groups having 1 to 6 carbon atoms such as methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, and hexyloxy groups; methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, and sec-butoxycarbonyl Examples include alkoxy-carbonyl groups with 1 to 6 carbon atoms, such as carbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, and isopentyloxycarbonyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; acyl groups with 1 to 6 carbon atoms, such as acetyl and propionyl groups; aralkyl groups; aralkyloxy groups; alkylamino groups with 1 to 6 carbon atoms; and dialkylamino groups with 1 to 6 carbon atoms in the alkyl group.

[0056] [Amino-modified silicone] Component (C) is more preferably a silicone having an amino group (hereinafter referred to as "amino-modified silicone") from the viewpoint of the stability of the film preparation composition.

[0057] As an amino-modified silicone, its kinematic viscosity at 25°C is 10 mmHg. 2 / s or more 20,000mm 2 / s or less, the following are preferred. Further, amino-modified silicone having an amino equivalent of 400 g / mol or more and 16,000 g / mol or less is preferably cited.

[0058] The kinematic viscosity at 25°C can be determined with an Ostwald viscometer. From the viewpoint of the strength during film formation, it is more preferably 20 mm 2 / s or more, still more preferably 50 mm 2 / s or more, and from the viewpoint of handling properties, it is more preferably 10,000 mm 2 / s or less, still more preferably 5,000 mm 2 / s or less.

[0059] Also, from the viewpoint of the strength during film formation, the amino equivalent is preferably 400 g / mol or more, more preferably 600 g / mol or more, still more preferably 800 g / mol or more. From the viewpoint of ease of bonding to anionic-modified cellulose fibers, it is preferably 16,000 g / mol or less, more preferably 14,000g / mol or less, still more preferably 12,000 g / mol or less. The amino equivalent is the molecular weight per nitrogen atom, and is determined by quantifying the amount of nitrogen atoms in the sample by elemental analysis and calculating the mass of the sample containing 1 mol of nitrogen atoms.

[0060] Specific examples of the amino-modified silicone include compounds represented by the general formula (a1).

[0061]

Chemical formula

[0062] [In the formula, R 1a , R 2a , R 3a 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 from the viewpoint of lubricity, it is preferably a methyl group or a hydroxy group. Incidentally, R 1a , R 2a , R 3aThese may be the same or different, and there may be multiple Rs. 2a These may be the same or different. B represents a side chain having at least one amino group. x and y each represent the average degree of polymerization, where x is an integer greater than or equal to 0 and y is an integer greater than or equal to 1, selected such that the kinematic viscosity and amino equivalent of the compound at 25°C are within the above range.

[0063] In the compound of general formula (a1), from the viewpoint of synovial properties, x is preferably a number between 10 and 10,000, more preferably a number between 20 and 5,000, and even more preferably a number between 30 and 3,000. Y is preferably a number between 1 and 1,000, more preferably a number between 1 and 500, and even more preferably a number between 1 and 200. From the viewpoint of film formation strength, 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. 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.

[0064] In general formula (a1), the following can be considered as side chain B having an amino group. -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 (Here, e, f, and g are numbers from 1 to 30.)

[0065] The amino-modified silicone used in the present invention can be produced, for example, by hydrolyzing an organoalkoxysilane represented by general formula (a2) with excess water to obtain a hydrolysate, and then heating the hydrolysate obtained from this hydrolysate with dimethylcyclopolysiloxane using a basic catalyst such as sodium hydroxide to 80-110°C to allow an equilibrium reaction to occur, and then neutralizing the basic catalyst with an acid when the reaction mixture reaches a desired viscosity (see Japanese Patent Publication No. 53-98499). H2N(CH2)2NH(CH2)3Si(CH3)(OCH3)2(a2)

[0066] Furthermore, the amino-modified silicone is preferably one or more selected from the group consisting of monoamino-modified silicone having one amino group in one of the side chains B and diamino-modified silicone having two amino groups in one of the side chains B, from the viewpoint of film formation strength, and more preferably one or more selected from the group consisting of compounds in which the amino-group-containing side chain B is represented by -C3H6-NH2 [hereinafter referred to as component (a1-1)] and compounds in which the amino-group-containing side chain B is represented by -C3H6-NH-C2H4-NH2 [hereinafter referred to as component (a1-2)].

[0067] In this invention, the amino-modified silicones are, in terms of performance, TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600) and TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800) from Momentive Performance Materials, and SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700), FZ-3710 (kinematic viscosity: 1000, amino equivalent: 1700), SF8457C (kinematic viscosity: 1200, amino equivalent: 1800), SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), SF8452C (kinematic viscosity: 600, amino equivalent: 6400), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), and BY16 -892 (kinematic viscosity: 1500, amino equivalent: 2000), BY16-898 (kinematic viscosity: 2000, amino equivalent: 2900), FZ-3760 (kinematic viscosity: 220, amino equivalent: 1600), BY16-213 (kinematic viscosity: 55, amino equivalent: 2700), KF-8002 (kinematic viscosity: 1100, amino equivalent: 1700) manufactured by Shin-Etsu Chemical Co., Ltd. ), KF-8004 (kinematic viscosity: 800, amino equivalent: 1500), KF-8005 (kinematic viscosity: 1200, amino equivalent: 11000), KF-867 (kinematic viscosity: 1300, amino equivalent: 1700), KF-864 (kinematic viscosity: 1700, amino equivalent: 3800), and KF-859 (kinematic viscosity: 60, amino equivalent: 6000) are preferred. (In parentheses, kinematic viscosity is measured at 25°C (unit: mm) 2 The value is expressed as ( / s), and the unit of amino equivalent is g / mol.

[0068] (a1-1) BY16-213 (kinematic viscosity: 55, amino equivalent: 2700) and BY16-853U (kinematic viscosity: 14, amino equivalent: 450) are more preferred as component (a1-1).

[0069] (a1-2) Component SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), FZ-3760 (kinematic viscosity: 220, amino equivalent: 1600), SF8452C (kinematic viscosity: 600, amino equivalent: 6400), KF-8002 (kinematic viscosity: 1100, amino equivalent: 1700), SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700), and FZ-3710 (kinematic viscosity: 1000, amino equivalent: 1700) are more preferred.

[0070] (ii) hydrocarbon compounds having cationic functional groups A hydrocarbon compound having a cationic functional group is a compound in which one or more hydrocarbon groups are bonded to one cationic functional group. From the viewpoint of synovial properties, the total number of carbon atoms in a hydrocarbon compound having a cationic functional group is preferably 16 or more, more preferably 18 or more, and from the viewpoint of handling properties, preferably 40 or less, more preferably 30 or less, and even more preferably 26 or less. In the case of a hydrocarbon compound having a cationic functional group, if the cationic functional group is a primary amine, secondary amine, tertiary amine, or quaternary ammonium, the hydrocarbon group is directly bonded to the nitrogen atom via a covalent bond. In the case of a hydrocarbon compound having a cationic functional group, if the cationic functional group is imidazolium, pyridinium, imidazoline, etc., the hydrocarbon group is a compound in which at least one or more hydrocarbon groups are bonded via a covalent bond to any position in the ring structure.

[0071] [Hydroxide group] Examples of hydrocarbon groups in the hydrocarbon compounds having the cationic functional group include chain saturated hydrocarbon groups, chain unsaturated hydrocarbon groups, cyclic saturated hydrocarbon groups, and aromatic hydrocarbon groups. From the viewpoint of availability, the number of carbon atoms in the hydrocarbon group is preferably 16 or more, more preferably 18 or more, and similarly, preferably 40 or less, more preferably 30 or less, and even more preferably 24 or less.

[0072] Note that, unless otherwise specified, the number of carbon atoms in a hydrocarbon group refers to the number of carbon atoms in a single hydrocarbon group. Specific examples of chain-type saturated hydrocarbon groups include, for example, hexadecyl groups, octadecyl groups, docosyl groups, and octacosanyl groups. Specific examples of chain-like unsaturated hydrocarbon groups include, for example, the hexadecenyl group and the octadecenyl group. Specific examples of cyclic saturated hydrocarbon groups include, for example, the cyclohexadecyl group and the cyclooctadecyl group.

[0073] [Examples of hydrocarbon compounds] The hydrocarbon compounds having the cationic functional group described above are preferably hydrocarbon compounds having an amino group, such as primary amines, secondary amines, tertiary amines, and quaternary ammonium compounds (hereinafter referred to as "hydrocarbon amines"). Specific examples of such hydrocarbon amines include hexadecylamine, stearylamine, oleylamine, dioctylamine, didecylamine, didodecylamine, trihexylamine, trioctylamine, tetrabutylammonium salt, tetrahexylammonium salt, dimethyldioctylammonium salt, dimethylddecylammonium salt, and trimethylhexadecylammonium salt.

[0074] The above hydrocarbon compounds may have some hydrogen atoms further substituted. Examples of substituents include fluorine atoms, chlorine atoms, bromine atoms, iodine atoms, hydroxyl groups, methoxy groups, ethoxy groups, carboxyl groups, aldehyde groups, ketone groups, and thiol groups.

[0075] [water] In this invention, water serves as a solvent and as one of the components of the film preparation composition.

[0076] [Nonionic thickener] In this invention, a nonionic thickener can be used. Examples of nonionic thickeners include nonionic association-type thickeners; cellulose-based thickeners such as methylcellulose, ethylcellulose, hydroxyethylcellulose, hydroxypropylcellulose, and hydroxypropylmethylcellulose; and polyvinyl alcohols. These can be used individually or in combination of two or more.

[0077] As nonionic associative thickeners, urethane associative thickeners having urethane bonds in their molecules are preferred, such as urethane-modified polyether type thickeners.

[0078] Examples of urethane-modified polyether type thickeners include urethane-modified polyethers that have urethane bonds and polyether chains in their molecules and hydrophobic groups at their terminals. Such urethane-modified polyether type thickeners are commercially available and include, for example, SN Thickener 660T, SN Thickener 621N, and SN Thickener 623N from Sunopco; the Adekanol series from ADEKA, such as Adekanol UH-814N, UH-752, UH-756VF, UH-420, and UH-462; Leolate 244 and Leolate 278 from Elementis Japan; and COAPUR 2025, COAPUR 2501, COAPUR 3025, COAPUR 520W, COAPUR 830W, COAPUR XS22, COAPUR XS71, and COAPUR XS83 from ARKEMA.

[0079] [Membrane reinforcement agent] In this invention, a membrane reinforcing agent can be used. Since membrane reinforcing agents are effective in improving the persistence of the synovial properties of membranes, such components may be included or blended. Examples of membrane reinforcing agents that can be used in the present invention include polymer compounds. Here, when the membrane reinforcing agent is a polymer compound, components (A), (B), or (C) are not included. In the present invention, from the viewpoint of ease of formulation, the membrane reinforcing agent is more preferably one that exists as an emulsion or dispersion in water.

[0080] If the film reinforcing agent is a polymer compound, it is preferable to use one or more selected from the group consisting of polymer compound (X) and polymer compound (Y) described below. Polymer compound (X): A polymer compound having an ester group, amide group, urethane group, amino group, ether group, or carbonate group in its main chain. Polymer compound (Y): Methacrylic or acrylic polymer compound having an ester group or amide group in its side chain.

[0081] The weight-average molecular weight of the polymer compound is preferably 10,000 or more, more preferably 20,000 or more, and even more preferably 30,000 or more, from the viewpoint of obtaining a film with excellent sustained synovial properties. Similarly, it is preferably 5 million or less, more preferably 1 million or less, and even more preferably 500,000 or less.

[0082] ·High molecular compound (X) Examples of polymer compounds (X) having an ester group in the main chain include condensates of dicarboxylic acids such as adipic acid, sebacic acid, dodecanediic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenyl succinic acid with diols such as ethylene glycol, propylene glycol, and butanediol, or condensates of compounds such as glycolic acid and lactic acid that have both a hydroxyl group and a carboxyl group in one molecule.

[0083] Examples of polymer compounds (X) having an amide group in the main chain include condensates of dicarboxylic acids such as adipic acid, sebacic acid, dodecanediic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenyl succinic acid with diamines such as aliphatic diamines such as ethylenediamine, hexamethylenediamine, and propylenediamine.

[0084] Examples of polymer compounds (X) having a urethane group in the main chain include polymers of diisocyanates such as triresin diisocyanate, diphenyl isocyanate, xylylene diisocyanate, and hexamethylene diisocyanate with diols such as ethylene glycol, propylene glycol, and butanediol.

[0085] Examples of polymer compounds (X) having amino groups in the main chain include polymers of alkylimines such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, and hexyleneimine.

[0086] Examples of polymer compounds (X) having an ether group in the main chain include polymers of alkylene oxides such as ethylene oxide, propylene oxide, and butylene oxide, and polymers of formaldehyde.

[0087] Examples of polymer compounds (X) having a carbonate group in the main chain include condensates of polyols such as 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, and 1,1-bis(4-hydroxyphenyl)cyclohexane with phosgene.

[0088] Copolymers of the above-mentioned condensates and polymers are also included in the category of polymeric compounds (X). Examples include polycarbonate-polyurethane copolymers and polyester-polyurethane copolymers.

[0089] ·High molecular compound (Y) Examples of methacrylic or acrylic polymers having ester or amide groups in their side chains (hereinafter also simply referred to as (meth)acrylic polymers) include polyalkyl (meth)acrylates such as polymethyl (meth)acrylate, polyethyl (meth)acrylate, and polybutyl (meth)acrylate; copolymers with acrylics such as acrylic styrene and urethane acrylic; and poly(meth)acrylamides such as poly(meth)acrylamide, polyN-methyl (meth)acrylamide, polyN,N-dimethyl (meth)acrylamide, and polyN-phenyl (meth)acrylamide.

[0090] Specific examples of polymer compounds that can be preferably used as membrane reinforcing agents include the DAOTAN series (e.g., DAOTAN TW 6450 / 30WA, DAOTAN TW 6460w / 35WA, DAOTAN TW 6464 / 36WA, DAOTAN TW 6493 / 35WA, etc.) from Daicel Ornex, the VIACRYL series (e.g., VIACRYL VSC 6286w / 45WA, VIACRYL SC 6828w / 45WA, etc.), the VISCOPOL series (e.g., VISCOPOL 6191, etc.), and the NeoCryl series (e.g., NeoCryl XK-188, NeoCryl A-1127, etc.) from DSM.

[0091] [Wetting agent] In the present invention, a wetting agent can be used. However, those corresponding to component (A) above are excluded. Wetting agents can be included or blended because they can prevent the coating from being repelled by the substrate by increasing the wettability to various substrates.

[0092] Examples of wetting agents that can be used in the present invention include wetting agents used in water-containing products such as water-based paints, water-based inks, daily necessities, and cosmetics. Preferred specific examples include polyether-modified silicones, organic solvents that are miscible with water such as ethanol and isopropanol, and surfactants such as sodium dodecyl sulfate. Among these, polyether-modified silicones are preferred from the viewpoint of improving the persistence of the film's synovial properties.

[0093] Examples of polyether-modified silicones include compounds having a methyl silicone chain as the main chain and side chains consisting of polyoxyethylene groups, and specifically, compounds represented by the following general formula.

[0094] [ka]

[0095] In the above general formula, R 1 R is a methylene group, an ethylene group, or a trimethylene group. 2 is an alkyl group having 1 to 4 carbon atoms, where m is an integer from 0 to 50, n is an integer from 1 to 10, p is an integer from 1 to 50, and q is an integer from 0 to 50. -R 1 (C2H4O) p (C3H6O) q R 2 In the group shown, (C2H4O) p and (C3H6O) q It can be random or blocky.

[0096] The HLB value of the polyether-modified silicone is preferably within a specific range from the viewpoint of synovial fluid persistence of the resulting film and stability of the composition. Specifically, it is preferably 1 or higher, and preferably 18 or lower.

[0097] When using two or more polyether-modified silicones with different HLB values, the HLB value used as a wetting agent should be the weighted average of those values, provided that it falls within the above range. The HLB value is an index representing the balance between hydrophilicity and lipophilicity, and in this invention, it refers to the value obtained by the following Griffin formula. HLB value = 20 × sum of molecular weights of hydrophilic bases / molecular weight

[0098] The kinematic viscosity of the polyether-modified silicone at 25°C is preferably within a specific range from the viewpoint of the synovial fluid persistence of the resulting film, and specifically, preferably 1 mm. 2 / s or more, more preferably 5mm 2 / s or more, more preferably 10mm 2 The value is 1 / s or more, preferably 1000 mm 2 / s or less, more preferably 500mm 2 / s or less, more preferably 200 mm 2 / s or less, more preferably 100 mm 2 It is less than or equal to / s.

[0099] The weight-average molecular weight of the polyether-modified silicone is preferably 300 or higher from the viewpoint of improving the synovial fluid persistence of the resulting film, and preferably 9,000 or lower from the same viewpoint.

[0100] Polyether-modified silicone compounds that can be preferably used as wetting agents are commercially available. 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, all manufactured by Shin-Etsu Chemical Co., Ltd. From the viewpoint of synovial fluid persistence of the resulting film, KF-640, KF-642, KF-643, KF-351A, KF-354L, and KF-355A can be preferably used. Commercially available products with structures that do not correspond to the above general formula (for example, KF-6028 and KF-6038, manufactured by Shin-Etsu Chemical Co., Ltd.) can also be used as wetting agents.

[0101] [Agglomeration inhibitor] In the present invention, a flocculation inhibitor can be used. The flocculation inhibitor is effective in suppressing the flocculation of hydrophobic components such as component (A), component (B), and component (C), or mixtures thereof, in water during step 1, and therefore such components can be included or blended.

[0102] The weight-average molecular weight of the flocculation inhibitor is preferably 100 or more, more preferably 200 or more, and even more preferably 300 or more, from the viewpoint of suppressing the flocculation of hydrophobic components such as component (A), component (B), and component (C) or mixtures thereof in water, and from the same viewpoint, it is preferably 9,000 or less, more preferably 8,000 or less, and even more preferably 7,000 or less.

[0103] Examples of flocculation inhibitors include anionic surfactants such as sodium dodecylbenzenesulfonate; and polymer compounds such as ammonium polyacrylate, which have anionic groups and whose countercations consist of one or more selected from the group consisting of ammonium ions and organic ammonium ions.

[0104] [Other ingredients] In addition to the components mentioned above, the film preparation composition may contain, to the extent that it does not impair the effects of the present invention, antifouling agents, antibacterial compounds (e.g., organic synthetic antibacterial agents, natural antibacterial agents, and inorganic antibacterial agents), plasticizers, nucleating agents, fillers (inorganic fillers, organic fillers), hydrolysis inhibitors, flame retardants, antioxidants, hydrocarbon waxes and anionic surfactants as lubricants, ultraviolet absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, 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 regulators; leveling agents; conductive agents; ultraviolet dispersants; deodorants, etc. Similarly, other polymer materials and other compositions may be added to the extent that they do not impair the effects of the present invention.

[0105] [Properties and composition of the film preparation composition] The film preparation composition preferably contains component (A) as an essential component, and further preferably includes one or more components selected from the group consisting of component (B), component (C), and water. By mixing a composition containing component (A), component (B), component (C), and water, an emulsified composition can be obtained, and such an emulsified composition is preferable from the viewpoint of ease of handling. The emulsified state is determined by observing the composition with an optical microscope, and if it can be confirmed that oil droplets are dispersed in water, it is considered to be in an emulsified state. The emulsified composition may be either an O / W type emulsion or a W / O type emulsion, but an O / W type emulsion is preferred.

[0106] The content of component (A) in the film preparation composition or during the preparation of the film preparation composition is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 2% by mass or more, and even more preferably 5% by mass or more, from the viewpoint of synovial properties, and preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 10% by mass or less, from the viewpoint of film formation.

[0107] When component (B) is used, the content of component (B) in the film preparation composition or during the preparation of the film preparation composition is preferably 0.02% by mass or more, more preferably 0.1% by mass or more, and even more preferably 0.4% by mass or more, from the viewpoint of emulsifying power, while from the viewpoint of handling properties, it is preferably 15% by mass or less, more preferably 10% by mass or less, even more preferably 5% by mass or less, and even more preferably 1% by mass or less.

[0108] When component (C) is used, the content of component (C) in the film preparation composition or during the preparation of the film preparation composition is preferably such that, from the viewpoint of the stability of the obtained film preparation composition, the cationic functional groups of component (C) are at least 0.5 equivalents, more preferably 0.8 equivalents, and even more preferably 1 equivalent, relative to the anionic groups, preferably carboxyl groups, of component (B). Similarly, it is preferably 8.5 equivalents or less, more preferably 5 equivalents or less, and even more preferably 3 equivalents or less.

[0109] When water is added or included, the water content in the film preparation composition or during the preparation of the film preparation composition is preferably 10% by mass or more, more preferably 50% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more, from the viewpoint of maintaining an emulsified state, and preferably 95% by mass or less, more preferably 90% by mass or less, and even more preferably 89% by mass or less, from the viewpoint of effective quantity.

[0110] The viscosity of the composition in this invention is set at 25°C and a shear rate of 1s, from the viewpoint of improving the synovial fluid persistence of the formed film. -1 The viscosity is preferably 10 mPa·s or more, more preferably 1,000 mPa·s or more, even more preferably 5,000 mPa·s or more, and even more preferably 10,000 mPa·s or more. On the other hand, from the viewpoint of handling, it is preferably 100,000 mPa·s or less, more preferably 50,000 mPa·s or less, and even more preferably 30,000 mPa·s or less. The viscosity of the composition in this invention at 25°C is measured by the method described in the examples below.

[0111] [Method for producing a film preparation composition] The film preparation composition can be manufactured by mixing the aforementioned component (A) and, if necessary, component (B), component (C), and / or water.

[0112] For the mixing process, a magnetic stirrer, mechanical stirrer, homomixer, vacuum emulsifier, low-pressure homogenizer, high-pressure homogenizer, grinder, cutter mill, ball mill, jet mill, short-screw extruder, twin-screw extruder, ultrasonic stirrer, household juicer mixer, etc. may be used. The mixing process may also be carried out by combining two or more operations.

[0113] The temperature and time during mixing are not particularly limited, but for example, the temperature range is preferably 5 to 50°C, and the time range is preferably 1 minute to 3 hours.

[0114] The preferred ranges for the content of each component and the ratios between components during mixing are the same as those preferred ranges for the aforementioned film preparation compositions.

[0115] In any stage of the manufacturing process of the film preparation composition, micrometer-scale cellulose fibers can be reduced to nanometer scale by subjecting the component or composition containing anionically modified cellulose fibers to a micronization treatment. Alternatively, pre-micronized anionically modified cellulose fibers may be blended as component (B). It is preferable to carry out such a micronization treatment process because reducing the average fiber diameter of the anionically modified cellulose fibers to the nanometer scale improves the stability of the film preparation composition and the strength during film formation.

[0116] For the micronization process, known dispersers are preferably used. For example, disintegrators, beaters, low-pressure homogenizers, high-pressure homogenizers, grinders, cutter mills, ball mills, jet mills, short-screw extruders, twin-screw extruders, ultrasonic stirrers, household juicer mixers, etc., can be used. Furthermore, the solid content in the material to be micronized is preferably 50% by mass or less. The operating conditions of the equipment during the micronization process can be appropriately set by those skilled in the art based on known operating conditions or the operating conditions described in the instruction manuals for each piece of equipment.

[0117] <Film having a synovial surface film> The film of the present invention is A resin layer and The resin layer has a synovial surface film on one of its surfaces. It is film, The aforementioned synovial fluid surface film is a film containing component (A): an organic compound that is liquid at 25°C and 1 atm.

[0118] One embodiment of the structure of the film of the present invention is one in which the above-described synovial surface film of the present invention is formed on one surface of a base film which is a resin layer. Such a film can be manufactured, for example, by applying the above-described film preparation composition to a base film and forming a film on the base film.

[0119] Therefore, the synovial surface film in the film of the present invention is more preferably one that contains anionically modified cellulose fibers of component (B) and / or a hydrophobic compound having a cationic functional group of component (C) (excluding those corresponding to component (A)).

[0120] Since the film of the present invention has the above-described synovial surface film, a preferred embodiment of the film of the present invention has the ability to restore the synovial surface properties of the synovial surface film by being left undisturbed for more than 5 minutes if the synovial surface film is damaged and the synovial surface properties decrease.

[0121] A preferred structure of the film of the present invention is one in which an adhesive layer is further provided on the surface opposite to the surface having a synovial surface film of the resin layer. Therefore, for example, a film of such a structure can be manufactured by applying a film preparation composition to the other surface of a substrate film that has an adhesive layer pre-applied to one surface and forming a film.

[0122] From the viewpoint of ensuring mechanical strength as a film, the thickness of the film of the present invention is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more. On the other hand, from the viewpoint of ensuring flexibility as a film, the thickness is preferably 500 μm or less, more preferably 300 μm or less, and even more preferably 100 μm or less.

[0123] The thickness of the synovial surface film in the film of the present invention is the same as the thickness of the synovial surface film having the above-described synovial surface properties.

[0124] From the viewpoint of ensuring the mechanical strength of the film, the thickness of the resin layer in the film of the present invention is preferably 5 μm or more, more preferably 10 μm or more. On the other hand, from the viewpoint of ensuring the flexibility of the film, it is preferably 300 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less.

[0125] From the viewpoint of ensuring adhesion, the thickness of the adhesive layer in the film of the present invention is preferably 1 μm or more, more preferably 5 μm or more, and even more preferably 10 μm or more. On the other hand, from the viewpoint of ensuring workability when applying the film, it is preferably 1000 μm or less, more preferably 500 μm or less, and even more preferably 300 μm or less.

[0126] The film of the present invention may include layers or films other than the resin layer, the synovial surface film, and the adhesive layer, such as a printed layer, a gas barrier layer, a sealant layer, and so on.

[0127] Examples of materials for the base film include polyolefin resin, polyvinyl chloride resin, polyamide resin, acrylic resin, polycarbonate resin, phenolic resin, melamine resin, furan resin, epoxy resin, phenoxy resin, polyester resin, and polyurethane resin.

[0128] The adhesive layer is formed by applying an adhesive known in the film industry.

[0129] The film of the present invention can be suitably used, for example, as an anti-fouling film, a snow-proof film, or an antibacterial film. Specific examples of target materials include, for instance, biologically derived contaminants such as animal excrement, mold and fungi caused by condensation, biofilms, algae, and aquatic organisms; environmentally derived contaminants such as rainwater, acid rain, snow, ice, frost, and mud; chemically derived contaminants such as various chemicals used in factories and laboratories, resins, and rust caused by the adhesion of water droplets; oily contaminants such as lubricating oil, engine oil, and cooking oil from automobiles and machinery; and human-derived contaminants such as sebum, sweat, cosmetics, blood, saliva, and other bodily fluids. Furthermore, the surfaces to which the film of the present invention is applied include, for example, the surfaces of vehicles such as railway cars, buses, automobile bodies, automobile windows, automobile mirrors, trucks, buses, and the exteriors of agricultural and industrial heavy machinery, as well as the tanks and seats of motorcycles; the surfaces of structures located outdoors such as windows, exterior walls, roofs, garage doors, window frames, balcony railings, signs, traffic lights, road signs, electronic display boards, solar panels, offshore equipment, wharves, and bridges; the surfaces of ships such as ship decks, hulls, propellers, observation equipment, ship windows, and portholes; the surfaces of aircraft such as airplane exteriors, helicopter exteriors, and drone exteriors; and factory machinery and walls. Examples include the surfaces of industrial equipment such as storage tanks, cooling towers, manufacturing equipment, piping, hoppers, drains, power plant equipment, and electric wires; window panes, shower doors, mirrors, bathtubs, toilets, washbasins, mirrors, floors, kitchen countertops, drains, refrigerator casings, washing machine and dryer casings, air conditioner casings, microwave oven casings, and other household and home appliance surfaces; the surfaces of outdoor equipment such as tents, campervans, barbecue grills, bicycles and cycling equipment; and medical devices such as X-ray machines, MRI machines, CT scanners, blood pressure monitors, electrocardiographs, pulse oximeters, ventilators, endoscopes, intubation tubes, hearing aids, wheelchairs, and walkers.

[0130] <Film Repair Agent> As described above, a film formed using the above-mentioned film preparation composition has the effect of restoring synovial surface properties by being left to stand for a predetermined time. Therefore, such a film preparation composition can be used as a film repair agent, and more specifically as a film repair agent that restores the synovial surface properties of a film.

[0131] That is, one embodiment of the film repair agent of the present invention is a film repair agent containing an organic compound of component (A) that is liquid at 25°C and 1 atm, and a preferred embodiment of the film repair agent of the present invention is a film repair agent that further contains anionic modified cellulose fibers of component (B) and / or a hydrophobic compound having a cationic functional group of component (C) (excluding those corresponding to component (A)). The preferred specific composition of the film repair agent of the present invention is the same as the preferred specific composition of the film preparation composition described above. [Examples]

[0132] The present invention will be specifically described below with reference to examples. The following examples are merely illustrative of the present invention and do not imply any limitation. "Normal pressure" refers to 101.3 kPa, and "room temperature" refers to 25°C.

[0133] [Anionic group content of anionic-modified cellulose fibers and hydrophobic-modified cellulose fibers] Place 0.5 g of the cellulose fiber to be measured (dry mass) into a 100 mL beaker, add deionized water or a methanol / water = 1 / 2 mixture to make a total volume of 55 mL, and add 5 mL of 0.01 M sodium chloride aqueous solution to prepare a dispersion. Stir the dispersion until the cellulose fiber to be measured is sufficiently dispersed. Add 0.1 M hydrochloric acid to this dispersion to adjust the pH to 2.5-3, and using an automatic titrator (Toa DKK Co., Ltd., AUT-701), add 0.05 M sodium hydroxide aqueous solution dropwise to the dispersion with a waiting time of 60 seconds, and measure the conductivity and pH values ​​every minute. Continue the measurement until the pH reaches approximately 11 to obtain a conductivity curve. From this conductivity curve, determine the amount of sodium hydroxide titration, and calculate the anionic group content of the cellulose fiber to be measured using the following formula. Anionic group content (mmol / g) = [Sodium hydroxide titration volume × Sodium hydroxide aqueous solution concentration (0.05M)] / [Mass of cellulose fiber to be measured (0.5g)]

[0134] [Solid content in the dispersion] Measurements are taken using an infrared moisture meter (Shimadzu Corporation, MOC-120H). Measurements are taken every 30 seconds at a constant temperature of 150°C for 1 g of sample, and the value at which the mass loss is 0.1% or less of the initial amount of sample is defined as the solid content.

[0135] [Glucose portion in anionically modified cellulose fibers] Regarding the mass of the glucose portion in anionically modified cellulose fibers and finely milled anionically modified cellulose fibers, the "mass of the glucose portion" was defined as the total mass of glucose units, including the anionic groups bonded to the glucose units, i.e., including glucose units in which the hydroxymethyl group has been converted to a carboxyl group.

[0136] [Anionic modified cellulose fiber] As the anionically modified cellulose fiber, we used one having the physical properties listed in Table 1, i.e., anionically modified cellulose fiber 1.

[0137] [Table 1]

[0138] Such anionically modified cellulose fibers can be prepared, for example, by the method described in the TEMPO oxidation treatment below.

[0139] [TEMPO oxidation treatment] In a 2L PP beaker equipped with a mechanical stirrer and stirring blades, weigh out 10g of bleached kraft pulp fiber from coniferous trees (as the raw material for natural cellulose fiber) and 990g of deionized water, and stir at 25°C and 100rpm for 30 minutes. Next, add 0.13g of TEMPO, 1.3g of sodium bromide, and 35.5g of 10.5% by mass sodium hypochlorite aqueous solution to 10g of pulp fiber in that order. Then, perform pH stat titration using an automatic titrator and add 0.5M sodium hydroxide aqueous solution dropwise to maintain the pH at 10.5. The reaction is carried out at 25°C for 120 minutes with a stirring speed of 100rpm.

[0140] Next, while stirring, 1M hydrochloric acid is added to adjust the pH of the suspension to 2. Then, the solids are filtered off by suction filtration. The process of dispersing the solids in deionized water and filtering them off by suction filtration is repeated until the conductivity of the filtrate is 200 μS / cm or less. The resulting solids are then dehydrated to obtain anionic modified cellulose fibers.

[0141] Next, while stirring, 1M hydrochloric acid is added to adjust the pH of the suspension to 2. Then, the solids are filtered off by suction filtration. The process of dispersing the solids in deionized water and filtering them off by suction filtration is repeated until the conductivity of the filtrate is 200 μS / cm or less. The resulting solids are then dehydrated to obtain the anionically modified cellulose fibers described in Table 1.

[0142] [Measurement of viscosity of composition] An E-type viscometer (Anton Paar, MCR300) and a measuring jig (CP50-1) were used, and measurements were taken at a temperature of 25°C as follows: Shear rate 0.1 s -1 from 7000s -1 After measuring the viscosity of the composition while gradually increasing the shear rate up to 7000s, the viscosity was then reversed to 7000s. -1 from 0.1s -1 Viscosity was measured while gradually decreasing the shear rate up to 0.1s. Then, the shear rate was reduced again to 0.1s. -1 from 7000s -1 Viscosity was measured while gradually increasing the shear rate up to 1s in the final cycle. -1 The viscosity at [location] was defined as the viscosity of the composition.

[0143] Preparation Example 1 [Preparation of Micronized Anion-Modified Cellulose Fibers] [Preparation of dispersion of micronized anion-modified cellulose fibers 1] Deionized water was added to the above-mentioned anionically modified cellulose fiber 1 to prepare 100 g of suspension (solid content 2.0% by mass). A 0.5 M sodium hydroxide aqueous solution was added to adjust the pH to 8, and then deionized water was added to make a total of 200 g. This suspension was subjected to micronization treatment three times at 150 MPa using a high-pressure homogenizer (Yoshida Machinery Co., Ltd., NanoVeta L-ES) to obtain a dispersion (solid content 1.0% by mass). 182 g of the obtained dispersion was weighed out, and deionized water was added to make a total of 400 g. 1.2 mL of 0.1 M sodium hydroxide aqueous solution and 120 mg of sodium borohydride were added, and the mixture was stirred at 25°C for 4 hours. Next, 9 mL of 1 M hydrochloric acid was added and the mixture was stirred to perform protonation. After stirring, the solid components in the dispersion were filtered off by suction filtration. Subsequently, the solid components were dispersed in deionized water, and the process of filtering off the solid components by suction filtration was repeated until the conductivity of the filtrate was 50 μS / cm or less, to obtain a dispersion of finely pulverized anion-modified cellulose fiber 1 (solid content 0.9 mass%). The obtained cellulose fibers had a carboxyl group content of 1.41 mmol / g, an average fiber diameter of 3.3 nm, an average fiber length of 600 nm, and a crystallinity of 60%.

[0144] Preparation Example 2 [Preparation of Composition for Film Preparation] [Preparation of film preparation composition 1] In a beaker, the dispersion of the finely milled anionically modified cellulose fiber 1, silicone oil, and amino-modified silicone were mixed to the composition shown in Table 2, 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 using a high-pressure homogenizer (NanoVeta L-ES, manufactured by Yoshida Machinery Co., Ltd.) to obtain composition 1 for film preparation. The obtained composition 1 was a turbid liquid, and since oil droplets were observed to be dispersed in water using an optical microscope, it was determined to be an emulsion. The average emulsion particle size measured by laser diffraction was 300 nm. The viscosity of the mixture at 25°C was 10 mPa·s.

[0145] [Table 2]

[0146] Examples 1-3 and Comparative Example 1 [Film preparation] A substrate film having an adhesive layer on one surface of the resin layer, as shown in Table 3, was prepared. Corona discharge treatment (energy: 0.92 kW, sweep speed: 0.20 r / min, number of sweeps: 1) was performed on the surface of each substrate film that lacked an adhesive layer, using a corona treatment station (manufactured by Kasuga Electric Co., Ltd., table-type processing device (aluminum type 5 electrode), high-frequency power supply: AGF-B10). Next, each base film was cut to 26mm x 60mm. 271 μL of the above-mentioned film preparation composition 1 was dropped onto the surface of the substrate film without the adhesive layer after cutting using a pipette, and spread uniformly over the entire surface. Subsequently, the film was allowed to form by standing it in a constant temperature and humidity chamber (ESPEC, PL-3J) set to 25°C and 40%RH for 24 hours, thereby preparing a film having a resin layer and a synovial surface film on the surface of the resin layer, with an adhesive layer on the surface opposite to the surface having the synovial surface film. Furthermore, assuming that components (A), (B), and (C) are solid components, if 271 μL of film preparation composition 1 with a solid content concentration of 11.5% by mass is evenly applied to the above substrate film, the thickness of the liquid film will be 174 μm, and assuming that components other than solid components volatilize, the film thickness can be calculated to be 20 μm.

[0147] [Slip Test] (After film formation) The adhesive surfaces of each prepared film were brought into contact with a glass slide and fixed in place. Next, the film was fixed together with the glass slide substrate on a stand tilted at a 45-degree angle to the vertical, with the dried film facing upwards. At 23°C, a 10 μL drop of water was placed near the top edge of the film, which was fixed to a stand, and it was visually confirmed whether the water droplet slid down to the bottom edge of the substrate within 20 seconds. Films on which the water droplet slid down within 20 seconds were evaluated as having "synovial surface properties" and were indicated with "○" in Table 3. Films on which the water droplet did not slid down within 20 seconds were evaluated as having "no synovial surface properties" and were indicated with "×" in Table 3. As a result, it was found that all of the dried films formed in Examples 1-4 and Comparative Example 1 had synovial surface properties.

[0148] (Immediately after the injury) With the film fixed to a stand tilted at a 45-degree angle, eight scratches were made using a cutter, parallel to the upper edge of the film and spaced 2 mm apart, as shown in Figure 2. The depth of the scratches was such that they reached the resin layer. Immediately afterward, a drop test using 10 μL of water droplets was performed at 23°C, similar to the above. The degree of deterioration of the synovial surface was determined by the number of scratches that the water droplet passed through within 20 seconds. Specifically, the result was judged on a scale of 0 to 8, with a smaller number indicating a greater degree of deterioration of the synovial surface. More specifically, a score of 0 was used if no water droplets passed through any scratches within the given time, and a score of 8 was used if the water droplets passed through all 8 scratches within the given time. The results are shown in Table 3.

[0149] (After standing process) The film with the aforementioned scratches was left to stand under either the following standing condition 1 or standing condition 2, at the relative humidity and time listed in Table 3, and the standing process was performed. Immediately after the standing process was completed, a sliding test using 10 μL of water droplets was performed at 23°C, as described above. The results are shown in Table 3.

[0150] (Evaluation of the degree of recovery of synovial fluid surface properties) A higher evaluation value in the drop test after the standing process indicates a greater degree of recovery of the synovial fluid surface properties. An evaluation value of 8 in the drop test after the standing process indicates that the synovial fluid surface properties have recovered to the same level as before the damage occurred. In this evaluation method, an evaluation value of 7 or higher in the drop test after the standing process was considered to indicate that the synovial fluid surface properties had recovered sufficiently.

[0151] [Stationing process] (Static conditions 1) Under conditions of 23°C, a dish containing a saturated potassium sulfate solution was placed in a desiccator, which was then sealed with a lid. After 24 hours, the lid was opened, a film was placed in the desiccator, and the lid was sealed again. After the time elapsed as shown in Table 3, the lid was opened, the sample was removed, and a sliding evaluation was performed. (Static conditions 2) Under conditions of 23°C, a dish containing a saturated potassium carbonate solution was placed in a desiccator, which was then sealed with a lid. After 24 hours, the lid was opened, a film was placed inside the desiccator, and the lid was sealed again. After the time elapsed as shown in Table 3, the lid was opened, the sample was removed, and a sliding evaluation was performed.

[0152] The humidity values ​​listed in Table 3 were calculated by substituting A0, A1, A2, and A3, as well as t (23), as shown in Table 1 of Reference 1, into the following formula described in Reference 1. Here, A0 is the constant term, representing the reference relative humidity independent of temperature, while A1, A2, and A3 represent the coefficients of the first, second, and third order terms of temperature, respectively, showing the change in relative humidity with respect to temperature changes. Specifically, the following was used. Static condition 1: A0:98.7792, A1:-0.0590502, A2:0, A3:0 Stationary condition 2: A0:43.1315, A1:0.00147523, A2:0, A3:0

[0153]

number

[0154] Reference 1: L. Greenspan, Journal of Research of the National Bureau of Standards-A. Physics and Chemistry, 81(1A) (1977)

[0155] Table 3 shows the main conditions and test results.

[0156] [Table 3]

[0157] As is clear from Table 3, when the standing time in the standing process exceeded 5 minutes, the slippage evaluation after standing improved significantly compared to the slippage evaluation immediately after scratching (Examples 1-4). From this, it was found that the synovial surface properties of the damaged synovial surface film were restored by the recovery method of the present invention. On the other hand, when the standing time in the standing process was 5 minutes, the slippage evaluation after standing was the same as the slippage evaluation immediately after scratching, indicating that the synovial surface properties did not recover (Comparative Example 1).

[0158] Details of the components used in the above examples are as follows: [Ingredients (A)] Silicone oil: Shin-Etsu Chemical Co., Ltd., KF-96-100cs, SP value: 7.3 This component (A) was a liquid at 25°C and 1 atmosphere. [Component (C)] Amino-modified silicone: Manufactured by Dow Toray Corporation, DOWSIL TM FZ-3710, kinematic viscosity at 25°C: 1,000 mm² 2 / s, amino equivalent: 1,700 g / mol [Base film] Polyolefin film: Sumilon Co., Ltd., VE-303W (Resin layer: Polyolefin, Adhesive layer: Rubber) Polyvinyl chloride film: 3M Scotchcal Overlaminate Film 8428G (Resin layer: polyvinyl chloride, Adhesive layer: acrylic resin)

[0159] [Preparation of anionically modified cellulose fiber 2] Even if an anionically modified cellulose fiber 2 with phosphate groups introduced is used instead of anionically modified cellulose fiber 1 with carboxyl groups introduced by TEMPO oxidation treatment, a film preparation composition exhibiting the same effects as in Examples 1 to 4 can be obtained. Such anionically modified cellulose fiber 2 can be prepared by the following phosphorylation treatment.

[0160] [Phosphorication treatment] To obtain chemically impregnated fibers, 100 parts by mass of bleached kraft pulp fibers from coniferous trees, which are the raw material for natural cellulose fiber, are impregnated with a mixed aqueous solution of ammonium dihydrogen phosphate and urea, and then pressed until the mixture contains 56 parts by mass of ammonium dihydrogen phosphate and 150 parts by mass of urea. The chemically impregnated fibers are dried in a dryer at 105°C to evaporate the moisture. The moisture-free fibers are then heated in a forced-air dryer set to 140°C for 4 minutes. To 100 parts by mass of the obtained fibers, 10,000 parts by mass of deionized water are added, and the mixture is stirred to disperse the fibers. Then, the solids are filtered off by suction filtration. To 100 parts by mass of the solids in the filtered cake, 10,000 parts by mass of deionized water are added, and the mixture is stirred to disperse the fibers. Then, the solids are filtered off by suction filtration. To the obtained cake, 10,000 parts by mass of deionized water is added, and a 1N sodium hydroxide aqueous solution is added dropwise while stirring to obtain a slurry with a pH of 12-13. Next, while stirring, 0.01M hydrochloric acid is added to adjust the pH of the suspension to 2. Then, the solid components are filtered off by suction filtration. The cake is dispersed in deionized water, and the cake is filtered off by suction filtration. This process is repeated until the electrical conductivity of the filtrate is 200 μS / cm or less. The resulting solid content is then dehydrated to obtain anionically modified cellulose fibers 2. [Industrial applicability]

[0161] The recovery method of the present invention can restore the surface properties of the synovial fluid surface film in a short time after damage to the synovial fluid surface film, making it effective for application to synovial fluid surface films and films in outdoor environments where damage from flying stones, snow, dust, rainwater, etc., is likely to occur. [Explanation of Symbols]

[0162] 1. Damaged area

Claims

1. A method for restoring the synovial surface properties of a synovial surface film, comprising a settling step of allowing the damaged synovial surface film, whose synovial surface properties have been reduced, to stand for more than 5 minutes, The synovial surface film is a synovial surface film containing the following component (A): A method for restoring the surface properties of a synovial fluid surface film. (A) Organic compounds that are liquid at 25°C and 1 atm

2. The method for restoring the surface properties of a synovial fluid according to claim 1, wherein the synovial fluid surface film contains the following component (B). (B) Anionic modified cellulose fibers

3. The method for restoring the surface properties of a synovial fluid according to claim 1, wherein the synovial fluid surface film contains the following component (C). (C) Hydrophobic compounds having cationic functional groups (excluding those corresponding to component (A) above).

4. The method for restoring the surface properties of a synovial fluid according to claim 1, wherein the relative humidity during the standing process is 40% RH or higher.

5. A film comprising a resin layer and a synovial surface film on one surface of the resin layer, The aforementioned synovial surface film is a synovial surface film having synovial surface properties and containing the following component (A). (A) Organic compounds that are liquid at 25°C and 1 atm

6. The film according to claim 5, which has the ability to restore synovial surface properties when damaged and its synovial surface properties are reduced.

7. The film according to claim 5, wherein the synovial fluid surface film contains the following component (B). (B) Anionic modified cellulose fibers

8. The film according to claim 5, wherein the synovial fluid surface film contains the following component (C). (C) Hydrophobic compounds having cationic functional groups (excluding those corresponding to component (A) above).

9. The film according to claim 5, which is for stain prevention and / or snow prevention.

10. The film according to claim 5, further having an adhesive layer on the surface opposite to the surface having a synovial surface film of the resin layer.

11. A film repair agent containing the following ingredient (A). (A) Organic compounds that are liquid at 25°C and 1 atm

12. The film repair agent according to claim 11, further comprising the following component (B) and / or component (C). (B) Anionic modified cellulose fibers (C) Hydrophobic compounds having cationic functional groups (excluding those corresponding to component (A) above).

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