Coating agent

Abstract

To provide a coating agent that can form a film with excellent release properties and durability. [Solution] A coating agent containing the following components (A) to (C). Component (A): Hydrophobic modified cellulose fiber to which one or more modifying groups selected from the group consisting of anionic groups and hydroxyl groups are attached; Component (B): Water; Component (C): Organic compound that is liquid at 25°C and 1 atm.

Description

Technical Field

[0001] The present invention relates to a coating agent.

Background Art

[0002] Conventionally, in the fields of manufacturing and molding of resins, rubbers, ceramics, cement, etc., reduction in productivity due to adhesion of these substances to manufacturing equipment and molding equipment has been a problem, and silicone oil, mineral oil, paraffin wax, fatty acid derivatives, glycols, talc, mica, etc. have been used as release agents. For example, Patent Document 1 discloses using a compound having a perfluoroalkyl group as a release agent.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, the releasability of conventional release agents cannot be said to be sufficient, and further improvement is required.

[0005] Therefore, an object of the present invention is to provide a coating agent capable of forming a film excellent in releasability and its durability.

Means for Solving the Problems

[0006] The present invention relates to the following [1] to [5]. [1] A coating agent containing the following components (A) to (C). (A) Hydrophobically modified cellulose fibers having one or more selected from the group consisting of anionic groups and hydroxy groups bonded thereto (B) Water (C) An organic compound that is liquid at 25°C and 1 atm [2] The coating agent according to [1], further comprising component (D) a polyether-modified silicone compound. [3] A coating agent as described in [1] or [2] above, for use as a mold release agent. [4] A coating film obtained by drying the coating agent described in any one of the above items [1] to [3]. [5] The coating film described in [4] above, which is a release agent film. [Effects of the Invention]

[0007] By using the coating agent provided by the present invention, a film with excellent release properties and durability can be formed. [Modes for carrying out the invention]

[0008] As a result of diligent research by the present inventors to solve the above problems, they discovered that when a film obtained by coating a composition containing hydrophobic modified cellulose fibers, which are formed by bonding a specific structural modification group to cellulose fibers, water, and an organic compound that is liquid at 25°C and 1 atm, onto a substrate and drying it, the resulting film exhibits surprisingly excellent release properties for resins and other materials, thus completing the present invention.

[0009] 1. Coating agent The coating agent of the present invention contains the following components (A) to (C). <Ingredient (A)> Component (A) is a hydrophobic modified cellulose fiber to which one or more modifying groups selected from the group consisting of anionic groups and hydroxyl groups are attached, and one or more hydrophobic modified cellulose fibers selected from the group consisting of (a) and (b) below are preferred. (a) Hydrophobic modified cellulose fibers formed by bonding polymer compounds to cellulose fibers (b) A hydrocarbon having a cationic group in the anionic group of an anionic-modified cellulose fiber. Hydrophobic modified cellulose fibers formed by ionic bonding of system compounds.

[0010] In this specification, hydrophobic modified cellulose fibers refer to cellulose fibers to which a polymer compound is bonded, or cellulose fibers to which a hydrocarbon compound is bonded. Preferably, a polymer compound and / or a hydrocarbon compound having a cationic group are bonded via ionic bonds to the anionic groups of anion-modified cellulose fibers. Here, the hydrocarbon compound preferably has a total of 16 to 40 carbon atoms.

[0011] [Cellulose type I crystal structure and degree of crystallinity] Hydrophobic modified cellulose fibers preferably have a cellulose type I crystalline structure due to the use of natural cellulose as their raw material. From the viewpoint of strength development during film formation, the degree of crystallinity of the hydrophobic 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. The degree of crystallinity of cellulose type I is measured by the method described in the examples below.

[0012] [Average fiber diameter of hydrophobic modified cellulose fibers] The average fiber diameter of the hydrophobic 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 handling ease, and preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less, from the viewpoint of film strength. The average fiber diameter of the hydrophobic modified cellulose fibers is measured by the method described in the examples below.

[0013] [Modifying group] One preferred embodiment of the hydrophobic modified cellulose fiber of component (a), preferably an anionic modified cellulose fiber to which a polymer compound is bonded, has a structure represented by the following general formula (T-Ce). Component (a) may also be a hydrophobic modified cellulose fiber in which a modifying group is bonded to the hydroxyl group of a cellulose fiber that does not have anionic groups.

[0014]

Chem.

[0015] (wherein X is -CH2OH, -CH2O-R , -C(=O)OH, -C(=O)O-R 1 , -C(=O)-O - H3N + -R 1 and -C(=O)-NH-R 1 is one or more groups selected from the group consisting of, and R 1 is a modifying group, R is each independently a hydrogen atom or a modifying group, and R 1 and R may be the same or different, and at least one of the plurality of R 1 and R is a modifying group. m is an integer of 20 or more and 3,000 or less.)

[0016] In the hydrophobic modified cellulose fiber formed by binding a polymer compound to cellulose fiber, the modifying group is a group derived from the polymer compound, and the structure of the modifying group (that is, R 1 and R in the above formula (T-Ce)) depends on the structure of the polymer compound used. The bonding mode of the modifying group to the cellulose fiber is preferably a covalent bond or an ionic bond. From the viewpoint of simplicity of production, an ionic bond is preferred, and from the viewpoint of stability of the formed film, a covalent bond is preferred. A compound for introducing a modifying group, such as a polymer compound and a hydrocarbon compound (preferably a hydrocarbon compound having a cationic group), may be described herein as a "modifying compound".

[0017] The bonding sites for modifying groups in cellulose fibers include hydroxyl groups and aldehyde groups present in the cellulose fibers, or functional groups introduced by chemical modification of the cellulose fibers. The functional groups introduced by chemical modification are anionic groups, and in this case, the cellulose fibers become anionically modified cellulose fibers. The preferred anionic group in anionically modified cellulose fibers is the carboxyl group. From the viewpoint of ease of preparation and mild reaction conditions, carboxyl group-containing cellulose fibers are more preferred as anionically modified cellulose fibers.

[0018] When the bonding site is a hydroxyl group of an anionically modified cellulose fiber, the bonding mode is a covalent bond, and examples include ether bonds, ester bonds, carbonate bonds, etc.

[0019] When the bonded site is an anionic group of anion-modified cellulose fiber, the bonded mode is either ionic or covalent. When the bonded mode is ionic, it refers to a state in which a modifying compound having a cationic group is bonded via electrostatic interaction. When the bonded mode is covalent, it refers to a state in which the bond is formed via ester bonds, amide bonds, etc. In particular, with respect to the carboxyl group of carboxyl group-containing cellulose fiber, the bond is formed via ester bonds, amide bonds, carbonate bonds, urethane bonds, etc.

[0020] For example, the modifying compound is an amino-modified silicone (referred to as "H2N-[alkylsilicone skeleton]"), and the cellulose fiber is a carboxyl group-containing cellulose fiber (referred to as "[cellulose skeleton]-C * Let's assume (=O)-OH. In the case where the bonding mode is an ionic bond, the hydrophobic modified cellulose fiber is "[cellulose backbone]-C * (=O)-O - H3N + The structure becomes like "-[alkylsilicone skeleton]", and the modifying group is "-[alkylsilicone skeleton]". On the other hand, if the bonding mode is an amide bond, the hydrophobic modified cellulose fiber becomes "[cellulose skeleton]-C *The structure becomes like "(=O)-NH-[alkylsilicone skeleton]", and the modifying group becomes "-[alkylsilicone skeleton]". Thus, the structure of the modifying group depends on the structure of the modifying compound used. Note that "C * " refers to the carbon atom at position 6 of the cellulose constituent unit.

[0021] Furthermore, the modifying groups of the hydrophobic modified cellulose fibers of component (b), that is, the hydrophobic modified cellulose fibers in which a hydrocarbon compound having a cationic group is bonded via ionic bonding to the anionic group of the anionic modified cellulose fiber, are derived from the hydrocarbon compound having a cationic group. In this case, the mode of bonding of the modifying group to the anionic group of the anionic modified cellulose fiber is ionic bonding, and the hydrophobic modified cellulose fibers of component (b) are in a state where the cationic group of the modifying group is adsorbed to the anionic group on the surface of the cellulose fiber via electrostatic interaction. In this specification, groups derived from polymer compounds and groups derived from hydrocarbon compounds (preferably hydrocarbon compounds having cationic groups) are collectively referred to as "modifying groups."

[0022] The amount of modifying groups (mmol / g) and the introduction rate (mol%) in hydrophobic modified cellulose fibers refer to the amount and proportion of modifying groups introduced into the hydrophobic modified cellulose fibers. Specifically, these are measured by the method described in the examples below. The amount of modifying groups and the introduction rate can be adjusted by the amount and type of modifying compound added, the reaction temperature, the reaction time, the solvent, etc.

[0023] From the viewpoint of obtaining a film with excellent release properties, the amount of modifying groups bound to the hydrophobic modified cellulose fibers 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. Furthermore, from the viewpoint of reactivity, it is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, and even more preferably 2 mmol / g or less.

[0024] Furthermore, from the viewpoint of obtaining a film with excellent release properties, the rate of introduction of modifying groups in hydrophobic modified cellulose fibers 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 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.

[0025] [Method for producing hydrophobic modified cellulose fibers] The hydrophobic modified cellulose fibers of component (A) can be obtained by a method comprising, for example, (1) introducing anionic groups into raw material cellulose fibers to obtain anionic modified cellulose fibers, and (2) bonding a polymer compound and / or a hydrocarbon compound having cationic groups to the anionic modified cellulose fibers to obtain hydrophobic modified cellulose fibers.

[0026] One embodiment of the process described in (2) above is: Ingredients (A-1) Anionic modified cellulose fiber, Component (A-2): One or more compounds selected from the group consisting of amino-modified silicones and hydrocarbon compounds having cationic groups. Ingredient (B) Water, and Components (C): Organic compounds that are liquid at 25°C and 1 atm. One example is the step of mixing the components. This embodiment is the same as the step in the method for producing the coating agent of the present invention described later, namely the step of mixing components (A-1), (A-2), (B), and (C). According to this embodiment, hydrophobic modified cellulose fibers and the coating agent of the present invention can be produced in the same process, and therefore it can be said to be a more preferable production method.

[0027] (1) Process for obtaining anionic 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 to introduce at least one anionic group and thereby anionically modify them.

[0028] The cellulose fibers to be anionically modified, i.e., the cellulose fibers used as raw materials for hydrophobically modified cellulose fibers and anionically 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.

[0029] The average fiber diameter of the cellulose fibers used as raw material is not particularly limited, but from the viewpoint of handling ease and cost, it is preferably 1 μm or more, and preferably 300 μm or less.

[0030] Furthermore, while the average fiber length of the raw cellulose fibers is not particularly limited, from the viewpoint of availability and cost, it 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 in which the average fiber length is 1 μm or more and 1,000 μm or less, obtained by shortening the raw cellulose fibers through alkaline hydrolysis treatment, acid hydrolysis treatment, etc.

[0031] Examples of anionic groups that can be introduced include carboxyl groups, sulfonic acid groups, or phosphate groups.

[0032] (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 at least one compound selected from the group consisting of compounds having carboxyl groups, acid anhydrides of compounds having carboxyl groups, and derivatives thereof.

[0033] The method for oxidizing the hydroxyl groups of the cellulose is not particularly limited, but for example, a method 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 can be applied. More specifically, known methods, such as the method described in Japanese Patent Application Publication No. 2011-140632, can be referred to.

[0034] 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 that is to be oxidized 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, such cellulose fibers may be referred to as "oxidized cellulose fibers." Oxidized cellulose fibers are preferred because they are easier to prepare than other anionically modified cellulose fibers. Therefore, one preferred embodiment of the hydrophobically modified cellulose fiber in the present invention is a hydrophobicly modified cellulose fiber obtained by bonding an amino-modified silicone to a carboxyl group-containing cellulose fiber.

[0035] 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.

[0036] (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.

[0037] (iii) Anionic modified cellulose fibers (component (A-1)) The anionic groups contained in the anionically modified cellulose fibers obtained in this way include, for example, carboxyl groups, sulfonic acid groups, and phosphate groups. From the viewpoint of the efficiency of introducing modifying groups into cellulose fibers, the anionic group is preferably a carboxyl group. Examples of counterions that pair with the anionic groups in the anionically modified cellulose fibers 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 acid.

[0038] 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 introducing modifying groups. Furthermore, from the viewpoint of improving handling properties, 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.

[0039] The average fiber diameter of the 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 handling ease, and preferably 200 nm or less, more preferably 100 nm or less, and even more preferably 50 nm or less, from the viewpoint of film strength. The average fiber diameter of the anion-modified cellulose fibers is measured by the method described in the examples below.

[0040] (2) Process for obtaining hydrophobic modified cellulose fibers The hydrophobic modified cellulose fibers of component (A) can be produced by bonding one or more compounds selected from the group consisting of polymer compounds and hydrocarbon compounds having cationic groups to the anionic modified cellulose fibers described above. As such a production method, a known method, for example, the method described in Japanese Patent Application Publication No. 2015-143336, can be used.

[0041] (i) Polymer compounds The polymer compounds used as modifying compounds in this invention can be commercially available or prepared according to known methods. One polymer compound may be used, or two or more polymer compounds may be used.

[0042] The polymer compounds used as modifying compounds in the present invention are preferably polymer compounds having a repeating structure linked by an oxygen atom, more preferably polymer compounds having a repeating structure linked by an oxygen atom, such as a polyoxyalkylene structure or a polysiloxane structure, and even more preferably silicone compounds. Examples of silicone compounds include amino-modified silicones, epoxy-modified silicones, carboxy-modified silicones, carbinol-modified silicones, and hydrogen-modified silicones, and the position of the reactive group may be either a side chain or a terminal of the silicone compound. Among these, amino-modified silicones are preferred from the viewpoint of ease of modification.

[0043] (ii) Amino-modified silicone Amino-modified silicones are silicone compounds that contain amino groups. For example, an amino-modified silicone has a kinematic viscosity of 10 mmHg at 25°C. 2 / s or more 20,000mm 2 A concentration of less than or equal to / s is preferred. Furthermore, amino-modified silicones with an amino equivalent of 400 g / mol to 16,000 g / mol are preferred.

[0044] The kinematic viscosity at 25°C can be determined using an Ostwald viscometer, and from the viewpoint of obtaining a film with excellent release properties, a 20 mm film is more preferable. 2 / s or more, more preferably 50mm 2 It is 10,000 mm or more, and more preferably from the standpoint of handling performance. 2 / s or less, more preferably 5,000 mm 2 It is less than or equal to / s.

[0045] Furthermore, 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 obtaining a film with excellent release properties, and 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. Note that the amino equivalent is the molecular weight per nitrogen atom, and is calculated as amino equivalent (g / mol) = weight-average molecular weight / number of nitrogen atoms per molecule. Here, the weight-average molecular weight is the value obtained using gel permeation chromatography with polystyrene as the standard substance, and the number of nitrogen atoms can be determined by elemental analysis.

[0046] A specific example of an amino-modified silicone is the compound represented by general formula (a1).

[0047] [ka]

[0048] [In the formula, R 1aR represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, an alkoxy group having 1 to 3 carbon atoms, or a hydrogen atom, and from the viewpoint of obtaining a film with excellent release properties, a methyl group or a hydroxyl group is preferred. 2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxyl group, or a hydrogen atom, and from a similar viewpoint, a methyl group or a hydroxyl group is preferred. B represents a side chain having at least one amino group, and R 3a x represents an alkyl group or hydrogen atom having 1 to 3 carbon atoms. x and y represent the average degree of polymerization, and are selected such that the kinematic viscosity and amino equivalent of the compound at 25°C are within the above range. Note that R 1a , R 2a , R 3a These may be the same or different, and there may be multiple Rs. 2a They may be the same or different.

[0049] In the compound of general formula (a1), from the viewpoint of obtaining a film with excellent mold release 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. The weight-average molecular weight of the compound of general formula (a1) is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000, and even more preferably 8,000 to 50,000.

[0050] 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.)

[0051] 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)

[0052] Furthermore, as the amino-modified silicone, from the viewpoint of obtaining a film with excellent mold release properties, it 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, and more preferably one or more selected from the group consisting of a compound in which the amino-group-containing side chain B is represented by -C3H6-NH2 [hereinafter referred to as component (a1-1)] and a compound in which the amino-group-containing side chain B is represented by -C3H6-NH-C2H4-NH2 [hereinafter referred to as component (a1-2)].

[0053] 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), 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: 2800) from Dow Toray. (Mino 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-80 Preferred are KF-8005 (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). 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.

[0054] (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).

[0055] (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), and SS-3551 (kinematic viscosity: 1000, amino equivalent: 1700) are more preferred.

[0056] Furthermore, polymer compounds may have substituents. Examples of substituents include: Examples 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 groups; alkoxy-carbonyl groups having 1 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, sec-butoxycarbonyl, tert-butoxycarbonyl, pentyloxycarbonyl, and isopentyloxycarbonyl groups; halogen atoms such as fluorine, chlorine, bromine, and iodine; acyl groups having 1 to 6 carbon atoms, such as acetyl and propionyl groups; aralkyl groups; aralkyloxy groups; alkylamino groups having 1 to 6 carbon atoms; and dialkylamino groups having 1 to 6 carbon atoms in the alkyl group.

[0057] (iii) hydrocarbon compounds In the present invention, hydrocarbon compounds having cationic groups are preferred as one of the modifying compounds. A hydrocarbon compound having cationic groups is one in which one or more hydrocarbon groups are bonded to one cationic group. From the viewpoint of obtaining a film with excellent release properties, the total number of carbon atoms in the hydrocarbon compound having cationic groups 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.

[0058] Hydrocarbon compounds containing a cationic group are compounds in which the hydrocarbon group is directly bonded to a nitrogen atom or 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., it is a compound in which the hydrocarbon group is covalently bonded to at least one of the nitrogen atoms or carbon atoms of the functional group. When the cationic group is an imidazolium, pyridinium, imidazoline, etc., it is a compound in which at least one hydrocarbon group is covalently bonded to any position in the ring structure. Hydrocarbon compounds having cationic groups are more preferably those that do not contain oxyalkylene groups.

[0059] (iv) hydrocarbon group Examples of hydrocarbon groups in the hydrocarbon compounds include chain-type saturated hydrocarbon groups, chain-type 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 1 or more, more preferably 2 or more, even more preferably 3 or more, even more preferably 12 or more, and even more preferably 16 or more. Similarly, from the same viewpoint, it is preferably 40 or less, more preferably 30 or less, and even more preferably 24 or less. Unless otherwise specified, the number of carbon atoms in a hydrocarbon group refers to the number of carbon atoms in a single hydrocarbon group.

[0060] Specific examples of chain-type saturated hydrocarbon groups include, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, pentyl group, tert-pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, octadecyl group, docosyl group, octacosanyl group, and the like.

[0061] Specific examples of chain-type unsaturated hydrocarbon groups include, for example, ethenyl group, propenyl group, butenyl group, isobutenyl group, isoprenyl group, pentenyl group, hexenyl group, heptenyl group, octenyl group, nonenyl group, decenyl group, dodecenyl group, tridecenyl group, tetradecenyl group, and octadecenyl group.

[0062] Specific examples of cyclic saturated hydrocarbon groups include, for example, cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group, cyclodecyl group, cyclododecyl group, cyclotridecyl group, cyclotetradecyl group, and cyclooctadecyl group.

[0063] Aromatic hydrocarbon groups are selected from the group consisting of, for example, aryl groups and aralkyl groups. The aryl group and aralkyl group may be either substituted or unsubstituted aromatic rings.

[0064] Examples of aryl groups include phenyl, naphthyl, anthryl, phenanthryl, biphenyl, triphenyl, terphenyl groups, and groups in which these groups are substituted with substituents described later.

[0065] Examples of aralkyl groups include benzyl, phenethyl, phenylpropyl, phenylpentyl, phenylhexyl, phenylheptyl, and phenyloctyl groups, as well as groups in which the aromatic groups of these groups are further substituted with substituents.

[0066] 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.

[0067] The hydrocarbon compounds having the cationic 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.

[0068] (v) Amount of modifying compound used In the process of obtaining hydrophobic modified cellulose fibers, the equivalent amount of functional groups of the modifying compound used that can react with the anionic groups of the anionic groups of the anionic modified cellulose fibers is preferably 0.1 equivalents or more, more preferably 0.5 equivalents or more, and even more preferably 1 equivalent or more, from the viewpoint of obtaining a film with excellent release properties. Similarly, it is preferably 20 equivalents or less, more preferably 10 equivalents or less, and even more preferably 2 equivalents or less.

[0069] (3) Miniaturization process By refining the cellulose at any stage of the method for producing hydrophobic modified cellulose fibers, micrometer-scale cellulose can be refined to a nanometer scale. Since reducing the average fiber diameter to nanometer size improves the strength during film formation, it is preferable to further perform the refinement process.

[0070] 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 of the reactant fibers in the micronization process is preferably 50% by mass or less.

[0071] <Ingredient (B)> In this invention, component (B) is water. Component (B) serves as a solvent in the production of hydrophobic modified cellulose fibers and as one of the constituent components of the coating agent of this invention.

[0072] <Ingredient (C)> In this invention, component (C) is a liquid organic compound at 25°C and 1 atm. Component (C) may also be a solvent used in the production of hydrophobic modified cellulose fibers. At 25°C and 1 atm, the solubility of a liquid organic compound in water is preferably 10g or less, and more preferably 1g or less, per 100g of water at 25°C. From the viewpoint of obtaining a film with excellent release properties, the molecular weight of component (C) 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, preferably 100 or more, and more preferably 200 or more.

[0073] Component (C) in the present invention specifically includes oils, organic solvents, polymerizable monomers, prepolymers, and the like. Component (C) in the present invention is preferably an oil, and as an oil, from the viewpoint of obtaining a film with excellent release properties, for example, one or more selected from the group consisting of alcohols, ester oils, hydrocarbon oils, silicone oils, ether oils, fats and oils, fluorinated inert liquids, and fatty acids are preferred, 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.

[0074] 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.

[0075] Examples of silicone oils include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane. 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.

[0076] From the viewpoint of obtaining a film with excellent mold release properties, the compound of component (C) 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.

[0077] 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).

[0078] Examples of oils with an SP value of 10 or less used in this 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 fluorine. Inert liquids (e.g., 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 oils (e.g., KF96-1cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7) Examples include 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.

[0079] <Ingredient (D)> The coating agent of the present invention may contain a polyether-modified silicone compound of component (D). By incorporating such component (D) into the coating agent, a film with improved mold release properties can be obtained. An example of component (D) is a compound having a methyl silicone chain as the main chain and side chains consisting of polyoxyethylene groups, and specifically, a compound represented by the following general formula can be mentioned.

[0080] [ka]

[0081] (In the formula, R 1R 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.)

[0082] From the viewpoint of obtaining a film with excellent release properties obtained by drying the coating agent, the HLB value of the polyether-modified silicone compound is preferably within a specific range, specifically preferably 1 or higher, more preferably 5 or higher, even more preferably 10 or higher, preferably 18 or lower, and more preferably 16 or lower.

[0083] When using two or more polyether-modified silicones with different HLB values, the weighted average of these values ​​should fall 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

[0084] The kinematic viscosity of the polyether-modified silicone compound at 25°C is preferably within a specific range from the viewpoint of obtaining a film with excellent release properties obtained by drying the coating agent. Specifically, it is preferably 1 mm. 2 / s or more, more preferably 5mm 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 It is less than or equal to / s.

[0085] Polyether-modified silicone compounds that can be preferably used as component (D) 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, KF-6043, etc., manufactured by Shin-Etsu Chemical Co., Ltd., and from the viewpoint of obtaining a film with excellent release properties upon drying of the coating agent, KF-640, KF-642, KF-643, KF-351A, KF-354L, KF-355A, etc. 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 component (D).

[0086] <Polymer compounds other than components (A) and (D)> The coating agent of the present invention may further contain polymer compounds other than components (A) and (D). From the viewpoint of obtaining a film with excellent release properties, such polymer compounds are preferably one or more selected from the group consisting of polymer compounds (X) and polymer compounds (Y) below, with polymer compound (X) being more preferred. Polymeric compound (X): A polymeric compound having an ester group, amide group, urethane group, amino group, ether group, or carbonate group in its main chain (however, polymeric compounds that fall under either component (A-1) or component (D) are not treated as polymeric compound (X)). Polymer compound (Y): Methacrylic or acrylic polymer having an ester group or amide group in its side chain.

[0087] The weight-average molecular weight of the polymer compound is preferably 1,000 or more from the viewpoint of obtaining a film with excellent release properties, and preferably 500,000 or less from the same viewpoint.

[0088] [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.

[0089] 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.

[0090] 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.

[0091] 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.

[0092] 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.

[0093] 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.

[0094] [High molecular compound (Y)] Examples of polymer compounds (Y), namely methacrylic or acrylic polymers having ester or amide groups in their side chains, include polyalkyl(meth)acrylates such as polymethyl(meth)acrylate, polyethyl(meth)acrylate, and polybutyl(meth)acrylate, as well as poly(meth)acrylamides such as poly(meth)acrylamide, polyN-methyl(meth)acrylamide, polyN,N-dimethyl(meth)acrylamide, and polyN-phenyl(meth)acrylamide.

[0095] <Other ingredients> In addition to the components mentioned above, the coating agent of the present invention may contain 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, antifungal agents, 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 regulators; leveling agents; conductive agents; ultraviolet dispersants; deodorants, etc., to the extent that they do not impair the effects of the present invention. Similarly, other polymer materials and other compositions may be added to the present invention, to the extent that they do not hinder the effects of the present invention.

[0096] <Properties of coating agents> The coating agent of the present invention is a composition containing the above-mentioned components (A), (B), and (C) as essential components, and is preferably an emulsified composition. Emulsification in the present invention is performed by applying mechanical force to a mixture of water and a liquid organic compound at 25°C and 1 atm, so that droplets of the other liquid are finely dispersed in one liquid. Either an o / w type emulsion or a w / o type emulsion may be used, but an o / w type emulsion is preferred.

[0097] From the viewpoint of emulsifying power, the content of component (A) in the coating agent or when mixed 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. On the other hand, from the viewpoint of handling properties, it is preferably 15% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less.

[0098] The content of component (B) in the coating agent or when mixed 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 maintaining an emulsified state, and preferably 98% by mass or less, from the viewpoint of effective quantity.

[0099] The content of component (C) in the coating agent or when mixed 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 an emulsified state, while from the viewpoint of solution viscosity and handling properties, it is preferably 70% by mass or less, more preferably 60% by mass or less, and even more preferably 50% by mass or less.

[0100] The mass ratio (A / C) of component (A) to component (C) in or during mixing of the coating agent is: From the viewpoint of obtaining a film with excellent properties, the value is preferably 0.0001 or higher, more preferably 0.001 or higher, even more preferably 0.004 or higher, even more preferably 0.01 or higher, and even more preferably 0.04 or higher. From the viewpoint of film formation, the value is preferably 20 or lower, more preferably 10 or lower, even more preferably 5 or lower, even more preferably 3 or lower, and even more preferably 2 or lower. From these viewpoints, the value is preferably 0.0001 to 20 or lower, more preferably 0.001 to 10 or lower, even more preferably 0.004 to 5 or lower, even more preferably 0.01 to 3 or even more preferably 0.04 to 2 or lower.

[0101] When component (D) is used, the content of component (D) in the coating agent or when mixed 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 obtaining a film with excellent release properties. On the other hand, from the same viewpoint, it is preferably 5% by mass or less, more preferably 2% by mass or less, and even more preferably 1% by mass or less.

[0102] When the coating agent of the present invention contains polymer compounds other than components (A) and (D), the content of the polymer compounds in the coating agent is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, from the viewpoint of film durability, while preferably 20% by mass or less, more preferably 10% by mass or less, and even more preferably 5% by mass or less, from the viewpoint of obtaining a film with excellent release properties.

[0103] The viscosity of the coating agent is not particularly limited, but from the viewpoint of handling, the viscosity at 25°C is preferably 0.5 mPa·s or more, more preferably 0.8 mPa·s or more, and even more preferably 1 mPa·s or more. Similarly, from the viewpoint of handling, it is preferably 30 Pa·s or less, more preferably 20 Pa·s or less, and even more preferably 10 Pa·s or less. Here, the viscosity was measured using a B-type viscometer with an appropriate rotor matched to the viscosity range of each sample, after stirring for 1 minute at 25°C and a rotation speed of 60 rpm.

[0104] The average particle size of the emulsion droplets in the coating agent, as measured by SEM observation, is preferably 10 nm or more, more preferably 50 nm or more, and even more preferably 100 nm or more, from the viewpoint of obtaining a film with excellent release properties. Similarly, it 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. It is preferably 10 nm to 2000 nm, more preferably 50 nm to 1000 nm, and even more preferably 100 nm to 500 nm.

[0105] 2. Method for manufacturing the coating agent The method for producing the coating agent of the present invention comprises a step of mixing the aforementioned components (A), (B), (C), etc. Here, an organic compound that is liquid at 25°C and 1 atm may be mixed with an aqueous dispersion of hydrophobic modified cellulose fibers, or the dispersion of the organic compound of hydrophobic modified cellulose fibers may be mixed with water. Effective organic compounds that are liquid at 25°C and 1 atm include alcohols such as ethanol and 2-propanol. By incorporating these, the wettability to the substrate can be improved. From the viewpoint of improving wettability, the content of the organic compound that is liquid at 25°C and 1 atm is preferably 5% by mass or more, and from the viewpoint of stability, it is preferably 90% by mass or less.

[0106] Alternatively, a method for producing the coating agent of the present invention includes a step of mixing component (A-1), component (A-2), component (B), and component (C). This method is more preferable because the steps of obtaining hydrophobic modified cellulose fibers and obtaining the coating agent can be achieved in a single step. There are no restrictions on the mixing order in this method. For example, component (A-1), component (A-2), and component (B) may be mixed first, followed by component (C), or component (A-1), component (A-2), and component (C) may be mixed first, followed by component (B). Preferably, the manufacturing method includes a step of mixing component (A-1) and component (A-2) in the presence of component (B) and component (C). Therefore, a preferred embodiment of the coating agent of the present invention contains component (A-1), component (A-2), component (B), and component (C). In this case, the content of component (A) is the total content of component (A-1) and component (A-2).

[0107] When incorporating component (D), component (D) may be mixed together with these raw materials, or component (D) may be added to a coating agent obtained using these raw materials.

[0108] By mixing the components, emulsification occurs, and a coating agent is obtained. 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, mascolloider, short-screw extruder, twin-screw extruder, ultrasonic stirrer, household juicer mixer, etc. The mixing process may be carried out by combining two or more operations.

[0109] The temperature and time for mixing each component 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.

[0110] The preferred range for the content of each component when mixed is the same as the preferred range for the content of each component in the coating agent of the present invention described above.

[0111] When using components (A-1) and (A-2) instead of component (A), it is preferable that the upper and lower limits of the preferred content of component (A) be set as the upper and lower limits of the total amount of both components. Here, the mixing ratio of component (A-1) and component (A-2) is such that, from the viewpoint of obtaining a film with excellent mold release properties relative to the anionic group of component (A-1), component (A-2) is preferably 0.1 equivalent or more, more preferably 0.3 equivalent or more, and even more preferably 0.5 equivalent or more, while from the viewpoint of the stability of the coating agent, it is preferably 3 equivalents or less, more preferably 2 equivalents or less, and even more preferably 1.5 equivalents or less.

[0112] Alternatively, the ratio of the total number of moles of [the number of amino groups of the amino-modified silicone] and [the number of cationic groups of the hydrocarbon compound having cationic groups] in component (A-2) to the number of moles of anionic groups in component (A-1) ([total number of moles of component (A-2)] / [number of moles of anionic groups in component (A-1)]) is preferably 0.1 or higher, more preferably 0.3 or higher, and even more preferably 0.5 or higher from the viewpoint of obtaining a film with excellent release properties, and preferably 3 or lower, more preferably 2.5 or lower, and even more preferably 2 or lower from the viewpoint of film formation properties. The number of moles of anionic groups in anionic-modified cellulose fibers can be obtained by multiplying the amount of anionic-modified cellulose fibers used (g) by the anionic group content (mmol / g), and the number of moles of amino groups in amino-modified silicone can be obtained by dividing the amount of amino-modified silicone used (g) by the amino equivalent (g / mol).

[0113] Furthermore, the mass ratio (A-2 / C) of component (A-2) to component (C) is preferably 0.0001 or higher, more preferably 0.001 or higher, even more preferably 0.004 or higher, even more preferably 0.01 or higher, and even more preferably 0.04 or higher, from the viewpoint of obtaining a film with excellent mold release properties, and preferably 20 or lower, more preferably 10 or lower, even more preferably 5 or lower, even more preferably 3 or lower, and even more preferably 2 or lower. From these viewpoints, it is preferably 0.0001 to 20 or lower, more preferably 0.001 to 10 or lower, even more preferably 0.004 to 5 or lower, even more preferably 0.01 to 3 or even more preferably 0.04 to 2 or lower.

[0114] 3. Method for producing a coating film obtained by drying the coating agent. The present invention provides a method for producing a coating film obtained by drying a coating agent, which includes a step of drying the coating agent of the present invention or a coating agent obtained by the method for producing the coating agent of the present invention.

[0115] Specifically, the coating agent is applied to a substrate, such as a hard surface made of paper, such as glass, resin, metal, ceramics, concrete, wood, stone, or fibers, skin, or hair. From the viewpoint of the film exhibiting its role as a release agent to the greatest extent possible, a hard surface is preferred as the substrate, and metal is more preferred. That is, metal is preferred as the target surface for the coating agent of the present invention. Examples of metals include iron, aluminum, copper, and alloys thereof (e.g., stainless steel, duralumin, brass). Methods of application include, but are not limited to, methods of application using an applicator, bar coater, spin coater, etc., hand application such as brush application or impregnation with cloth or paper, spraying such as air spray, airless spray, trigger spray, aerosol spray, etc., and dip coating.

[0116] The thickness of the coating film on the substrate is preferably 10 μm or more, more preferably 20 μm or more, and even more preferably 30 μm or more, from the viewpoint of film durability, and preferably 2000 μm or less, and more preferably 1500 μm or less, from the viewpoint of coatability.

[0117] Next, the coating film can be dried to obtain a coated film. The drying conditions can be under reduced pressure or atmospheric pressure, and the temperature range is preferably between 15°C and 75°C. The drying time is preferably between 10 minutes and 24 hours.

[0118] 4. Drying film of the coating agent

[0119] The thickness of the film of the present invention is not particularly limited. 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 2000 μm or less, more preferably 1200 μm or less, even more preferably 500 μm or less, and even more preferably 200 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 amount of coating and the ratio of the medium when using a spray or the like. The film thickness can be measured according to the method described in the examples below.

[0120] The amount of hydrophobic modified cellulose fibers in the film of the present invention is preferably 1% by mass or more, more preferably 10% by mass or more, from the viewpoint of film durability, and preferably 65% ​​by mass or less, more preferably 36% by mass or less, and even more preferably 16% by mass or less, from the viewpoint of obtaining a film with excellent release properties. The amount of hydrophobic modified cellulose fibers in the film can be determined by considering the amount of volatile components (e.g., water and some oils) in the coating agent. The preferred range of amounts of component (C) and component (D) in the film of the present invention corresponds to the preferred range of amounts of those components in the coating agent.

[0121] The film of the present invention may contain optional components that do not impair the effects of the present invention.

[0122] By applying the film of the present invention to a solid surface, the solid surface can be given release properties for resins and the like. That is, the coating film obtained by drying the coating agent of the present invention can be suitably used as a release agent film. The film of the present invention not only has excellent release properties but also excellent durability, allowing it to maintain its effects for a long period of time. Therefore, it can be used in various applications, such as molds and rubber molds for resin and rubber molding, and molded articles such as those produced by injection molding and sheet molding. Examples of resins that are effective as mold release agents include thermoplastic resins such as polyester, polylactic acid, polyolefin, polystyrene, nylon, polyoxymethylene, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyethersulfone, and elastomers, as well as thermosetting resins such as epoxy resins and silicone resins, and rubber. [Examples]

[0123] The present invention will be specifically described below with reference to examples. Note that the following examples are merely illustrative of the present invention and do not imply any limitation.

[0124] [Average fiber diameter, average fiber length, and average aspect ratio of anionically modified cellulose fibers and hydrophobically modified cellulose fibers] Water is added to the cellulose fibers to be measured to prepare a dispersion with a water content of 0.0001% by mass. This dispersion is dropped onto mica and dried to create an observation sample. An atomic force microscope (AFM) (Digital Instruments, Nanoscope II Tappingmode AFM; probe used: Nanosensors, Point Probe (NCH)) is used to measure the fiber height (difference in height between areas with and without fibers) of the cellulose fibers in the observation sample. At that time, more than 100 cellulose fibers are extracted from the microscope image in which the cellulose fibers can be confirmed, and the average fiber diameter is calculated from their fiber heights. The average fiber length is calculated from the distance in the direction of the fibers. The average aspect ratio is calculated from the average fiber length / average fiber diameter. The height analyzed in the AFM image can be considered as the fiber diameter.

[0125] [Average fiber diameter and average fiber length of the cellulose fibers used as raw material] A dispersion containing 0.01% by mass of deionized water is prepared by adding deionized water to the cellulose fibers to be measured. This dispersion is measured using a wet dispersion type image analysis particle size distribution analyzer (Jusco International, IF-3200) 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, sampling: 15%. More than 100 cellulose fibers are measured, and their average ISO fiber diameter is used as the average fiber diameter, and their average ISO fiber length is used as the average fiber length.

[0126] [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)]

[0127] [Aldehyde group content of oxidized cellulose fibers] The carboxyl group content of the oxidized cellulose fiber to be measured is determined by the method for measuring the anionic group content described above. Separately, 100 g of an aqueous dispersion of the oxidized cellulose fibers to be measured (solid 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 are added to a beaker and stirred at 25°C for 16 hours to oxidize the aldehyde groups remaining in the oxidized cellulose fibers. After the reaction is complete, the fibers are washed with deionized water to obtain cellulose fibers from which the aldehyde groups have been oxidized. The reaction solution is freeze-dried, and the carboxyl group content of the resulting dried product is measured using the method for measuring the anionic group content described above to calculate the "carboxyl group content of the oxidized cellulose fibers." Subsequently, the aldehyde group content of the oxidized cellulose fibers to be measured is calculated using Equation 1.

[0128] Aldehyde group content (mmol / g) = (Carboxyle group content of oxidized cellulose fiber) - (Carboxyle group content of oxidized cellulose fiber to be measured) ... Equation 1

[0129] [Solid content in the dispersion] Measurements are performed using a halogen 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.

[0130] [Confirmation of the crystal structure in hydrophobic modified cellulose fibers] The crystal structure of hydrophobic modified cellulose fibers is confirmed by measuring it using an X-ray diffractometer (MiniFlexII, Rigaku Corporation) under the following conditions. The measurement conditions are as follows: X-ray source: Cu / Kα-radiation, tube voltage: 30kV, tube current: 15mA, measurement range: diffraction angle 2θ = 5~45°, X-ray scan speed: 10° / min. The sample area for measurement is 320mm². 2 The material is prepared by compressing it into pellets with a thickness of 1 mm. Furthermore, the degree of crystallinity of the cellulose type I crystal structure is calculated from the obtained X-ray diffraction intensity based on the following formula A.

[0131] <Formula A> Cellulose type I crystallinity (%) = [(I22.6 -I 18.5 ) / I 22.6 ]×100 [In the formula, I 22.6 This is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6°) in X-ray diffraction, I 18.5 This shows the diffraction intensity of the amorphous region (diffraction angle 2θ = 18.5°).

[0132] On the other hand, if the degree of crystallinity obtained by formula A above is 35% or less, from the viewpoint of improving calculation accuracy, it is preferable to calculate it based on the following formula B, in accordance with the description on pages 199-200 of the "Manual for Experiments in Wood Science" (edited by the Japan Wood Research Society; published April 2000). Therefore, if the degree of crystallinity obtained by formula A above is 35% or less, the value calculated based on formula B below can be used as the degree of crystallinity.

[0133] <Formula B> Cellulose type I crystallinity (%) = [A c / ( A c +A a )] × 100 [In the ceremony, A c This 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 This shows the peak area of ​​the amorphous region (diffraction angle 2θ = 18.5°), and each peak area is obtained by fitting the obtained X-ray diffraction chart with a Gaussian function.

[0134] [Cellulose fiber (equivalent amount) in hydrophobic modified cellulose fibers] The cellulose fiber (equivalent amount) in hydrophobic modified cellulose fibers is measured by the following method. (1) When only one type of "modifying compound" is added The amount of cellulose fiber (converted amount) is calculated using the following formula C. <Formula C> Cellulose fiber content (converted amount) (g) = Mass of hydrophobic modified cellulose fiber (g) / [1 + Molecular weight of modifying compound (g / mol) × Amount of modifying group attached (mmol / g) × 0.001] (2) When there are two or more types of "modifying compounds" added The amount of cellulose fiber (converted amount) is calculated by considering the molar ratio of each compound (i.e., the molar ratio when the total molar amount of the added compounds is set to 1).

[0135] [Measurement of the viscosity of the coating agent] Using a Type B viscometer (Toki Sangyo TVB-10) with rotor No. 1, the viscosity was measured at 25°C, a rotation speed of 60 RPM, and after 1 minute.

[0136] [Observation of coating agent using Cryo-SEM] Observation of the coating agent using Cryo-SEM is performed using a Scios DualBeam field emission scanning electron microscope manufactured by FEI. Observation is performed while gradually sublimating the water from the frozen coating agent. Observation is performed at an acceleration voltage of 2kV and a magnification of 25,000x.

[0137] [Measuring the particle size of emulsified droplets using laser diffraction] The particle size of emulsion droplets is measured using the LA-960 laser diffraction method manufactured by Horiba, Ltd. Measurement conditions: Water is added to the measurement cell, and the volume particle size distribution and the median volume particle size (D) are measured at a concentration that allows the absorbance to fall within the appropriate range. 50 The following conditions are met: relative refractive index 1.20, temperature 25°C, circulation pump ON, circulation speed 5, and stirring speed 5.

[0138] [Preparation of anionically modified cellulose fibers] Preparation Example 1 Bleached coniferous kraft pulp (Hinton, manufactured by Westfrother) was used as the raw material for the natural cellulose fiber. A commercially available product (Free radical, manufactured by Aldrich, 98% by mass) was used as the TEMPO. Commercially available products were used for sodium hypochlorite, sodium bromide, and sodium hydroxide.

[0139] First, 10 g of bleached kraft pulp fiber and 990 g of deionized water were weighed into a 2 L PP beaker equipped with a mechanical stirrer and stirring blades. After stirring at 25°C and 100 rpm for 30 minutes, 0.13 g of TEMPO, 1.3 g of sodium bromide, and 35.5 g of 10.5% by mass sodium hypochlorite aqueous solution were added to 10 g of pulp fiber in that order. Using an automatic titrator (Toa DKK Co., Ltd., AUT-701), pH stat titration was performed, and 0.5 M sodium hydroxide aqueous solution was added dropwise to maintain the pH at 10.5. The reaction was carried out at 25°C for 120 minutes at a stirring speed of 100 rpm, after which the addition of sodium hydroxide aqueous solution was stopped, and a suspension of anionically modified cellulose fiber was obtained.

[0140] The suspension of the obtained anionically modified cellulose fibers was adjusted to pH=2 by adding 0.01 M hydrochloric acid. The filtrate was then thoroughly washed with deionized water until its conductivity, measured using a compact electrical conductivity meter (Horiba, Ltd., LAQUAtwin EC-33B), was 200 μs / cm or less. The fibers were then dehydrated to obtain anionically modified cellulose fibers. The carboxyl group content of these anionically modified cellulose fibers was 1.50 mmol / g, and the aldehyde group content was 0.23 mmol / g.

[0141] Preparation Example 2 (Production of finely textured anion-modified cellulose fibers) In Preparation Example 1, 100 g of a suspension (solid content 2.0% by mass) was prepared by adding deionized water to the anionically modified cellulose fibers finally obtained. A 0.5 M sodium hydroxide aqueous solution was added to adjust the pH to 8, and then deionized water was added to bring the total volume to 200 g. This suspension was subjected to three micronization treatments at 150 MPa using a high-pressure homogenizer (Yoshida Machinery Co., Ltd., NanoVeta L-ES) to obtain a dispersion of micronized anionically modified cellulose fibers (solid content 1.0% by mass). The counterions of the carboxyl groups in these micronized anionically modified cellulose fibers were sodium ions. These micronized anionically modified cellulose fibers are abbreviated as "TCNF (Na type)".

[0142] Preparation Example 3 (Production of finely textured anionic modified cellulose fibers with reduced aldehyde groups) 182 g of the finely pulverized anionic modified cellulose fiber dispersion (solid content 1.0% by mass) obtained in Preparation Example 2 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 to carry out protonation. After the reaction was complete, the mixture was filtered, and the resulting cake was washed six times with deionized water to remove the salt and hydrochloric acid, obtaining a finely pulverized anionic modified cellulose fiber dispersion (solid content 0.9% by mass) in which the aldehyde groups had been reduced. The carboxyl group content of the obtained cellulose fibers was 1.50 mmol / g, and the aldehyde group content was 0.02 mmol / g. The carboxyl groups in these finely pulverized anionic modified cellulose fibers are in the free acid form (COOH), and are abbreviated as "TCNF (H type)". The crystallinity of these finely textured anion-modified cellulose fibers was 30%, the average fiber diameter was 3.3 nm, and the average fiber length was 600 nm.

[0143] [Preparation of hydrophobic modified cellulose fibers and coating agents] Example 1 In a beaker, 83.3 g of the finely milled anionically modified cellulose fiber dispersion obtained in Preparation Example 3 (solid content 0.9% by mass), 7.5 g of silicone oil, and 2.4 g of amino-modified silicone (corresponding to 1.25 equivalents relative to the carboxyl groups of the anionically modified cellulose fibers) were mixed, and deionized water was added to make a total of 100 g. After stirring this solution with a mechanical stirrer for 5 minutes, it was subjected to 10 passes at 150 MPa using a high-pressure homogenizer (Yoshida Machinery Co., Ltd., NanoVeta L-ES) to obtain an emulsion composition containing hydrophobic modified cellulose fibers in which amino-modified silicone was linked to anionically modified cellulose fibers. This emulsion composition was used as the coating agent in Example 1. The obtained composition was a cloudy liquid, and observation with an optical microscope and cryo-SEM revealed that oil droplets were dispersed in the water, so it was determined to be in an emulsified state.

[0144] Example 2 100 g of the emulsified composition obtained in Example 1 was weighed into a beaker, 0.25 g of polyether-modified silicone was added thereto, and the mixture was stirred at 25°C for 30 minutes to obtain a coating agent.

[0145] Examples 3-12 Each compound was mixed to obtain the emulsified composition in the same manner as in Example 1, and then polyether-modified silicone was mixed in the same manner as in Example 2 to obtain the coating agent in the amount shown in Tables 1 and 2.

[0146] Comparative Example 4 Each compound was mixed according to the proportions shown in Table 2, and then diluted with acetone to obtain a coating agent that does not contain hydrophobic modified cellulose fibers.

[0147] Details of the representative components used in the examples are summarized below. [Modification compound] Amino-modified silicone 1: DOWSIL manufactured by Dow Toray Corporation TM SS-3551, kinematic viscosity: 1,000, amino equivalent: 1,700 Oleylamine: Manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., Amino equivalent: 267.5, Total number of carbon atoms: 18 [Component (C)] Silicone oil 1: Shin-Etsu Chemical Co., Ltd. "KF-96-100cs", SP value: 7.3 Silicone oil 2: Shin-Etsu Chemical Co., Ltd. "KF-96-10cs", SP value: 7.3 Silicone oil 3: Shin-Etsu Chemical Co., Ltd. "KF-96-3000cs", SP value: 7.3 Silicone oil 4: Shin-Etsu Chemical Co., Ltd. "KF-96-10,000 cs", ​​SP value: 7.3 [Component (D)] Polyether-modified silicone 1: Shin-Etsu Chemical Co., Ltd. "KF-642", HLB: 14

[0148] [Preparation of a dried film] The coating agent prepared in Example 1 was uniformly applied at a rate of 3g to a stainless steel deep tray (manufactured by Sanbo Co., Ltd., external dimensions: 135 x 106 x H59 mm, volume 650 mL) using an air sprayer (Anest Iwata, WIDER1-10E1G, nozzle diameter Φ1.0 mm), and dried for 1 hour at 1 atmosphere, 25°C, and approximately 40% RH humidity to form a film. The thickness of the film in Example 1 was measured to be 7 μm using the measurement method described below. The coating agents prepared in Examples 2-12 and Comparative Example 4 were applied in amounts adjusted to achieve the same film thickness as in Example 1, and a film was created on the inner surface of a deep stainless steel tub.

[0149] Comparative Examples 1-3 Comparative Example 1 used a stainless steel deep-type tray itself. Comparative Example 2 involved applying 3g of a commercially available silicone-based mold release agent (Shin-Etsu Chemical Co., Ltd., KM-9782, 10% effective content) to a deep stainless steel tray in the same manner as in the example, and then drying it to produce a film. Comparative Example 3 involved applying 3g of a commercially available fluorine-based release agent (Neos Co., Ltd., FreeRelease 20A, 10% effective content) to a deep stainless steel tray in the same manner as in the example, and then drying it to create a film.

[0150] [Measurement of film thickness] The thickness of the film after drying was measured using a laser microscope (Keyence Corporation, VK-9710) as follows: Measurements were taken under fixed conditions. The measurement conditions were: 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 to expose the glass substrate, and the sample was measured. The height of the glass substrate and the height of the portion with the film were measured using built-in image processing software, and the film thickness was determined by taking the difference between these two values.

[0151] [Resin release properties evaluation 1] Amorphous polyester resin (Toyobo Co., Ltd., Byron 600™) in a stainless steel container was softened on a hot plate heated to 300°C. 500g of this resin was poured into stainless steel deep trays treated with the coating agents of Examples 1-12 and Comparative Examples 2-4, or into an untreated stainless steel deep tray (Comparative Example 1). After cooling and curing at room temperature for 12 hours, the release properties of the resin were evaluated according to the following criteria. A higher number indicates better release properties of the resin. In Example 2 and Comparative Example 3, the resin was repeatedly filled multiple times, and the release properties were evaluated. However, no additional coating agent was applied.

[0152] 5: The resin fell out just by flipping the bat over. 4: The resin fell off with a light impact, such as flipping the bat over and hitting it against the ground. 3. I turned the bat upside down and hit the bottom of the bat once with a hammer, causing the resin to fall out. 2. Turn the bat upside down and hit the bottom of the bat 2 to 5 times with a hammer, causing the resin to fall off. 1: Even after hitting it 5 times, some resin remained on the bat. The results are shown in Tables 1 and 2.

[0153] [Table 1]

[0154] [Table 2]

[0155] From Tables 1 and 2, the following was found: From Example 2 and Comparative Examples 1-3, an untreated stainless steel tray or a commercially available silicone-based It was found that the coating agent of the present invention exhibits higher release properties and superior durability when used repeatedly compared to fluorine-based release agents. Examples 1-3 showed that when an appropriate amount of polyether-modified silicone component D is included, the mold release properties are excellent. This is thought to be because the wettability of the coating agent on the stainless steel tray is improved, allowing for the formation of a uniform film. Examples 2, 4, and 5 showed that a greater number of modifying groups on the anionically modified cellulose resulted in superior mold release properties. This is thought to be because the amount of surface exposure of anionic groups that can interact with the resin is reduced. From Example 12, it was found that while alkylamines also exhibit the effect as a modifying species, amino-modified silicones are even more effective. Examples 2, 6-8 showed that while component (C) is effective with a wide range of oils, it is more effective with relatively low-viscosity oils. Examples 2, 9-11 showed that a higher proportion of component (C) in the dried film resulted in a greater effect. On the other hand, Comparative Example 4 showed that the effect was not achieved without hydrophobic modified cellulose fibers. This is thought to be because component (C) could not remain on the surface of the stainless steel tray.

[0156] [Resin mold release properties evaluation 2] The coating agent prepared in Example 2 was used to create a dried film on a glass substrate, and its release properties were evaluated. Specifically, the coating agent prepared in Example 2 was applied to a glass substrate (MATSUNAMI Micro Slide Glass S2112) (surface area 15.6 cm²). 2 0.3 mL was applied to the glass and spread over the entire surface. Then, the film was dried for 3 hours at 1 atmosphere, 25°C, and approximately 40% RH. The thickness of the film was measured using the above measurement method and was found to be 20 μm.

[0157] The release properties of various resins shown in Table 3 were evaluated using the coating agent from Example 2 applied to a glass substrate. Specifically, 10g of each resin was placed in an aluminum cup (8cm in diameter), heated on a hot plate to melt or soften it, and then 0.5g was placed on the glass substrate on which the film had been prepared. The resin was then cooled and solidified at room temperature, and the release properties of the resin were evaluated according to the following criteria.

[0158] 5: It will fall off just by tilting the glass substrate. 4: Can be peeled off with light finger pressure. 3: It can be removed using a tool (using a stainless steel spatula). 2: Some residue remains even after using tools (using a stainless steel spatula). 1: Not removable. The results are shown in Table 3.

[0159] [Table 3]

[0160] Table 3 shows that, regardless of which resin was used in the experiment, the resin would fall off simply by tilting the glass substrate. From the above, it was found that the coating agent of the present invention, when applied to a target substrate and forming a film, exhibits release properties for a wide range of resins, including general-purpose thermoplastics, engineering plastics, and elastomers. In particular, it is considered useful for nylon and elastomers, as they adhere strongly and are difficult to release when untreated.

[0161] [Resin release properties evaluation 3] On a 200 x 130 x t3 mm glass substrate, the coating agent from Example 2 was applied using the same method as the substrate used in Resin Release Properties Evaluation 2, so that the film thickness after drying was 20 μm. Two of these substrates were fixed together with clips using a Φ3 mm silicone rubber spacer to create a casting mold. Epoxy resin (Mitsubishi Chemical Corporation, jER828) was then poured in and cured in a hot air circulating open PH200 (ESPEC Corporation) at 80°C for 1 hour and then at 150°C for 1 hour. The same procedure was performed on an untreated glass substrate, and the release properties of the cured resin were evaluated.

[0162] As a result, the resin could not be removed from the untreated glass substrate at all, even with tools, whereas the resin on the glass substrate coated with the coating agent of Example 2 could be easily removed by inserting a spatula. From this, it was found that the coating agent of the present invention also exhibits excellent mold release properties after curing of thermosetting resins.

[0163] [Resin release properties evaluation 4] The coating agent prepared in Example 2 was applied to a mold using an air spray, dried, and its release properties were evaluated using an injection molding machine. Specifically, the coating agent produced in Example 2 was applied to the entire mold (dumbbell: JIS K7139 Type A1, prismatic test piece: 63mm x 13mm x 6.4mm, flat test piece: 70mm x 40mm x 2mm) and sprue of an injection molding machine (Japan Steel Works J110AD-180H) using an air spray (Anest Iwata WIDER110E1G, Φ1.0, spray pressure 0.2MPa), and dried at room temperature for 1 minute. Then, styrene elastomer AR-SC-45 (Aron Kasei Co., Ltd.) was injection molded under the conditions of resin temperature 190℃, mold temperature 30℃, and cooling time 5 seconds. As a result, in molds without the coating agent, the molded body became stuck in the mold and was difficult to remove, and resin clogged the sprue, making removal difficult without tools. On the other hand, when the coating agent of Example 2 was applied, the mold could be easily removed without resin clogging the mold, and the resin could be easily extracted from the sprue, demonstrating excellent release properties. Furthermore, it was found that the excellent release properties were maintained even after 10 consecutive injection moldings without recoating. [Industrial applicability]

[0164] The coating agent of the present invention can be applied to a target surface by a simple method such as spraying, and possesses durability that allows it to repeatedly exhibit release properties. Therefore, it is considered to be extremely useful in fields such as resin and resin compound manufacturing equipment, injection molding and sheet molding, rubber molding, and the production of release paper and release films by applying the coating agent of the present invention to paper or sheets.

Claims

1. A coating agent containing the following components (A) to (C). (A) Hydrophobic modified cellulose fibers to which one or more modifying groups selected from the group consisting of anionic groups and hydroxyl groups are attached. (B) Water (C) Organic compounds that are liquid at 25°C and 1 atm

2. The coating agent according to claim 1, wherein component (A) is a hydrophobic modified cellulose fiber obtained by bonding a polymer compound to a cellulose fiber, and / or a hydrophobic modified cellulose fiber obtained by bonding a hydrocarbon compound having a cationic group to the anionic group of an anionic modified cellulose fiber.

3. The coating agent according to claim 1 or 2, further comprising component (D) a polyether-modified silicone compound.

4. A coating agent according to any one of claims 1 to 3, which is an emulsified composition.

5. A coating agent according to any one of claims 1 to 4, wherein the target surface is a hard surface.

6. A coating agent according to any one of claims 1 to 5, for use as a mold release agent.

7. A coating film obtained by drying the coating agent according to any one of claims 1 to 6.

8. The coating film according to claim 7, which is a release agent film.

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