JP2022103135A - Coating agent - Google Patents

Abstract

To provide a coating agent that can form a coat excelling in releasability and its durability.SOLUTION: A coating agent contains the following components (A)-(C). Component (A): a hydrophobically modified cellulose fiber including at least one selected from the group consisting of an anionic group and a hydroxy group with a modifying group bound thereto. Component (B): water. Component (C): an organic compound that is liquid at 25°C and at 1 atmospheric pressure.SELECTED DRAWING: None

Description

The present invention relates to a coating agent.

Conventionally, in the fields of manufacturing and molding of resins, rubbers, ceramics, cements, etc., the problem of reduced productivity due to the adhesion of these substances to manufacturing equipment and molding equipment has been a problem, and silicone oils, mineral oils, paraffin waxes, and fatty acid derivatives have become issues. , Glycols, talc, mica and the like were used as mold release agents. For example, Patent Document 1 discloses that a compound having a perfluoroalkyl group is used as a mold release agent.

Japanese Unexamined Patent Publication No. 2012-207169

However, it cannot be said that the conventional mold release agent has sufficient releasability, and further improvement is required.

Therefore, an object of the present invention is to provide a coating agent capable of forming a film having excellent releasability and durability thereof.

The present invention relates to the following [1] to [5].
[1] A coating agent containing the following components (A) to (C).
(A) Hydrophobic modified cellulose fiber in which a modifying group is bonded to one or more selected from the group consisting of an anionic group and a hydroxy group (B) Water (C) Organic compound liquid at 25 ° C. and 1 atm [2] The coating agent according to the above [1], further containing the component (D) a polyether-modified silicone compound.
[3] The coating agent according to the above [1] or [2], which is for a mold release agent.
[4] A coating film obtained by drying the coating agent according to any one of the above [1] to [3].
[5] The coating film according to the above [4], which is a film for a mold release agent.

By using the coating agent provided by the present invention, a film having excellent releasability and durability thereof can be formed.

As a result of diligent studies by the present inventors to solve the above-mentioned problems, it contains a hydrophobically modified cellulose fiber in which a modifying group having a specific structure is bonded to the cellulose fiber, and an organic compound which is liquid at 25 ° C. and 1 atm. When a resin or the like is applied to a film obtained by applying the composition to be formed on a substrate and drying it, it has been found that the obtained film is surprisingly excellent in releasability of the resin or the like. The present invention has been completed.

1. 1. Coating agent The coating agent of the present invention contains the following components (A) to (C).
<Ingredient (A)>
The component (A) is a hydrophobically modified cellulose fiber in which a modifying group is bonded to one or more selected from the group consisting of an anionic group and a hydroxy group, and is selected from the group consisting of the following (a) and (b). One or more hydrophobically modified cellulose fibers are preferred.
(a) Hydrophobic modified cellulose fiber formed by binding a polymer compound to cellulose fiber
(b) Hydrocarbon-modified cellulose fiber in which a hydrocarbon compound having a cationic group is ionically bonded to the anionic group of the anionic-modified cellulose fiber.

The hydrophobically modified cellulose fiber in the present specification is one in which a polymer compound is bonded to the cellulose fiber, or one in which a hydrocarbon-based compound is bonded to the cellulose fiber, and preferably, the anionic group of the anion-modified cellulose fiber is used. A polymer compound and / or a hydrocarbon-based compound having a cationic group is bonded via an ionic bond. Here, the hydrocarbon compound preferably has a total carbon number of 16 or more and 40 or less.

[Cellulose type I crystal structure and crystallinity]
The hydrophobically modified cellulose fiber preferably has a cellulose type I crystal structure due to the fact that natural cellulose is used as a raw material thereof. The crystallinity of the hydrophobically modified cellulose fiber is preferably 10% or more, more preferably 15% or more, still more preferably 20% or more, from the viewpoint of developing strength at the time of film formation. Further, from the viewpoint of raw material availability, it is preferably 90% or less, more preferably 85% or less, still more preferably 80% or less, still more preferably 75% or less. Cellulose type I crystallinity is measured by the method described in Examples below.

[Average fiber diameter of hydrophobic modified cellulose fiber]
The average fiber diameter of the hydrophobically modified cellulose fiber is preferably 0.1 nm or more, more preferably 1.0 nm or more, still more preferably 2.0 nm or more from the viewpoint of handleability, and from the viewpoint of strength at the time of film formation. Therefore, it is preferably 200 nm or less, more preferably 100 nm or less, and further preferably 50 nm or less. The average fiber diameter of the hydrophobically modified cellulose fiber is measured by the method described in Examples described later.

[Modifying group]
One preferred embodiment of the hydrophobically modified cellulose fiber of the component (a), preferably the hydrophobically modified cellulose fiber in which a polymer compound is bonded to the anion-modified cellulose fiber, has a structure represented by the following general formula (T-Ce). Have. The component (a) may be a hydrophobically modified cellulose fiber in which a modifying group is bonded to a hydroxy group of a cellulose fiber having no anionic group.

(In the formula, X is -CH ₂ OH, -CH ₂ O-R ¹ , -C (= O) OH, -C (= O) O-R ¹ , -C (= O) -O ^- H ₃ N One or more groups selected from the group consisting of ⁺ -R ¹ and -C (= O) -NH-R ¹ , where R ¹ is a modifying group and R is an independent hydrogen atom or modifying group, respectively. Yes, 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.)

The modifying group in the hydrophobically modified cellulose fiber formed by binding the polymer compound to the cellulose fiber is a group derived from the polymer compound, and the structure of the modifying group (that is, ^R1 and R in the above formula (T-Ce)) is It depends on the structure of the polymer compound used. The mode of binding of the modifying group to the cellulose fiber is preferably a covalent bond or an ionic bond. An ionic bond is preferable from the viewpoint of ease of production, and a covalent bond is preferable from the viewpoint of the stability of the formed membrane. Compounds for introducing a modifying group, such as polymer compounds and hydrocarbon compounds (preferably hydrocarbon compounds having a cationic group), may be referred to herein as "modifying compounds". ..

Examples of the bonding site of the modifying group in the cellulose fiber include a hydroxy group, an aldehyde group, and a functional group introduced by chemically modifying the cellulose fiber. The functional group introduced by the chemical modification is an anionic group, and the cellulose fiber in this case becomes an anionic modified cellulose fiber. The preferred anionic group in the anion-modified cellulose fiber is a carboxy group. As the anion-modified cellulose fiber, a carboxy group-containing cellulose fiber is more preferable from the viewpoint of easy preparation and mild reaction conditions.

When the bonding portion is a hydroxy group of an anion-modified cellulose fiber, the bonding mode is a covalent bond, and examples thereof include an ether bond, an ester bond, and a carbonate bond.

When the bonding site is an anionic group of an anionic modified cellulose fiber, the bonding mode is an ionic bond or a covalent bond. When the bond mode is an ionic bond, the modifying compound having a cationic group is bonded via an electrostatic interaction, and when the bond mode is a covalent bond, an ester bond, an amide bond, etc. are formed. It refers to a state of being bonded via an ester bond, an amide bond, a carbonate bond, a urethane bond, or the like with respect to the carboxy group of a carboxy group-containing cellulose fiber.

For example, the modifying compound is amino-modified silicone (referred to as " _H2N- [alkyl silicone skeleton]"), and the cellulose fiber is a carboxy group-containing cellulose fiber ("[cellulose skeleton] -C ^* (= O)-". In the case of "OH"), if the bonding mode is an ionic bond, the hydrophobically modified cellulose fiber is "[cellulose skeleton] -C ^* (= O) -O ^- H ₃ N ⁺ -[alkyl silicone skeleton]. , And the modifying group is "-[alkyl silicone skeleton]". On the other hand, if the bonding mode is an amide bond, the hydrophobically modified cellulose fiber has a structure like "[cellulose skeleton] -C ^* (= O) -NH- [alkyl silicone skeleton]", and the modifying group is "-[alkyl]. Silicone skeleton] ”. Thus, the structure of the modifying group depends on the structure of the modifying compound used. In addition, "C ^* " means a carbon atom at the 6-position of a cellulose constituent unit.

Further, a modifying group of the hydrophobically modified cellulose fiber formed by bonding a hydrocarbon compound having a cationic group to the anionic group of the hydrophobically modified cellulose fiber of the component (b), that is, the anionic modified cellulose fiber via an ionic bond. Is derived from a hydrocarbon compound having a cationic group. In this case, the bonding mode of the modifying group to the anionic group of the anion-modified cellulose fiber is an ionic bond, and the hydrophobically modified cellulose fiber of the component (b) has a cationic group possessed by the modifying group on the anionic group on the surface of the cellulose fiber. Is adsorbed through electrostatic interaction.
In the present specification, a group derived from a polymer compound and a group derived from a hydrocarbon compound (preferably a hydrocarbon compound having a cationic group) are collectively referred to as a "modifying group".

The binding amount (mmol / g) and introduction rate (mol%) of the modifying group in the hydrophobically modified cellulose fiber are the amount and ratio of the modifying group introduced into the hydrophobically modified cellulose fiber. Specifically, it is measured by the method described in Examples described later. The binding amount and introduction rate of the modifying group can be adjusted by the addition amount, type, reaction temperature, reaction time, solvent and the like of the modifying compound.

The amount of the modifying group bonded to the hydrophobically modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.2 mmol / g or more, still more preferably 0.5 mmol / g, from the viewpoint of obtaining a film having excellent releasability. That is all. Further, from the viewpoint of reactivity, it is preferably 3 mmol / g or less, more preferably 2.5 mmol / g or less, and further preferably 2 mmol / g or less.

The introduction rate of the modifying group in the hydrophobically modified cellulose fiber is preferably 10 mol% or more, more preferably 20 mol% or more, still more preferably 40 mol% or more, still more preferably, from the viewpoint of obtaining a film having excellent releasability. Is 50 mol% or more, and from the viewpoint of reactivity, it is preferably 99 mol% or less, more preferably 97 mol% or less, still more preferably 95 mol% or less, still more preferably 90 mol% or less.

[Manufacturing method of hydrophobically modified cellulose fiber]
The hydrophobically modified cellulose fiber of the component (A) is, for example, (1) a step of introducing an anionic group into the raw material cellulose fiber to obtain an anion-modified cellulose fiber, and (2) a polymer compound in the anion-modified cellulose fiber. And / or a method comprising a step of binding a hydrocarbon-based compound having a cationic group to obtain a hydrophobically modified cellulosic fiber.

As one aspect of the step (2),
Ingredient (A-1) Anion-modified cellulose fiber,
Component (A-2) One or more compounds selected from the group consisting of amino-modified silicone and hydrocarbon compounds having a cationic group Component (B) Water, and Component (C) Liquid organic at 25 ° C. and 1 atm. Examples include the step of mixing the compounds. Such an embodiment is the same as the step in the method for producing a coating agent of the present invention described later, that is, the step of mixing the component (A-1), the component (A-2), the component (B) and the component (C). .. According to this aspect, since the hydrophobically modified cellulose fiber and the coating agent of the present invention can be produced in the same process, it can be said to be a more preferable production method.

(1) Step of Obtaining Anion-Modified Cellulose Fiber In the anion-modified cellulose fiber used in the present invention, at least one or more anionic groups are introduced by subjecting the raw material cellulose fiber to an oxidation treatment or an anionic group addition treatment. It can be obtained by anion modification.

The cellulose fiber to be anion-modified, that is, the hydrophobic-modified cellulose fiber or the cellulose fiber as a raw material of the anion-modified cellulose fiber is preferably a natural cellulose fiber from an environmental point of view, for example, coniferous pulp, broad-leaved pulp and the like. Wood pulp; cotton pulp such as cotton linter and cotton lint; non-wood pulp such as straw pulp and bagus pulp; bacterial cellulose and the like, and one of these may be used alone or in combination of two or more. can.

The average fiber diameter of the raw material cellulose fiber is not particularly limited, but is preferably 1 μm or more, and preferably 300 μm or less, from the viewpoint of handleability and cost.

The average fiber length of the raw material cellulose fiber is not particularly limited, but 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 the average fiber length of the raw material cellulose fiber can be measured according to the method described in Examples described later. From the viewpoint of dispersibility, it is preferable to use cellulose fibers having an average fiber length of 1 μm or more and 1,000 μm or less obtained by shortening the raw material cellulose fibers by alkaline hydrolysis treatment or acid hydrolysis treatment. ..

Examples of the anionic group to be introduced include a carboxy group, a sulfonic acid group or a phosphoric acid group.

(i) When introducing a carboxy group as an anionic group into a cellulose fiber As a method of introducing a carboxy group into a cellulose fiber, for example, a method of oxidizing a hydroxy group of cellulose to convert it into a carboxy group, or a method of introducing a hydroxy group of cellulose into a hydroxy group of cellulose. Examples thereof include a method of reacting at least one selected from the group consisting of a compound having a carboxy group, an acid anhydride of the compound having a carboxy group and a derivative thereof.

The method for oxidizing the hydroxy group of the cellulose is not particularly limited, and for example, sodium hypochlorite or the like using 2,2,6,6-tetramethyl-1-piperidin-N-oxyl (TEMPO) as a catalyst is used. A method of reacting an oxidizing agent and a bromide such as sodium bromide to perform an oxidation treatment can be applied. More specifically, a known method, for example, the method described in JP-A-2011-140632 can be referred to.

By performing the oxidation treatment of the cellulose fiber using TEMPO as a catalyst, the hydroxymethyl group (-CH ₂ OH) at the C6 position of the cellulose constituent unit is selectively converted into a carboxy group. In particular, this method is advantageous in that the selectivity of the hydroxy group at the C6 position to be oxidized on the surface of the raw material cellulose fiber is excellent, and the reaction conditions are mild. Therefore, a preferred embodiment of the anion-modified cellulose fiber in the present invention is a cellulose fiber in which the C6 position of the cellulose constituent unit is a carboxy group. In the present specification, such cellulose fibers may be referred to as "oxidized cellulose fibers". Oxidized cellulose fibers are preferable because they are easier to prepare than other anion-modified cellulose fibers. Therefore, one of the preferred embodiments of the hydrophobically modified cellulose fiber in the present invention is the hydrophobically modified cellulose fiber obtained by binding amino-modified silicone to the carboxy group-containing cellulose fiber.

By further subjecting the oxidized cellulose fiber to an additional oxidation treatment or a reduction treatment, an oxidized cellulose fiber from which the remaining aldehyde group has been removed can be prepared.

(ii) When introducing a sulfonic acid group or a phosphate group as an anionic group into a cellulose fiber As a method of introducing a sulfonic acid group as an anionic group into a cellulose fiber, a method of adding sulfuric acid to the cellulose fiber and heating the cellulose fiber, etc. Can be mentioned.
As a method for introducing a phosphoric acid group as an anionic group into a cellulose fiber, a method of mixing a powder or an aqueous solution of a phosphoric acid or a phosphoric acid derivative with a dry or wet cellulose fiber, or a method of mixing phosphorus in a dispersion liquid of the cellulose fiber. Examples thereof include a method of adding an aqueous solution of an acid or a phosphoric acid derivative. When these methods are adopted, generally, after mixing or adding a powder or an aqueous solution of phosphoric acid or a phosphoric acid derivative, dehydration treatment, heat treatment and the like are performed.

(iii) Anion-modified cellulose fiber (component (A-1))
Examples of the anionic group contained in the anion-modified cellulose fiber thus obtained include a carboxy group, a sulfonic acid group and a phosphoric acid group. The anionic group is preferably a carboxy group from the viewpoint of the efficiency of introducing the modifying group into the cellulose fiber. Examples of the ion (counter ion) paired with the anionic group in the anion-modified cellulose fiber include metal ions such as sodium ion, potassium ion, calcium ion and aluminum ion generated in the presence of alkali during production, and these metals. Examples thereof include protons generated by substituting an ion with an acid.

The anionic group content in the anion-modified cellulose fiber is preferably 0.1 mmol / g or more, more preferably 0.4 mmol / g or more, still more preferably 0.6 mmol / g, from the viewpoint of introducing a modifying group. The above is more preferably 0.8 mmol / g or more. Further, from the viewpoint of improving handleability, it is preferably 3 mmol / g or less, more preferably 2 mmol / g or less, and further preferably 1.8 mmol / g or less. The "anionic group content" means the total amount of anionic groups in the cellulose constituting the cellulose fiber, and is specifically measured by the method described in Examples described later.

The average fiber diameter of the anion-modified cellulose fiber is preferably 0.1 nm or more, more preferably 1.0 nm or more, still more preferably 2.0 nm or more from the viewpoint of handleability, and from the viewpoint of strength at the time of film formation. Therefore, it is preferably 200 nm or less, more preferably 100 nm or less, and further preferably 50 nm or less. The average fiber diameter of the anion-modified cellulose fiber is measured by the method described in Examples described later.

(2) Step for Obtaining Hydrophobic Modified Cellulose Fiber The hydrophobic modified cellulose fiber of the component (A) is one selected from the group consisting of a polymer compound and a hydrocarbon-based compound having a cationic group in the above-mentioned anion-modified cellulose fiber. It can be produced by binding the above compounds. As such a production method, a known method, for example, the method described in JP-A-2015-143336 can be used.

(i) Polymer compound The polymer compound used as the modifying compound in the present invention can be prepared by using a commercially available product or by a known method. Only one kind of polymer compound may be used, or two or more kinds may be used.

The polymer compound used as the modifying compound in the present invention is preferably a polymer compound having a repeating structure linked by a structure having an oxygen atom, and more preferably a polyoxyalkylene structure, a polysiloxane structure or the like. It is a polymer compound having a repeating structure linked by oxygen atoms, and more preferably a silicone-based compound. Examples of the silicone-based compound include amino-modified silicone, epoxy-modified silicone, carboxy-modified silicone, carbinol-modified silicone, and hydrogen-modified silicone, and the position of the reactive group may be the side chain or the terminal of the silicone compound. Among these, amino-modified silicone is preferable from the viewpoint of ease of modification.

(ii) Amino-modified silicone Amino-modified silicone is a silicone-based compound having an amino group. As the amino-modified silicone, those having a kinematic viscosity at 25 ° C. of 10 mm ² / s or more and 20,000 mm ² / s or less are preferable. Further, amino-modified silicone having an amino equivalent of 400 g / mol or more and 16,000 g / mol or less is preferable.

The kinematic viscosity at 25 ° C. can be determined with an Ostwald type viscometer, and is more preferably 20 mm ² / s or more, further preferably 50 mm ² / s or more, and handleability from the viewpoint of obtaining a film having excellent mold releasability. From the viewpoint of the above, it is more preferably 10,000 mm ² / s or less, and further preferably 5,000 mm ² / s or less.

Further, 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, and binding to the anion-modified cellulose fiber from the viewpoint of obtaining a film having excellent releasability. From the viewpoint of ease of formation, it is preferably 16,000 g / mol or less, more preferably 14,000 g / mol or less, and further preferably 12,000 g / mol or less. The amino equivalent is the molecular weight per nitrogen atom, and is determined by amino equivalent (g / mol) = weight average molecular weight / number of nitrogen atoms per molecule. Here, the weight average molecular weight is a value obtained by gel permeation chromatography using polystyrene as a standard substance, and the number of nitrogen atoms can be obtained by an elemental analysis method.

Specific examples of the amino-modified silicone include a compound represented by the general formula (a1).

[In the formula, R ^1a represents a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, an alkoxy group having 1 to 3 carbon atoms or a hydrogen atom, and is preferable from the viewpoint of obtaining a film having excellent releasability. It is a methyl group or a hydroxy group. R ^2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group or a hydrogen atom, and is preferably a methyl group or a hydroxy group from the same viewpoint. B represents a side chain having at least one amino group, and R ^3a represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. x and y indicate the average degree of polymerization, respectively, and are selected so that the kinematic viscosity and amino equivalent of the compound at 25 ° C. are within the above ranges. R ^1a , R ^2a , and R ^3a may be the same or different from each other, and a plurality of R ^2a may be the same or different from each other. ]

In the compound of the general formula (a1), x is preferably a number of 10 or more and 10,000 or less, more preferably a number of 20 or more and 5,000 or less, and further preferably 30 or more, from the viewpoint of obtaining a film having excellent releasability. The number is 3,000 or less. y is preferably a number of 1 or more and 1,000 or less, more preferably a number of 1 or more and 500 or less, and further preferably a number of 1 or more and 200 or less. The weight average molecular weight of the compound of the general formula (a1) is preferably 2,000 or more and 1,000,000 or less, more preferably 5,000 or more and 100,000 or less, and further preferably 8,000 or more and 50,000 or less. be.

In the general formula (a1), examples of the side chain B having an amino group include the following.
-C ₃ H ₆ -NH ₂
-C ₃ H ₆ -NH-C ₂ H ₄ -NH ₂
-C ₃ H ₆ -NH- [C ₂ H ₄ -NH] _e -C ₂ H ₄ -NH ₂
-C ₃ H ₆ -NH (CH ₃ )
-C ₃ H ₆ -NH-C ₂ H ₄ -NH (CH ₃ )
-C ₃ H ₆ -NH- [C ₂ H ₄ -NH] _f -C ₂ H ₄ -NH (CH ₃ )
-C ₃ H ₆ -N (CH ₃ ) ₂
-C ₃ H ₆ -N (CH ₃ ) -C ₂ H ₄ -N (CH ₃ ) ₂
-C ₃ H ₆ -N (CH ₃ )-[C ₂ H ₄ -N (CH ₃ )] _g -C ₂ H ₄ -N (CH ₃ ) ₂
-C ₃ H ₆ -NH-cyclo-C ₅ H ₁₁
(Here, e, f, and g are numbers 1 to 30, respectively.)

The amino-modified silicone used in the present invention is, for example, a hydrolyzate obtained by hydrolyzing an organoalkoxysilane represented by the general formula (a2) with excess water, and dimethylcyclopolysiloxane in sodium hydroxide. It can be produced by heating to 80 to 110 ° C. for an equilibrium reaction using such a basic catalyst, and neutralizing the basic catalyst with an acid when the reaction mixture reaches a desired viscosity. (See Japanese Patent Application Laid-Open No. 53-98499).
H ₂ N (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (CH ₃ ) (OCH ₃ ) ₂ (a2)

The amino-modified silicone is preferably a monoamino-modified silicone having one amino group in one side chain B and an amino in one of the side chains B from the viewpoint of obtaining a film having excellent releasability. One or more selected from the group consisting of a diamino-modified silicone having two groups, and more preferably a compound in which the side chain B having an amino group is represented by -C _{3H 6} -NH ₂ [hereinafter, (a1-). 1) Component] and a compound whose side chain B having an amino group is represented by -C ₃ H ₆ -NH-C ₂ H ₄ -NH ₂ [hereinafter referred to as (a1-2) component]. It is one or more kinds.

The amino-modified silicone in the present invention includes TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600), TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800), Dow, manufactured by Momentive Performance Materials, Inc. from the viewpoint of performance. -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) manufactured by Toray Co., Ltd. : 600, amino equivalent: 6400), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), 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) manufactured by Shinetsu Chemical Industry Co., Ltd. Equivalent: 1700), 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 preferable. In (), the kinematic viscosity shows a measured value (unit: mm ² / s) at 25 ° C., and the unit of amino equivalent is g / mol.

As the component (a1-1), BY16-213 (kinematic viscosity: 55, amino equivalent: 2700) and BY16-853U (kinematic viscosity: 14, amino equivalent: 450) are more preferable.

The components (a1-2) include 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) are more preferable.

The polymer compound may have a substituent. Examples of the substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a pentyloxy group, an isopentyloxy group, a hexyloxy group and the like. An alkoxy group having 1 to 6 carbon atoms; a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a pentyloxycarbonyl group. An alkoxy-carbonyl group having 1 to 6 carbon atoms such as a group and an alkoxy group such as an isopentyloxycarbonyl group; a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; and 1 carbon number such as an acetyl group and a propionyl group. Examples thereof include an acyl group of up to 6; an aralkyl group; an aralkyloxy group; an alkylamino group having 1 to 6 carbon atoms; and a dialkylamino group having 1 to 6 carbon atoms in the alkyl group.

(iii) Hydrocarbon-based compound As the hydrocarbon-based compound which is one of the modifying compounds in the present invention, a hydrocarbon-based compound having a cationic group is preferable. A hydrocarbon-based compound having a cationic group is one in which one or more hydrocarbon groups are bonded to one cationic group. The total number of carbon atoms of the hydrocarbon compound having a cationic group is preferably 16 or more, more preferably 18 or more from the viewpoint of obtaining a film having excellent releasability, and preferably 40 or less from the viewpoint of handleability. It is more preferably 30 or less, still more preferably 26 or less.

In the hydrocarbon compound having a cationic group, when the cationic group is a primary amine, a secondary amine, a tertiary amine, a quaternary ammonium, a phosphonium or the like, the hydrocarbon group is covalently bonded to a nitrogen atom or a phosphorus atom. It is a compound directly bound via. When the cationic group is amidine, guanidine or the like, it is a compound bonded to at least one of the nitrogen atom or the carbon atom of the functional group via a covalent bond. When the cationic group is imidazolium, pyridinium, imidazoline or the like, it is a compound in which at least one or more hydrocarbon groups are bonded to any position of the ring structure via a covalent bond.
The hydrocarbon compound having a cationic group is more preferably one that does not contain an oxyalkylene group.

(iv) Hydrocarbon groups Examples of the hydrocarbon groups in the hydrocarbon-based compounds include chain-type saturated hydrocarbon groups, chain-type unsaturated hydrocarbon groups, cyclic-type saturated hydrocarbon groups, and aromatic hydrocarbon groups. Be done. From the viewpoint of availability, the number of carbon atoms of the hydrocarbon group is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, still more preferably 12 or more, still more preferably 16 or more, and from the same viewpoint. It is preferably 40 or less, more preferably 30 or less, still more preferably 24 or less. The number of carbon atoms in a hydrocarbon group means the number of carbon atoms in one hydrocarbon group unless otherwise specified.

Specific examples of the chain saturated hydrocarbon group include, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group, an isobutyl group, a pentyl group, and a tert-pentyl group. Examples thereof include an isopentyl group, a hexyl group, an isohexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a nonyl group, a decyl group, a dodecyl group, a tridecyl group, a tetradecyl group, an octadecyl group, a docosyl group and an octacosanyl group.

Specific examples of the chain unsaturated hydrocarbon group include an ethenyl group, a propenyl group, a butenyl group, an isobutenyl group, an isoprenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, a decenyl group and a dodecenyl group. , Tridecenyl group, tetradecenyl group, octadecenyl group.

Specific examples of the cyclic saturated hydrocarbon group include, for example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclononyl group, a cyclodecyl group, a cyclododecyl group, a cyclotridecyl group, and the like. Examples thereof include a cyclotetradecyl group and a cyclooctadecyl group.

As the aromatic hydrocarbon group, for example, it is selected from the group consisting of an aryl group and an aralkyl group. As the aryl group and the aralkyl group, the aromatic ring itself may be substituted or unsubstituted.

Examples of the aryl group include a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a triphenyl group, a terphenyl group, and a group in which these groups are substituted with a substituent described later.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group, and a group in which the aromatic group of these groups is further substituted with a substituent. And so on.

In the above hydrocarbon compound, some hydrogen atoms may be further substituted. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, a hydroxy group, a methoxy group, an ethoxy group, a carboxy group, an aldehyde group, a ketone group, a thiol group and the like.

The hydrocarbon-based compound having a cationic group is preferably a hydrocarbon-based compound having an amino group such as a primary amine, a secondary amine, a tertiary amine, and a quaternary ammonium (in the present specification, "hydrocarbon-based compound". It is called "amine"). Specific examples of such hydrocarbon-based amines include hexadecylamine, stearylamine, oleylamine, dioctylamine, didecylamine, diddecylamine, trihexylamine, trioctylamine, tetrabutylammonium salt, tetrahexylammonium salt, and dimethyldioctylammonium. Salts, dimethyldidecylammonium salts, trimethylhexadecylammonium salts and the like are preferred.

(v) Amount of modification compound used The equivalent of a functional group capable of reacting with the anionic group of the modifying compound to be used with respect to the anionic group of the anion-modified cellulose fiber in the step of obtaining the hydrophobically modified cellulose fiber is demolding. From the viewpoint of obtaining a film having excellent properties, it is preferably 0.1 equivalent or more, more preferably 0.5 equivalent or more, still more preferably 1 equivalent or more, and from the same viewpoint, preferably 20 equivalent or less, more preferably 10 equivalent. Equivalent or less, more preferably 2 equivalents or less.

(3) Miniaturization treatment step By refining cellulose at any stage of the method for producing hydrophobically modified cellulose fibers, micrometer-scale cellulose can be miniaturized to nanometer scale. By reducing the average fiber diameter to the nanometer size, the strength at the time of film formation is improved, so it is preferable to further carry out the miniaturization treatment step.

A known disperser is preferably used as an apparatus used in the miniaturization process. For example, a breaker, a beater, a low-pressure homogenizer, a high-pressure homogenizer, a grinder, a cutter mill, a ball mill, a jet mill, a short-screw extruder, a twin-screw extruder, an ultrasonic stirrer, a household juicer mixer and the like can be used. Further, the solid content of the reactant fiber in the micronization treatment is preferably 50% by mass or less.

<Ingredient (B)>
The component (B) in the present invention is water. The component (B) has a role as a solvent in the production of the hydrophobically modified cellulose fiber and as one of the constituent components of the coating agent of the present invention.

<Ingredient (C)>
The component (C) in the present invention is an organic compound that is liquid at 25 ° C. and 1 atm. The component (C) may be a solvent for producing the hydrophobically modified cellulose fiber.
The solubility of the organic compound liquid at 25 ° C. at 1 atm in water is preferably 10 g or less, more preferably 1 g or less, per 100 g of water at 25 ° C.
The molecular weight of the component (C) is preferably 100,000 or less, more preferably 50,000 or less, still more preferably 10,000 or less from the viewpoint of obtaining a film having excellent releasability, and is preferable from the same viewpoint. Is 100 or more, more preferably 200 or more.

Specific examples of the component (C) in the present invention include oil agents, organic solvents, polymerizable monomers, prepolymers and the like. The component (C) in the present invention is preferably an oil agent, and the oil agent is, for example, alcohol, ester oil, hydrocarbon oil, silicone oil, ether oil, fat, oil, or fluorine from the viewpoint of obtaining a film having excellent mold releasability. One or more selected from the group consisting of system inert liquids and fatty acids is mentioned, and one or more selected from the group consisting of ester oils, silicone oils, ether oils, fats and oils, and fluorine-based inert liquids is preferable. , Esther oil, and one or more selected from the group consisting of ether oil are more preferable, and silicone oil and / or ester oil are further preferable.

Examples of the ester oil include monoester oil, diester oil, and triester oil. Specific examples thereof include isopropyl myristate, octyldodecyl myristate, myristyl myristate, 2-hexyldecyl myristate, isopropyl palmitate, and tri-2. -Examples include aliphatic or aromatic monocarboxylic acids or dicarboxylic acid esters having 2 to 18 carbon atoms such as glycerin ethylhexanoate and glycerin triisostearate.

Examples of the silicone oil include dimethylpolysiloxane, methylpolysiloxane, methylphenylpolysiloxane, octamethylcyclotetrasiloxane, and decamethylcyclopentasiloxane.
Examples of fats and oils include vegetable oils such as soybean oil, palm oil, flaxseed oil, cottonseed oil, rapeseed oil, and castor oil, and animal oils.

The compound of the component (C) preferably has an SP value of 10 or less, more preferably 9.5 or less, still more preferably 9.0 or less, still more preferably 8.5, from the viewpoint of obtaining a film having excellent releasability. From the same viewpoint, it is preferably 6.0 or more, more preferably 6.5 or more.

The SP value in the present specification indicates a solubility parameter (unit: (cal / cm ³ ) ^1/2 ) calculated by the Fedors method, and for example, the reference "SP value basics / applications and calculation methods" (Information Mechanism). , 2005), Polymer handbook Third edition (A Wiley-Interscience publication, 1989), etc.

Examples of the oil agent having an SP value of 10 or less used in the present invention include oleic acid (SP value: 9.2), D-lymonen (SP value: 9.4), and 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), Johova oil (SP value: 8.6), Squalane (SP value: 7.9), Liquid paraffin (SP value: 7.9), Fluoride inert liquid (for example, Florinate FC-40 (3M) , SP value: 6.1), Florinate FC-43 (3M company, SP value: 6.1), Florinate FC-72 (3M company, SP value: 6.1), Florinate FC-770 (manufactured by 3M company, SP value: 6.1) 3M, SP value: 6.1)), silicone oil (for example, KF96-1cs (Shinetsu Chemical Co., SP value: 7.3), KF-96-10cs (Shinetsu Chemical Co., SP value: 7) .3), KF-96-50cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3), KF-96-1000cs (Shinetsu Chemical Co., Ltd.) Manufactured by the company, SP value: 7.3), KF-96H-10,000 cs (manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3), etc.).

<Component (D)>
The coating agent of the present invention may contain the polyether-modified silicone compound of the component (D). By blending such a component (D) with a coating agent, a film having improved releasability can be obtained. Examples of the component (D) include a compound having a methyl silicone chain as a main chain and a side chain composed of a polyoxyethylene group, and specific examples thereof include a compound represented by the following general formula.

(In the formula, R ¹ is a methylene group, an ethylene group or a trimethylene group, R ² is an alkyl group having 1 to 4 carbon atoms, m is an integer of 0 to 50, n is an integer of 1 to 10, and p is. An integer of 1 to 50 and q indicate an integer of 0 to 50, respectively.-R ¹ (C ₂ H ₄ O) _p (C ₃ H ₆ O) _{q In} the group represented by R ² , (C ₂ H ₄ ) O) _p and (C ₃ H ₆ O) _q may be random or block.)

The HLB value of the polyether-modified silicone compound is preferably within a specific range from the viewpoint of obtaining a film having excellent releasability obtained by drying the coating agent, and specifically, preferably 1 or more, more preferably. It is 5 or more, more preferably 10 or more, preferably 18 or less, and more preferably 16 or less.

When two or more kinds of polyether-modified silicones having different HLB values are used, the HLB value obtained by the weighted average of them may be within the above range. The HLB value is an index showing the balance between hydrophilicity and lipophilicity, and in the present invention, it refers to a value obtained by the following Griffin formula.
HLB value = 20 x total molecular weight of hydrophilic base / molecular weight

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 having excellent releasability obtained by drying the coating agent, and specifically, preferably 1 mm ² /. It is s or more, more preferably 5 mm ² / s or more, preferably 1000 mm ² / s or less, more preferably 500 mm ² / s or less, still more preferably 200 mm ² / s or less.

A polyether-modified silicone compound that can be preferably used as the component (D) is commercially available, and commercially available products include KF-615A, KF-640, KF-642, KF-643, and KF-644 manufactured by Shin-Etsu Chemical Co., Ltd. , KF-351A, KF-354L, KF-355A, KF-6011, KF-6012, KF-6015, KF-6016, KF-6017, KF-6020, KF-6043, etc. From the viewpoint of obtaining a film having excellent releasability, KF-640, KF-642, KF-643, KF-351A, KF-354L, KF-355A and the like can be preferably used. Commercially available products having a structure that does 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 the component (D).

<Polymer compounds other than component (A) and component (D)>
The coating agent of the present invention may further contain a polymer compound other than the component (A) and the component (D).
From the viewpoint of obtaining a film having excellent releasability, the polymer compound is preferably one or more selected from the group consisting of the following polymer compound (X) and polymer compound (Y), and the polymer compound (X) is preferable. ) Is more preferable.
Polymer compound (X): A polymer compound having an ester group, an amide group, a urethane group, an amino group, an ether group or a carbonate group in the main chain (provided that it is one of the component (A-1) and the component (D). The applicable polymer compound is not treated as the polymer compound (X).)
Polymer compound (Y): A methacrylic or acrylic polymer having an ester group or an amide group in the side chain.

The weight average molecular weight of the polymer compound is preferably 1,000 or more from the viewpoint of obtaining a film having excellent releasability, and preferably 500,000 or less from the same viewpoint.

[Polymer compound (X)]
Examples of the polymer compound (X) having an ester group in the main chain include dicarboxylic acids such as adipic acid, sebacic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenyl succinic acid, and ethylene glycol. , A condensate with a diol such as propylene glycol or butanediol, or a condensate of a compound having both a hydroxy group and a carboxyl group in one molecule such as succinic acid and lactic acid.

Examples of the polymer compound (X) having an amide group in the main chain include dicarboxylic acids such as adipic acid, sebacic acid, dodecanedic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenylsuccinic acid, and ethylenediamine. Examples thereof include a condensate with a diamine such as an aliphatic diamine such as hexamethylenediamine and propylenediamine.

The polymer compound (X) having a urethane group in the main chain is a polymer of diisocyanate such as triresin diisocyanate, diphenyl isocyanate, xylylene diisocyanate, hexamethylene diisocyanate and diols such as ethylene glycol, propylene glycol and butanediol. And so on.

Examples of the polymer compound (X) having an amino group in the main chain include polymers of alkylimines such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine and hexyleneimine.

Examples of the polymer compound (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.

Examples of the polymer compound (X) having a carbonate group in the main chain include 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) butane, and 1,1-bis (4-hydroxyphenyl). Examples thereof include a condensate of a polyol such as hydroxyphenyl) cyclohexane and a phosgen.

[Polymer compound (Y)]
Examples of the polymer compound (Y), that is, a methacrylic or acrylic polymer having an ester group or an amide group in the side chain, include polymethyl (meth) acrylate, polyethyl (meth) acrylate, and polybutyl (meth) acrylate. Poly (meth) acrylamide such as polyalkyl (meth) acrylate, poly (meth) acrylamide, poly N-methyl (meth) acrylamide, poly N, N-dimethyl (meth) acrylamide, poly N-phenyl (meth) acrylamide, etc. Can be mentioned.

<Other ingredients>
In addition to the above components, the coating agent of the present invention includes a plasticizer, a crystal nucleating agent, a filler (inorganic filler, organic filler), a hydrolysis inhibitor, a flame retardant, an antioxidant, a hydrocarbon wax and an anion. Type surfactants such as lubricants, UV absorbers, antistatic agents, antifogging agents, light stabilizers, pigments, antifungal agents, antibacterial agents, foaming agents, surfactants; polysaccharides such as starches and alginic acids; gelatin , Nikawa, casein and other natural proteins; tannins, zeolites, ceramics, metal powders and other inorganic compounds; fragrances; flow regulators; leveling agents; conductive agents; ultraviolet dispersants; deodorants, etc., the effects of the present invention. Can be contained within a range that does not impair. Similarly, other polymer materials and other compositions can be added as long as the effects of the present invention are not impaired.

<Characteristics of coating agent>
The coating agent of the present invention is a composition containing the above-mentioned component (A), component (B) and component (C) as essential components, and is preferably an emulsified composition, that is, an emulsified composition. The emulsification in the present invention is to apply a mechanical force in a state where water and a liquid organic compound are mixed at 25 ° C. and 1 atm so that the other droplets 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 preferable.

The content of the component (A) in the coating agent or at the time of mixing is preferably 0.02% by mass or more, more preferably 0.05% by mass or more, still more preferably 0.1% by mass, from the viewpoint of emulsifying power. On the other hand, from the viewpoint of handleability, it is preferably 15% by mass or less, more preferably 10% by mass or less, and further preferably 5% by mass or less.

The content of the component (B) in the coating agent or at the time of mixing is preferably 10% by mass or more, more preferably 20% by mass or more, still more preferably 30% by mass or more, from the viewpoint of maintaining an emulsified state. From the viewpoint of the effective amount, it is preferably 98% by mass or less.

The content of the component (C) in the coating agent or at the time of mixing is preferably 0.1% by mass or more, more preferably 0.5% by mass or more, still more preferably 1% by mass, from the viewpoint of maintaining the emulsified state. On the other hand, from the viewpoint of solution viscosity and handleability, it is preferably 70% by mass or less, more preferably 60% by mass or less, and further preferably 50% by mass or less.

The mass ratio (A / C) of the component (A) to the component (C) in the coating agent or at the time of mixing is preferably 0.0001 or more, more preferably 0., from the viewpoint of obtaining a film having excellent releasability. It is 001 or more, more preferably 0.004 or more, still more preferably 0.01 or more, still more preferably 0.04 or more, and from the viewpoint of film forming property, it is preferably 20 or less, more preferably 10 or less, still more preferably. It is 5 or less, more preferably 3 or less, still more preferably 2 or less. From these viewpoints, it is preferably 0.0001 or more and 20 or less, more preferably 0.001 or more and 10 or less, still more preferably 0.004 or more and 5 or less, still more preferably 0.01 or more and 3 or less, still more preferably 0.04. It is 2 or less.

When the component (D) is used, the content of the component (D) in the coating agent or at the time of mixing is preferably 0.01% by mass or more, more preferably 0. It is 05% by mass or more, more preferably 0.1% by mass or more, and from the same viewpoint, it is preferably 5% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less.

When the coating agent of the present invention contains a polymer compound other than the component (A) and the component (D), the content of the polymer compound in the coating agent is preferably 0 from the viewpoint of film durability. .1% by mass or more, more preferably 0.5% by mass or more, while preferably 20% by mass or less, more preferably 10% by mass or less, still more preferably 5 from the viewpoint of obtaining a film having excellent releasability. It is less than mass%.

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, still more preferably 1 mPa · s or more, and the same. From the viewpoint of the above, it is preferably 30 Pa · s or less, more preferably 20 Pa · s or less, and further preferably 10 Pa · s or less. Here, the viscosity is measured by a B-type viscometer after stirring for 1 minute under the conditions of 25 ° C. and a rotation speed of 60 rpm using an appropriate rotor suitable for the viscosity range of each sample.

The average particle size of the emulsified droplet in the coating agent is preferably 10 nm or more, more preferably 50 nm or more, still more preferably 100 nm or more from the viewpoint of obtaining a film having excellent mold releasability in the measurement by SEM observation, and the same viewpoint. Therefore, it is preferably 2000 nm or less, more preferably 1000 nm or less, further preferably 700 nm or less, further preferably 500 nm or less, preferably 10 nm or more and 2000 nm or less, more preferably 50 nm or more and 1000 nm or less, still more preferably 100 nm or more and 500 nm or less. be.

2. 2. Method for Producing Coating Agent The method for producing a coating agent of the present invention comprises a step of mixing the above-mentioned components (A), component (B), component (C) and the like. Here, a liquid organic compound may be mixed with the aqueous dispersion of the hydrophobically modified cellulose fiber at 25 ° C. and 1 atm, or the organic compound dispersion of the hydrophobically modified cellulose fiber may be mixed with water. As the organic compound liquid at 25 ° C. and 1 atm, alcohols such as ethanol and 2-propanol are effective. By blending these, the wettability to the base material can be enhanced. The content of the organic compound liquid at 25 ° C. and 1 atm is preferably 5% by mass or more from the viewpoint of improving wettability, and preferably 90% by mass or less from the viewpoint of stability.

Alternatively, as a method for producing the coating agent of the present invention, a production method including a step of mixing the component (A-1), the component (A-2), the component (B), and the component (C) can be mentioned. In the above case, the step of obtaining the hydrophobically modified cellulose fiber and the step of obtaining the coating agent can be achieved in one step, which is more preferable. There is no limitation on the mixing order of such methods. For example, the component (A-1), the component (A-2), and the component (B) may be mixed and then mixed with the component (C), or the component (A-1) and the component (A-2) may be mixed. And the component (C) may be mixed and then mixed with the component (B).
A production method including a step of mixing the component (A-1) and the component (A-2) in the presence of the component (B) and the component (C) is preferable.
Therefore, a preferred embodiment of the coating agent of the present invention contains a component (A-1), a component (A-2), a component (B), and a component (C). In that case, the content of the component (A) is the total content of the component (A-1) and the component (A-2).

When the component (D) is blended, the component (D) may be mixed with these raw materials, or the component (D) may be added to the coating agent obtained by using these raw materials.

By mixing each component, emulsification occurs and a coating agent is obtained. Such mixing processes include magnetic stirrers, mechanical stirrers, homomixers, vacuum emulsifiers, low-pressure homogenizers, high-pressure homogenizers, grinders, cutter mills, ball mills, jet mills, mass colloiders, short-screw extruders, twin-screw extruders, and super A sonic stirrer, a household juicer mixer, or the like can be used. The mixing process may be performed by combining two or more types of operations.

The temperature and time at the time of mixing each component are not particularly limited, and are, for example, preferably in the temperature range of 5 to 50 ° C., and preferably in the range of 1 minute to 3 hours.

The preferable range of the content of each component at the time of mixing is the same as the preferable range of the content of each component in the coating agent of the present invention described above.

When the component (A-1) and the component (A-2) are used instead of the component (A), the upper limit and the lower limit of the preferable content of the component (A) are set as the upper limit and the lower limit of the total amount of both components. It is preferably a value. Here, the compounding ratio of the component (A-1) and the component (A-2) is as follows: From the viewpoint of obtaining a film having excellent releasability with respect to the anionic group of the component (A-1), the component ( A-2) is preferably 0.1 equivalent or more, more preferably 0.3 equivalent or more, still more preferably 0.5 equivalent or more, while preferably 3 equivalent or less from the viewpoint of the stability of the coating agent. It is more preferably 2 equivalents or less, still more preferably 1.5 equivalents or less.

Alternatively, for [the number of moles of the anionic group of the component (A-1)], [the number of moles of the amino group of the amino-modified silicone of the component (A-2)] and [the number of molars of the hydrocarbon compound having a cationic group]. The ratio of [total number of moles of cationic group] to [[total number of moles of component (A-2)] / [number of moles of anionic group of component (A-1)]) is demolding. From the viewpoint of obtaining a film having excellent properties, it is preferably 0.1 or more, more preferably 0.3 or more, still more preferably 0.5 or more, and from the viewpoint of film forming property, preferably 3 or less, more preferably 2 It is 5.5 or less, more preferably 2 or less. The number of moles of anionic groups in the anionic-modified cellulose fiber may be obtained by multiplying the amount (g) of the anionic-modified cellulose fiber used by the anionic group content (mmol / g), and the number of moles of the amino groups of the amino-modified silicone fiber is , The amount (g) of the amino-modified silicone used may be divided by the amino equivalent (g / mol).

The mass ratio (A-2 / C) of the component (A-2) to the component (C) is preferably 0.0001 or more, more preferably 0.001 from the viewpoint of obtaining a film having excellent releasability. The above is more preferably 0.004 or more, further preferably 0.01 or more, still more preferably 0.04 or more, and from the viewpoint of film forming property, it is preferably 20 or less, more preferably 10 or less, still more preferably 5. Below, it is more preferably 3 or less, still more preferably 2 or less. From these viewpoints, it is preferably 0.0001 or more and 20 or less, more preferably 0.001 or more and 10 or less, still more preferably 0.004 or more and 5 or less, still more preferably 0.01 or more and 3 or less, still more preferably 0.04. It is 2 or less.

3. 3. A method for producing a coating film obtained by drying a coating agent The method for producing a coating film obtained by drying a coating agent according to the present invention is obtained by the above-mentioned coating agent of the present invention or the method for producing the coating agent of the present invention. The step of drying the coated coating agent is included.

Specifically, the coating agent is applied to a substrate, for example, a hard surface made of paper such as glass, resin, metal, ceramics, concrete, wood, stone, or fibers, skin, hair, or the like. From the viewpoint that the film predominantly exerts a role as a mold release agent, a hard surface is preferable as a substrate, and a metal is more preferable. That is, a metal is preferable as the target surface of the coating agent of the present invention. Metals include, for example, iron, aluminum, copper, and alloys thereof (eg, stainless steel, duralumin, brass). As the method of application, for example, a method of applying using an applicator, a bar coder, a spin coater, etc., a method of applying with a brush, a method of impregnating with cloth or paper, and the like, air spray, airless spray, trigger Examples thereof include sprays, sprays such as aerosol sprays, and dip coats, but the present invention is not limited thereto.

The thickness of the coating film of the coating agent on the substrate is preferably 10 μm or more, more preferably 20 μm or more, still more preferably 30 μm or more from the viewpoint of film durability, and preferably 2000 μm or less from the viewpoint of coatability. , More preferably 1500 μm or less.

Then, the coating film of the coating agent can be dried to obtain a coating film. The drying conditions may be under reduced pressure or normal pressure, and the temperature range is preferably 15 ° C. or higher and 75 ° C. or lower. The time for drying is preferably 10 minutes or more and 24 hours or less.

4. Dry film of coating agent

The thickness of the film of the present invention is not particularly limited, and is preferably 1 μm or more, more preferably 3 μm or more, still more preferably 5 μm or more from the viewpoint of film durability, and preferably 2000 μm or less from the viewpoint of economy. It is more preferably 1200 μm or less, still more preferably 500 μm or less, still more preferably 200 μm or less. The film thickness can be set to a desired value by setting the coating film thickness with a coating tool such as an applicator, adjusting the coating amount with a spray or the like, and adjusting the ratio of the medium. The thickness of the film can be measured according to the method described in Examples described later.

The amount of the hydrophobically modified cellulose fiber in the membrane of the present invention is preferably 1% by mass or more, more preferably 10% by mass or more from the viewpoint of the durability of the membrane, and from the viewpoint of obtaining a membrane having excellent releasability. It is preferably 65% by mass or less, more preferably 36% by mass or less, still more preferably 16% by mass or less. The amount of hydrophobically modified cellulose fibers in the membrane can be determined in consideration of the amount of volatile components (for example, water or some oils) in the coating agent.
The range of preferable amounts of the component (C) and the component (D) in the film of the present invention also corresponds to the range of their preferred amounts in the coating agent.

The film of the present invention may contain an optional component that does not impair the effects of the present invention.

By applying the film of the present invention to a solid surface, it is possible to impart releasability of a resin or the like to the solid surface. That is, the coating film obtained by drying the coating agent of the present invention can be suitably used as a film for a mold release agent.
The film of the present invention is not only excellent in releasability, but also excellent in durability of the film itself, so that the effect can be maintained for a long period of time. It can be used for molded bodies such as molding and sheet molding.
Resins that are effective as a mold release agent include polyester, polylactic acid, polyolefin, polystyrene, nylon, polyoxymethylene, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyether sulfone, thermoplastic resins such as elastomers, and epoxy resins. Examples thereof include thermoplastic resins such as silicone resins and rubber.

Hereinafter, the present invention will be specifically described with reference to Examples and the like. It should be noted that the following examples are merely examples of the present invention and do not mean any limitation.

[Average fiber diameter, average fiber length, average aspect ratio of anionic-modified cellulose fibers and hydrophobic-modified cellulose fibers]
Water is added to the cellulose fibers to be measured to prepare a dispersion having a content of 0.0001% by mass. Atomic force microscope (AFM) (Nanoscope II Tappingmode AFM, manufactured by Digital instrument, Nanoscope II Tappingmode AFM; probe manufactured by Nanosensors, Point Probe (AFM) Using NCH)), the fiber height (difference in height between the presence and absence of fibers) of the cellulose fibers in the observation sample is measured. At that time, in a microscope image in which the cellulose fibers can be confirmed, 100 or more cellulose fibers are extracted, and the average fiber diameter is calculated from the fiber heights thereof. The average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated from the average fiber length / average fiber diameter. The height analyzed in the image by AFM can be regarded as the fiber diameter.

[Average fiber diameter and average fiber length of raw material cellulose fiber]
Deionized water is added to the cellulose fiber to be measured to prepare a dispersion having a content of 0.01% by mass. Using a wet dispersion type image analysis particle size distribution meter (Jasco International, IF-3200), the dispersion is used for front lens: 2x, telecentric zoom lens: 1x, image resolution: 0.835 μm / pixel, syringe inner diameter. Measurement is performed under the conditions of: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghost, threshold value: 8, analysis sample volume: 1 mL, sampling: 15%. 100 or more cellulose fibers are measured, and the average ISO fiber diameter thereof is taken as the average fiber diameter, and the average ISO fiber length is calculated as the average fiber length.

[Anionic group content of anionic-modified cellulose fibers and hydrophobic-modified cellulose fibers]
Take the cellulose fiber to be measured with a dry mass of 0.5 g in a 100 mL beaker, add deionized water or a mixed solvent of methanol / water = 2/1 to make a total of 55 mL, and add 5 mL of 0.01 M sodium chloride aqueous solution to this. Prepare a dispersion. The dispersion is stirred until the cellulose fibers to be measured are sufficiently dispersed. Add 0.1 M hydrochloric acid to this dispersion to adjust the pH to 2.5 to 3, and use an automatic titrator (AUT-701, manufactured by Toa DKK) to apply a 0.05 M sodium hydroxide aqueous solution and wait 60. It is added dropwise to the dispersion under the condition of seconds, and the electric conductivity and pH values are measured every minute. Continue the measurement until the pH reaches about 11, and obtain an electric conductivity curve. From this conductivity curve, the quantification of sodium hydroxide titration is obtained, and the anionic group content of the cellulose fiber to be measured is calculated by the following formula.
Anionic group content (mmol / g) = [sodium hydroxide droplet quantification x sodium hydroxide aqueous solution concentration (0.05 M)] / [mass of cellulose fiber to be measured (0.5 g)]

[Aldehyde group content of oxidized cellulose fiber]
The carboxy group content of the oxidized cellulose fiber to be measured is measured by the above-mentioned method for measuring the anionic group content.
On the other hand, separately from this, in a beaker, 100 g (solid content content: 1.0% by mass) of an aqueous dispersion of the oxidized cellulose fiber to be measured, 100 g of an acetate buffer (pH 4.8), 2-methyl-2-butene. 0.33 g and 0.45 g of sodium chlorite are added and stirred at 25 ° C. for 16 hours to oxidize the aldehyde group remaining on the oxidized cellulose fiber. After completion of the reaction, the cells are washed with deionized water to obtain cellulose fibers obtained by oxidizing an aldehyde group. The reaction solution is freeze-dried, and the carboxy group content of the obtained dried product is measured by the above-mentioned method for measuring the anionic group content, and the "carboxy group content of the oxidized cellulose fiber" is calculated. Subsequently, the aldehyde group content of the oxidized cellulose fiber to be measured is calculated by the formula 1.

Oxidation group content (mmol / g) = (Carboxy group content of oxidized cellulose fiber)-(Carboxy group content of oxidized cellulose fiber to be measured) ... Equation 1

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

[Confirmation of crystal structure in hydrophobically modified cellulose fibers]
The crystal structure of the hydrophobically modified cellulose fiber is confirmed by measuring under the following conditions using an X-ray diffractometer (MiniFlexII manufactured by Rigaku Co., Ltd.).
The measurement conditions are X-ray source: Cu / Kα-radiation, tube voltage: 30 kv, tube current: 15 mA, measurement range: diffraction angle 2 θ = 5 to 45 °, and X-ray scan speed: 10 ° / min. The measurement sample is prepared by compressing it into pellets having an area of 320 mm ² x a thickness of 1 mm. Further, the crystallinity of the cellulose type I crystal structure is calculated by calculating the obtained X-ray diffraction intensity based on the following formula A.

<Formula A>
Cellulose Type I Crystallinity (%) = [(I _22.6 -I _18.5 ) / I _22.6 ] x 100
[In the formula, I _22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6 °) in X-ray diffraction, and I _18.5 is the amorphous portion (diffraction angle 2θ = 18.5). °) Diffraction intensity]

On the other hand, when the crystallinity obtained by the above formula A is 35% or less, from the viewpoint of improving the calculation accuracy, P199-200 of "Wood Science Experiment Manual" (edited by Japan Wood Society; published in April 2000). It is preferable to calculate based on the following formula B in accordance with the description of.
Therefore, when the crystallinity obtained by the above formula A is 35% or less, the value calculated based on the following formula B can be used as the crystallinity.

<Equation B>
Cellulose type I crystallinity (%) = [ _Ac / ( _Ac + A _a )] × 100
[In the equation, _Ac is a lattice plane (002 plane) (diffraction angle 2θ = 22.6 °), (011 plane) (diffraction angle 2θ = 15.1 °) and (0-11 plane) in X-ray diffraction. The sum of the peak areas of (diffraction angle 2θ ₌ 16.2 °), Aa indicates the peak area of the amorphous part (diffraction angle 2θ = 18.5 °), and each peak area is the obtained X-ray diffraction chart. Obtained by fitting with a Gaussian function]

[Cellulose fiber (converted amount) in hydrophobic modified cellulose fiber]
The cellulose fiber (converted amount) in the hydrophobically modified cellulose fiber is measured by the following method.
(1) When one kind of "modifying compound" is added The amount of cellulose fibers (converted amount) is calculated by the following formula C.
<Formula C>
Cellulose fiber amount (converted amount) (g) = mass of hydrophobically modified cellulose fiber (g) / [1 + molecular weight of modifying compound (g / mol) × bonding amount of modifying group (mmol / g) × 0.001]
(2) When there are two or more types of "modifying compounds" to be added The amount of cellulose fibers in consideration of the molar ratio of each compound (that is, the molar ratio when the total molar amount of the added compounds is 1). Calculate (converted amount).

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

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

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

[Preparation of anion-modified cellulose fibers]
Preparation Example 1
Softwood bleached kraft pulp (Hinton, manufactured by West Freder) was used as the raw material for natural cellulose fibers. As the TEMPO, a commercially available product (ALDRICH, Free radical, 98% by mass) was used. Commercially available products were used as sodium hypochlorite, sodium bromide and sodium hydroxide.

First, 10 g of the bleached kraft pulp fiber and 990 g of deionized water were weighed in a 2 L PP beaker equipped with a mechanical stirrer and a stirring blade, and the mixture was stirred 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 a 10.5 mass% sodium hypochlorite aqueous solution were added in this order. Using a pH stat titration with an automatic titrator (AUT-701 manufactured by DKK-TOA CORPORATION), a 0.5 M aqueous sodium hydroxide solution was added dropwise to maintain the pH at 10.5. After the reaction was carried out at a stirring speed of 100 rpm at 25 ° C. for 120 minutes, the dropping of the aqueous sodium hydroxide solution was stopped to obtain a suspension of anion-modified cellulose fibers.

After adding 0.01 M hydrochloric acid to the obtained suspension of anionic-modified cellulose fibers to adjust the pH to 2, in the measurement of the conductivity of the filtrate with a compact electric conductivity meter (LAQUAtwin EC-33B, manufactured by Horiba, Ltd.). It was thoroughly washed with deionized water until it became 200 μs / cm or less, and then dehydrated to obtain anionic-modified cellulose fibers. The carboxy group content of the anion-modified cellulose fiber was 1.50 mmol / g, and the aldehyde group content was 0.23 mmol / g.

Preparation Example 2 (Production of Micronized Anion-Modified Cellulose Fiber)
Deionized water was added to the anion-modified cellulose fiber finally obtained in Preparation Example 1 to prepare 100 g of a suspension (solid content content: 2.0% by mass). A 0.5 M aqueous sodium hydroxide solution was added to adjust the pH to 8, and then deionized water was added to bring the total amount to 200 g. This suspension was subjected to a micronization treatment at 150 MPa three times using a high-pressure homogenizer (NanoVeta L-ES, manufactured by Yoshida Machinery Co., Ltd.), and the miniaturized anion-modified cellulose fiber dispersion liquid (solid content content 1.0% by mass) was performed. ) Was obtained. The counter ion of the carboxy group of this miniaturized anion-modified cellulose fiber was sodium ion. This refined anion-modified cellulose fiber is abbreviated as "TCNF (Na type)".

Preparation Example 3 (Production of Micronized Anion-Modified Cellulose Fiber with Reduction Treatment of Aldehyde Group)
182 g of the finely divided anion-modified cellulose fiber dispersion (solid content content 1.0% by mass) obtained in Preparation Example 2 was weighed, and deionized water was added to make a total of 400 g. 1.2 mL of 0.1 M aqueous sodium hydroxide solution and 120 mg of sodium borohydride were added thereto, and the mixture was stirred at 25 ° C. for 4 hours. Next, 9 mL of 1M hydrochloric acid was added for protonation. After completion of the reaction, the cake was filtered and washed with deionized water 6 times to remove salts and hydrochloric acid, and the aldehyde group was reduced. The finely divided anion-modified cellulose fiber dispersion (solid content content 0. 9% by mass) was obtained. The obtained cellulose fiber had a carboxy group content of 1.50 mmol / g and an aldehyde group content of 0.02 mmol / g. The carboxy group of the micronized anion-modified cellulose fiber is a free acid type (COOH) and is abbreviated as "TCNF (H type)". The crystallinity of the finely divided anion-modified cellulose fibers was 30%, the average fiber diameter was 3.3 nm, and the average fiber length was 600 nm.

[Preparation of hydrophobic modified cellulose fiber and coating agent]
Example 1
In a beaker, 83.3 g (solid content content: 0.9% by mass) of the finely divided anion-modified cellulose fiber dispersion obtained in Preparation Example 3, 7.5 g of silicone oil, and 12.4 g of amino-modified silicone (anion-modified). (Equivalent to 1.25 equivalents to the carboxy group of the cellulose fiber) was mixed, and deionized water was added thereto to make a total of 100 g. This solution is stirred with a mechanical stirrer for 5 minutes and then treated with a high-pressure homogenizer (NanoVeta L-ES manufactured by Yoshida Machinery Co., Ltd.) at 150 MPa for 10 passes. An emulsified composition containing the hydrophobically modified cellulose fibers linked together was obtained. This emulsified composition was used as the coating agent in Example 1. The obtained composition was a cloudy liquid, and it was determined that it was in an emulsified state because it was observed that oil droplets were dispersed in water by observation with an optical microscope and Cryo-SEM.

Example 2
100 g of the emulsified composition obtained in Example 1 was weighed into a beaker, 0.25 g of 1 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.

Examples 3-12
Each compound is mixed so as to have the blending ratios shown in Tables 1 and 2, and an emulsified composition is obtained by the same method as in Example 1, and then the polyethers are blended so as to have the blending amounts shown in Tables 1 and 2. The modified silicone was mixed in the same manner as in Example 2 to obtain a coating agent.

Comparative Example 4
Each compound was mixed so as to have the compounding ratio shown in Table 2 and diluted with acetone to obtain a coating agent containing no hydrophobically modified cellulose fiber.

The details of the typical ingredients used in the examples are summarized below.
[Modifying compound]
Amino-modified silicone 1: "DOWNSIL ^TM SS-3551" manufactured by Dow Toray, kinematic viscosity: 1,000, amino equivalent: 1,700
Oleylamine: Wako Pure Chemical Industries, Ltd., amino equivalent: 267.5, total carbon number: 18
[Ingredient (C)]
Silicone oil 1: "KF-96-100cs" manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3
Silicone oil 2: "KF-96-10cs" manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3
Silicone oil 3: "KF-96-3000cs" manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3
Silicone oil 4: "KF-96-10,000cs" manufactured by Shin-Etsu Chemical Co., Ltd., SP value: 7.3
[Component (D)]
Polyether-modified silicone 1: "KF-642" manufactured by Shin-Etsu Chemical Co., Ltd., HLB: 14

[Preparation of dry membrane]
The coating agent produced in Example 1 was used with an air spray (manufactured by Anest Iwata, WIDER1-10E1G, nozzle diameter Φ1.0 mm) to make a deep stainless steel bat (manufactured by Sanposha, external dimensions: 135 × 106 × H59 mm). , A volume of 650 mL) was uniformly applied to 3 g, and dried at 1 atm, 25 ° C., and a humidity of about 40% RH for 1 hour to prepare a film. When the thickness of the film of Example 1 was measured by the following measuring method, it was 7 μm.
For the coating agents prepared in Examples 2 to 12 and Comparative Example 4, the coating amount was adjusted so as to have the same film thickness as in Example 1, and a film was prepared on the inner surface of the stainless steel deep assembly vat.

Comparative Examples 1 to 3
In Comparative Example 1, a stainless steel deep assembly bat itself was used.
In Comparative Example 2, 3 g of a commercially available silicone-based mold release agent (manufactured by Shin-Etsu Chemical Co., Ltd., KM-9782, effective content 10%) was applied to a stainless steel deep-type assembly vat in the same manner as in Example, dried and a film was formed. Was produced.
In Comparative Example 3, 3 g of a commercially available fluorine-based mold release agent (manufactured by Neos Co., Ltd., Furelease 20A, effective content 10%) was applied to a stainless steel deep-type assembly vat in the same manner as in Example, and dried to prepare a film. did.

[Measurement of film thickness]
The thickness of the film after drying was measured using a laser microscope (manufactured by KEYENCE, VK-9710) under the following measurement conditions. The measurement conditions were an objective lens: 10 times, a light intensity of 3%, a brightness of 1548, and a Z pitch of 0.5 μm. A part of the film is scraped off with a metal spatula, the sample with the glass substrate exposed is measured, the height of the glass substrate and the height of the part with the film are measured using the built-in image processing software, and the difference between them. The thickness of the film was determined by taking.

[Resin releasability evaluation 1]
Atypical polyester resin (Byron 600TM, manufactured by Toyobo Co., Ltd.) placed in a stainless steel container on a hot plate heated to 300 ° C. was softened and treated with the coating agents of Examples 1 to 12 and Comparative Examples 2 to 4. After pouring 500 g into a deep-made bat or an untreated deep-made stainless steel bat (Comparative Example 1), cooling at room temperature for 12 hours and curing, the releasability of the resin was evaluated according to the following criteria. The larger the number, the better the releasability of the resin.
In Example 2 and Comparative Example 3, the resin was repeatedly filled a plurality of times, and the releasability was evaluated. However, no additional coating was applied.

5: The resin fell just by turning the bat over.
4: The bat was turned over and the resin fell with a light impact that hit the ground.
3: The resin fell when the bat was turned over and the bottom of the bat was hit once with a hammer.
2: The resin fell when the bat was turned over and the bottom of the bat was hit with a hammer 2 to 5 times.
The resin remained on the bat even after hitting 1: 5.
The results are shown in Tables 1 and 2.

The following was found from Tables 1 and 2.
From Examples 2 and Comparative Examples 1 to 3, the coating agent of the present invention exhibited higher releasability than the untreated stainless steel vat or a commercially available silicone-based or fluorine-based mold release agent, and was used repeatedly. It was also found to be excellent in durability.
From Examples 1 to 3, it was found that when an appropriate amount of the polyether-modified silicone of the component D was contained, the releasability was excellent. It is considered that this is because the wettability of the coating agent on the stainless steel vat is improved and a uniform film can be formed.
From Examples 2, 4 and 5, it was found that the larger the number of modifying groups for the anion-modified cellulose, the better the releasability. It is considered that this is because the amount of exposure on the surface of the anionic group that can interact with the resin is reduced.
From Example 12, it was found that the modifying group exhibited the effect even with an alkylamine, but the amino-modified silicone was more effective.
From Examples 2 and 6 to 8, it was found that the effect was exhibited with a wide range of oils as the component (C), but the effect was higher with the oil having a relatively low viscosity.
It was found that the effect was higher when the ratio of the component (C) in the dry membrane was larger than in Examples 2 and 9-11. On the other hand, from Comparative Example 4, it was found that the effect was not exhibited without the hydrophobically modified cellulose fiber. It is considered that this is because the component (C) cannot stay on the surface of the stainless steel bat.

[Resin releasability evaluation 2]
With the coating agent produced in Example 2, a dry film was formed on a glass substrate, and the releasability was evaluated.
That is, 0.3 mL of the coating agent prepared in Example 2 was applied on a glass substrate (Matso-Made: Micro Slide Glass S2112) (surface area 15.6 cm ² ) and spread over the entire glass surface. Then, the film was prepared by drying at 1 atm, 25 ° C. and a humidity of about 40% RH for 3 hours. When the thickness of the film was measured by the above measuring method, it was 20 μm.

The peelability of various resins shown in Table 3 was evaluated using the coating agent of Example 2 treated on a glass substrate. That is, 10 g of each resin is put in an aluminum cup (diameter 8 cm), heated with a hot plate to melt or soften, and then 0.5 g is placed on the glass substrate on which the film is prepared and cooled and solidified at room temperature. The mold releasability of the resin was evaluated according to the following criteria.

5: It falls just by tilting the glass substrate 4: It can be peeled off with a light finger force.
3: Can be removed with a tool (using a stainless spatula).
2: Part of it remains even if a tool is used (using a stainless spatula).
1: Cannot be peeled off.
The results are shown in Table 3.

From Table 3, it was found that with any of the resins used in the experiment, the resin could be removed simply by tilting the glass substrate.
From the above, it was found that the coating agent of the present invention can be applied to a target substrate to form a film, thereby exhibiting releasability for a wide range of resins such as general-purpose thermoplastic resins, engineering plastics, and elastomers. In particular, nylon and elastomer are considered to be useful because they have strong adhesion when untreated and are difficult to release.

[Resin releasability evaluation 3]
The coating agent of Example 2 was applied onto a glass substrate having a size of 200 × 130 × t3 mm in the same manner as the substrate used in the resin releasability evaluation 2 so that the film thickness after drying was 20 μm. Two pieces of this substrate were fixed with a clip using Φ3 mm silicone rubber as a spacer to prepare a casting mold. Next, an epoxy resin (manufactured by Mitsubishi Chemical Corporation, jER828) was poured and cured in a hot air circulation open PH200 (manufactured by Espec) under the conditions of 80 ° C. for 1 hour and 150 ° C. for 1 hour. The same operation was performed on an untreated glass substrate, and the releasability of the resin after curing was evaluated.

As a result, the resin could not be peeled off at all from the untreated glass substrate even by using a tool, whereas the resin could be easily peeled off by inserting a spatula in the glass substrate coated with the coating agent of Example 2. Was made.
From this, it was also found that the coating agent of the present invention is excellent in releasability after curing of the thermosetting resin.

[Resin releasability evaluation 4]
The coating agent produced in Example 2 was applied to a mold using an air spray, dried, and the releasability was evaluated using an injection molding machine.
That is, the coating agent manufactured in Example 2 was applied to a mold (dumbbell: JIS K7139 type A1, square pillar test piece: 63 mm × 13 mm × 6.4 mm) provided in an injection molding machine (J110AD-180H manufactured by Japan Steel Works, Ltd.). A flat plate test piece (70 mm × 40 mm × 2 mm) was applied to the whole and sprue using an air spray (WIDER110E1G, Φ1.0, spray pressure 0.2 MPa manufactured by Anest Iwata Co., Ltd.) and dried at room temperature for 1 minute. Next, the styrene-based elastomer AR-SC-45 (manufactured by Aronkasei Co., Ltd.) was injection-molded under the conditions of a resin temperature of 190 ° C., a mold temperature of 30 ° C., and a cooling time of 5 seconds.
As a result, in the mold in which the coating agent was not applied, it was difficult to take out the molded product because it was stuck in the mold, and the sprue was clogged with resin, and it was difficult to take out without using a tool. On the other hand, when the coating agent of Example 2 is coated, the resin can be easily taken out without clogging the mold, and the resin can be easily taken out from the sprue, and excellent mold release property can be exhibited. Do you get it. It was also found that excellent mold releasability was maintained even after injection molding 10 times in a row without recoating.

The coating agent of the present invention can be treated on the target surface by a simple method such as spraying, and has durability to repeatedly exhibit releasability. Therefore, it is considered to be very useful in the fields of mold release paper and release film by applying the coating agent of the present invention to paper and sheets, as well as manufacturing equipment for resins and resin compounds, injection molding and sheet molding, rubber molding. Be done.

Claims (8)

A coating agent containing the following components (A) to (C).
(A) Hydrophobic modified cellulose fiber in which a modifying group is bonded to one or more selected from the group consisting of an anionic group and a hydroxy group (B) Water (C) An organic compound liquid at 25 ° C. and 1 atm. The component (A) is hydrophobic, which is formed by binding a hydrocarbon-based compound having a cationic group to an anionic group of a hydrophobically modified cellulose fiber in which a polymer compound is bonded to the cellulose fiber and / or an anionic modified cellulose fiber. The coating agent according to claim 1, which is a modified cellulose fiber. The coating agent according to claim 1 or 2, further containing the component (D) a polyether-modified silicone compound. The coating agent according to any one of claims 1 to 3, which is an emulsified composition. The coating agent according to any one of claims 1 to 4, wherein a hard surface is the target surface. The coating agent according to any one of claims 1 to 5, which is for a mold release agent. A coating film obtained by drying the coating agent according to any one of claims 1 to 6. The coating film according to claim 7, which is a film for a mold release agent.