JP7280220B2 - Composition for promoting defoaming - Google Patents

Description

TECHNICAL FIELD The present invention relates to a composition for promoting defoaming.

Many industrial products such as concrete, ceramics, plastics, resins, and foodstuffs are produced by filling uncured curable compositions into molds and curing them by drying or chemical reaction in the post-process to obtain cured products. Manufactured by One of the factors that determine the value of the cured product is the appearance of the surface. This literally means the beauty of the surface of the cured product, and the more excellent the surface beauty, the higher the product value tends to be evaluated.

One of the reasons for impairing the appearance of the surface of the cured body is air bubbles exposed on the surface of the cured body. This is a defect that air bubbles entrained in the composition before curing appear on the surface during curing. In order to reduce defects caused by such air bubbles, countermeasures have been taken, such as adding an antifoaming agent that promotes breakage, coalescence and floating of air bubbles, and providing a separate process for repair after curing. However, the addition of antifoaming agents is troublesome and may adversely affect the physical properties of the curable composition. Furthermore, use of an antifoaming agent is not desirable when it is desired to secure the amount of air in the cured product. In addition, it is not preferable from the viewpoint of securing costs and manpower to repair defects by providing a separate process after curing.

On the other hand, an agent for improving the appearance of the surface of the curable composition and a mold release agent to be applied to the mold used when curing the curable composition have also been proposed. For example, Patent Document 1 discloses a surface aesthetic improver containing a specific amide. Further, Patent Document 2 discloses a surface aesthetic improver for hydraulic compositions containing a specific fatty acid alkanolamide, a polycarboxylic acid-based dispersant and a specific solvent. Further, Patent Document 3 discloses a mold release agent containing a specific fatty acid alkanolamide.

Japanese Unexamined Patent Application Publication No. 2007-77008 JP 2019-104673 A JP 2018-130957 A

The present invention provides a defoaming promoting composition for promoting defoaming of foam-containing substances, such as foam-containing fluids.

The present invention relates to a defoaming promoting composition containing (A) hydrophobically modified cellulose fibers [hereinafter referred to as component (A)].

The present invention also relates to a method for controlling fluid foaming, comprising contacting a fluid containing bubbles with the composition for promoting defoaming of the present invention, and suppressing appearance of bubbles on the surface of the fluid at the contact position.

The present invention also relates to a method for producing a cured body, comprising bringing a curable composition containing air bubbles into contact with a support coated with the composition for promoting defoaming of the present invention and curing the composition.

In the present invention, a hydraulic composition containing air bubbles is filled in a mold coated with the defoaming accelerating composition of the present invention, cured, and then the resulting cured body is removed from the mold. , relates to a method for producing a hardened body of a hydraulic composition.

The present invention also provides a curable composition containing air bubbles, which is cured by contacting it with the coating film obtained from the defoaming promoting composition of the present invention to reduce air bubble traces on the surface of the cured body. The present invention relates to a method for improving the surface appearance of a cured body.

INDUSTRIAL APPLICABILITY According to the present invention, there is provided a defoaming promoting composition that promotes defoaming of a substance containing bubbles, such as a fluid containing bubbles.

The present inventors have found that when a defoaming promoting composition containing the hydrophobically modified cellulose fibers of the component (A) is brought into contact with a fluid containing bubbles, defoaming from the fluid is promoted. Found it. More specifically, for example, when the composition for promoting defoaming of the present invention is applied to a mold, and the mold is filled with a curable composition and cured, the surface bubble marks of the cured product are reduced. It was found that the surface aesthetics were improved. Although the reason why such an effect is exhibited is not necessarily clear, it is presumed as follows.
When the composition for promoting defoaming of the present invention contacts with a fluid containing air bubbles, such as a hydraulic composition, the surface free energy is reduced, thereby reducing the adhesive force of the fluid. This means that the fluid is more likely to move at the site of contact with the defoaming promoting composition of the present invention, and as a result, the filling of the mold or the like with the fluid is improved. At this time, since the composition for promoting defoaming of the present invention provides a smooth and dense surface, the filling property is further improved, and the bubbles of the fluid are more likely to move inside the fluid than at the contact sites. For example, when the hydraulic composition is filled in a mold coated with the defoaming promoting composition of the present invention, the surface of the hydraulic composition, that is, the mold applied to the mold due to such an action mechanism It is thought that the air bubbles appearing at the site of contact with the composition of the invention sequentially move into the hydraulic composition, reduce air bubble traces on the surface, and improve the aesthetic appearance of the surface.
In the case of producing a fluid cured body using the defoaming promoting composition of the present invention, if the defoaming promoting composition of the present invention migrates and adheres to the cured body, An effect of imparting antifouling properties to the surface of the cured product can be expected. That is, for example, when the composition for promoting defoaming of the present invention is used to produce a cured product of a hydraulic composition, the composition for promoting defoaming of the present invention adheres to the surface of the cured product and is cured. In addition, antifouling properties are imparted to suppress the adhesion of dust and the like that adhere during storage of the cured body, and it is expected that the surface appearance will be maintained.

<Composition for promoting defoaming>
Component (A) is a hydrophobically modified cellulose fiber. Hydrophobically modified cellulose fibers are, for example, fibers made of cellulose to which hydrophobic groups are attached.

Component (A) preferably exhibits dispersibility in the oil of component (B), which will be described later. Having dispersibility in oil means, for example, measuring the viscosity of a mixed liquid of oil and the target hydrophobically modified cellulose fiber with an E-type viscometer (25 ° C., 1 rpm, after 1 minute, standard cone rotor, rotor code: 01 ) means that thickening is observed when measured using For example, as the hydrophobically-modified cellulose in the present invention, the viscosity of the dispersion liquid prepared by adjusting the concentration of cellulose fibers to 0.5% by mass in squalane, which is a representative example of oil, is 50 mPa·s or more after refining treatment. is preferable. In addition, the miniaturization treatment can be performed by a method described later.

The crystallinity of component (A) is preferably 10% or more from the viewpoint of surface property, film-forming property and workability. The surface properties, film-forming properties and workability are physical properties when the composition for promoting defoaming of the present invention is applied to a support or the like (the same shall apply hereinafter). Moreover, from the viewpoint of raw material availability, it is preferably 90% or less. In this specification, the crystallinity of cellulose is the cellulose type I crystallinity calculated from the diffraction intensity value by the X-ray diffraction method, and can be measured according to the method described in Examples below. The cellulose type I is a crystalline form of natural cellulose, and the degree of cellulose type I crystallinity means the ratio of the amount of crystalline regions to the entire cellulose. The presence or absence of the cellulose type I crystal structure can be determined by the presence of a peak at 2θ=22.6° in X-ray diffraction measurement.

Preferred ranges of the average fiber diameter, average fiber length, and average aspect ratio of component (A) are the average fiber diameter, average fiber length, and average aspect ratio of the fine cellulose fibers described later, from the viewpoint of surface properties, film-forming properties, and processability. It is the same as the preferred range of the ratio. Also, it can be obtained by the measuring method described in the examples below.

Component (A) includes, for example, hydrophobically-modified cellulose fibers (A) in which modifying groups are bonded to the anionic groups of cellulose fibers having anionic groups (hereinafter also referred to as "anion-modified cellulose fibers"), Hydrophobic modified cellulose fibers (B) in which modifying groups are ether-bonded to hydroxyl groups on the surface of cellulose fibers (hereinafter, also referred to as "etherified cellulose fibers"), which are preferable from the viewpoint that the effects of the present invention can be exhibited more effectively. is the hydrophobically modified cellulose fiber (A).

More specifically, component (A) includes hydrophobically modified cellulose fibers in which modifying groups are bonded to hydroxyl groups of cellulose fibers.
Component (A) also includes hydrophobically modified cellulose fibers in which modifying groups are bonded to the anionic groups of cellulose fibers having anionic groups.
Component (A) also includes hydrophobically modified cellulose fibers in which one or more modified groups selected from anionic groups and hydroxyl groups of cellulose fibers having anionic groups are bonded.
These modifying groups may be hydrophobic modifying groups.

(cellulose fiber)
The cellulose fiber as the raw material of the hydrophobically modified cellulose fiber is preferably a natural cellulose fiber from an environmental point of view. For example, wood pulp such as softwood pulp and hardwood pulp; cotton pulp such as cotton linter and cotton lint; non-wood pulp such as pulp and bagasse pulp; bacterial cellulose; and the like.

The average fiber diameter of the raw material cellulose fibers is not particularly limited, but from the viewpoint of handleability and cost, it is preferably 1 μm or more, more preferably 5 μm or more, still more preferably 15 μm or more, and preferably 300 μm. or less, more preferably 100 μm or less, and still more preferably 60 μm or less.

The average fiber length of the raw cellulose fiber is not particularly limited, but from the viewpoint of availability and cost, it is preferably 100 µm or more, more preferably 500 µm or more, and still more preferably 1,000 µm or more. is 5,000 μm or less, more preferably 4,000 μm or less, and still more preferably 3,000 μm or less. The average fiber diameter and average fiber length of the raw material cellulose fibers can be measured according to the methods described in Examples below.

<Hydrophobic modified cellulose fiber (A)>
The hydrophobically-modified cellulose fiber (A) in the present invention is a cellulose fiber in which a compound for introducing a modifying group is bonded to the anionic group of the anion-modified cellulose fiber.

(Anion modified cellulose fiber)
The anionic group contained in the anion-modified cellulose fiber includes, for example, a carboxy group, a sulfonic acid group, a phosphoric acid group, and the like, and from the viewpoint of efficiency of introduction into the cellulose fiber, the carboxy group is preferred. Examples of ions (counter ions) that form pairs of anionic groups in anion-modified cellulose fibers include, for example, metal ions such as sodium ions, potassium ions, calcium ions and aluminum ions generated in the presence of alkali during production, and these metal ions. Examples include protons generated by substituting ions with acids.

(Anionic group content)
The anionic group content in the anion-modified cellulose fiber used in the present invention is preferably 0.1 mmol/g or more, more preferably 0.4 mmol/g or more, and even more preferably, from the viewpoint of introducing a modifying group. It is 0.6 mmol/g or more, more preferably 0.8 mmol/g or more. In addition, from the viewpoint of improving handleability, it is preferably 3 mmol/g or less, more preferably 2 mmol/g or less, and still more 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 below.

In addition, the preferred ranges of the average fiber diameter, average fiber length and average aspect ratio of the anion-modified cellulose fibers are the same as those of the hydrophobically-modified cellulose fibers described above, and the preferred ranges of the average fiber diameter and average fiber length of the fine cellulose fibers described later. are the same. Also, it can be obtained by the measuring method described in the examples below.

(Step of introducing anionic group)
The anion-modified cellulose fiber used in the present invention can be obtained by subjecting the target cellulose fiber to an oxidation treatment or an anionic group addition treatment to introduce at least one or more anionic groups for anion modification. .
Cellulose fibers to be anion-modified include raw material cellulose fibers. From the viewpoint of dispersibility (hereinafter also referred to as dispersibility) in the composition for promoting defoaming, the average fiber length of 1 μm or more obtained by shortening the raw material cellulose fiber by alkali hydrolysis treatment, acid hydrolysis treatment, etc. and it is preferable to use cellulose fibers having a diameter of 1,000 μm or less.

Hereinafter, more specific explanation will be given separately for (i) the case of introducing a carboxy group as an anionic group into cellulose fibers and (ii) the case of introducing a sulfonic acid group or a phosphoric acid group as an anionic group into cellulose fibers. do.

(i) When a carboxy group is introduced as an anionic group into cellulose fiber As a method for introducing a carboxy group as an anionic group into cellulose fiber, for example, a method of oxidizing the hydroxyl group of cellulose to convert it to a carboxy group, or a method of converting the hydroxyl group of cellulose into a carboxy group, A method of reacting at least one selected from the group consisting of compounds having a carboxyl group in a hydroxyl group, acid anhydrides of compounds having a carboxyl group, and derivatives thereof may be mentioned.

(oxidized cellulose fiber)
Cellulose fibers having carboxy groups are referred to herein as "oxidized cellulose fibers". Oxidized cellulose fibers, for example, use 2,2,6,6,-tetramethyl-1-piperidine-N-oxyl (TEMPO) as a catalyst, further oxidizing agents such as sodium hypochlorite, sodium bromide, etc. can be produced by applying a method of oxidizing hydroxyl groups of cellulose fibers to carboxy groups by using a bromide of . For more details, the method described in JP-A-2011-140632 can be referred to, and furthermore, by performing additional oxidation treatment or reduction treatment, oxidized cellulose fibers from which aldehydes have been removed can be prepared. Oxidized cellulose fibers are preferable to other anion-modified cellulose fibers from the viewpoint of surface properties, film formability and workability.

(ii) In the case of introducing a sulfonic acid group or a phosphoric acid group as an anionic group into cellulose fibers As a method for introducing a sulfonic acid group as an anionic group into cellulose fibers, there is a method of adding sulfuric acid to cellulose fibers and heating the same. mentioned.

Methods for introducing a phosphate group as an anionic group into cellulose fibers include a method of mixing powder or an aqueous solution of phosphoric acid or a phosphoric acid derivative with cellulose fibers in a dry or wet state, or a method of adding phosphoric acid to a dispersion of cellulose fibers. A method of adding an aqueous solution of an acid or a phosphoric acid derivative can be used. When these methods are employed, dehydration treatment, heat treatment, and the like are generally performed after mixing or adding a powder or aqueous solution of phosphoric acid or a phosphoric acid derivative.

(Modifying group)
As used herein, the bonding of the modifying group in the hydrophobically-modified cellulose fiber (A) means that the modifying group is ionic and/or covalently bonded to the anionic group, preferably to the carboxyl group, on the surface of the cellulose fiber. means that The mode of bonding to the anionic group includes ionic bonding and covalent bonding. Examples of covalent bonds here include amide bonds, ester bonds, and urethane bonds. is an amide bond. From the viewpoint of workability and stability, the hydrophobically modified cellulose fiber (A) in the present invention is obtained by ionically bonding and/or amide bonding a compound for introducing a modifying group to the carboxyl group already present on the surface of the cellulose fiber. Those obtained by

(Compound for introducing modifying group)
As the compound for introducing the modifying group, any compound can be used as long as it can introduce the modifying group described below. In the case of ionic bonding, any of primary amines, secondary amines, tertiary amines, quaternary ammonium compounds and phosphonium compounds may be used. Among these, primary amines, secondary amines, tertiary amines and quaternary ammonium compounds are preferred from the viewpoint of dispersibility. From the viewpoint of reactivity, the anion component of the ammonium compound or phosphonium compound is preferably halogen ion such as chloride ion or bromide ion, hydrogen sulfate ion, perchlorate ion, tetrafluoroborate ion, hexa Examples include fluorophosphate ions, trifluoromethanesulfonate ions, and hydroxy ions, more preferably hydroxy ions. In the case of covalent bonding, the following can be used depending on the functional group to be substituted.

In the modification to the carboxy group, in the case of an amide bond, either primary amine or secondary amine may be used. In the case of an ester bond, alcohols such as butanol, octanol, and dodecanol are exemplified. For urethane bonds, isocyanate compounds are preferred.

A hydrocarbon group or the like can be used as the modifying group in the hydrophobically modified cellulose fiber (A). These may be bonded (introduced) to the cellulose fibers either singly or in combination of two or more.

(hydrocarbon group)
The hydrocarbon group includes, for example, a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, a cyclic saturated hydrocarbon group and an aromatic hydrocarbon group, from the viewpoint of suppressing side reactions and from the viewpoint of stability. Therefore, it is preferably a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group or an aromatic hydrocarbon group. The number of carbon atoms in the hydrocarbon group is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, from the viewpoint of surface properties and film-forming properties, and from the same viewpoint, preferably 30 or less. , more preferably 24 or less, and still more preferably 18 or less.

A chain saturated hydrocarbon group may be linear or branched. The number of carbon atoms in the chain saturated hydrocarbon group is preferably 1 or more, more preferably 2 or more, still more preferably 3 or more, and still more preferably 6 in one modifying group from the viewpoint of surface properties and film-forming properties. 8 or more, more preferably 8 or more. From the same point of view, it is preferably 30 or less, more preferably 24 or less, even more preferably 18 or less, still more preferably 16 or less. In addition, hereinafter, the number of carbon atoms in a hydrocarbon group means the number of carbon atoms in one modifying group.

Specific examples of chain 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, etc. and from the viewpoint of film-forming properties, preferably 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 octyl group, 2-ethylhexyl group, nonyl group, decyl group, dodecyl group, tridecyl group, tetradecyl group, octadecyl group, docosyl group and octacosanyl group. These may be introduced singly or in an arbitrary ratio of two or more.

A chain unsaturated hydrocarbon group may be linear or branched. The number of carbon atoms in the chain unsaturated hydrocarbon group is preferably 1 or more, more preferably 2 or more, and still more preferably 3 or more, from the viewpoint of handleability. From the viewpoint of availability, it is preferably 30 or less, more preferably 18 or less, even more preferably 12 or less, and even more preferably 8 or less.

Specific examples of chain unsaturated hydrocarbon groups include ethylene group, propylene group, butene group, isobutene group, isoprene group, pentene group, hexene group, heptene group, octene group, nonene group, decene group and dodecene group. . group, nonene group, decene group and dodecene group. These may be introduced singly or in an arbitrary ratio of two or more.

The number of carbon atoms in the cyclic saturated hydrocarbon group is preferably 3 or more, more preferably 4 or more, and still more preferably 5 or more, from the viewpoint of handleability. From the standpoint of availability, it is preferably 20 or less, more preferably 16 or less, even more preferably 12 or less, still more preferably 8 or less.

Specific examples of cyclic saturated hydrocarbon groups include cyclopropane, cyclobutyl, cyclopentane, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclododecyl, and cyclotridecyl groups. , cyclotetradecyl group, cyclooctadecyl group and the like, and from the viewpoint of surface properties and film-forming properties, preferably cyclopropane group, cyclobutyl group, cyclopentane group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclononyl group , a cyclodecyl group, and a cyclododecyl group. These may be introduced singly or in an arbitrary ratio of two or more.

The aromatic hydrocarbon group is, for example, selected from the group consisting of aryl groups and aralkyl groups. The aryl group and aralkyl group may be substituted or unsubstituted in the aromatic ring itself.

The total carbon number of the aryl group may be 6 or more, and from the viewpoint of surface properties and film-forming properties, it is preferably 24 or less, more preferably 20 or less, even more preferably 14 or less, still more preferably 12 or less, and still more preferably. is 10 or less.

The total carbon number of the aralkyl group is 7 or more, preferably 8 or more from the viewpoint of surface properties and film-forming properties, and from the same viewpoint, preferably 24 or less, more preferably 20 or less, and still more preferably. is 14 or less, more preferably 13 or less, still more preferably 11 or less.

Examples of the aryl group include phenyl, naphthyl, anthryl, phenanthryl, biphenyl, triphenyl, terphenyl, and groups in which these groups are substituted with substituents described later. Each species may be introduced singly or two or more species may be introduced in an arbitrary ratio. Among them, a phenyl group, a biphenyl group, and a terphenyl group are preferable from the viewpoint of surface properties and film-forming properties.

Aralkyl groups include, for example, a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, a phenylheptyl group, a phenyloctyl group, and groups in which the aromatic groups of these groups are substituted with the substituents described later. and the like, and these may be introduced singly or in combination of two or more in an arbitrary ratio. Among them, a benzyl group, a phenethyl group, a phenylpropyl group, a phenylpentyl group, a phenylhexyl group, and a phenylheptyl group are preferable from the viewpoint of surface properties and film-forming properties.

Primary amines, secondary amines, tertiary amines, quaternary ammonium compounds, phosphonium compounds, acid anhydrides, and isocyanate compounds for introducing the hydrocarbon group are commercially available products or known methods. can be prepared according to

The primary to tertiary amines preferably have 1 or more carbon atoms, more preferably 2 or more carbon atoms, and still more preferably 3 or more carbon atoms from the viewpoint of workability and stability. The number is preferably 20 or less, more preferably 18 or less, and still more preferably 16 or less (excluding amino-modified silicone compounds). Specific examples of primary to tertiary amines include ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, dihexylamine, octylamine, dioctylamine, trioctylamine, and dodecylamine. , didodecylamine, stearylamine, distearylamine, monoethanolamine, diethanolamine, triethanolamine, aniline and benzylamine, and amino-modified silicone compounds. Examples of quaternary ammonium compounds include tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetraethylammonium chloride, tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), tetra butylammonium chloride, lauryltrimethylammonium chloride, dilauryldimethylchloride, stearyltrimethylammonium chloride, distearyldimethylammonium chloride, cetyltrimethylammonium chloride and alkylbenzyldimethylammonium chloride. Among these, propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, dihexylamine, octylamine, dioctylamine, trioctylamine, dodecylamine and didodecyl are preferred from the viewpoint of workability and stability. Amine, distearylamine, amino-modified silicone compound, tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide (TPAH), aniline, more preferably propylamine, dodecylamine, amino-modified Silicone compounds, tetrabutylammonium hydroxide (TBAH), aniline, and more preferably amino-modified silicone compounds.

Among these compounds, hydrophobically modified cellulose fibers obtained by using amino-modified silicone compounds are especially useful as raw materials for films of the composition of the present invention, especially coating films. Accordingly, one aspect of the present invention provides a hydrophobically modified cellulose fiber in which an amino-modified silicone compound is bound to an anionic group of anionically modified cellulose fiber. A membrane containing such hydrophobically modified cellulose fibers can exhibit excellent defoaming properties.

(Amino-modified silicone compound)
As the amino-modified silicone compound, an amino-modified silicone compound having a kinematic viscosity at 25° C. of 10 mm ² /s or more and 20,000 mm ² /s or less and an amino equivalent of 400 g/mol or more and 8,000 g/mol or less is preferable. .

The kinematic viscosity at 25° C. can be determined with an Ostwald viscometer, and from the viewpoint of workability and stability, it is more preferably 200 mm ² /s or more, still more preferably 500 mm ² /s or more, and more preferably 10 ,000 mm ² /s or less, more preferably 5,000 mm ² /s or less.

In addition, from the viewpoint of stability, 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 preferably 8,000 g/mol or less, more preferably 5 ,000 g/mol or less, more preferably 3,000 g/mol or less. The amino equivalent is the molecular weight per nitrogen atom, and is determined by amino equivalent (g/mol)=mass average molecular weight/number of nitrogen atoms per molecule. Here, the mass average molecular weight is a value determined by gel permeation chromatography using polystyrene as a standard substance, and the number of nitrogen atoms can be determined by elemental analysis.

Specific examples of amino-modified silicone compounds include compounds represented by 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 from the viewpoint of surface properties and film-forming properties, preferably methyl or hydroxy group. R ^2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group and a hydrogen atom, preferably a methyl group or a hydroxy group from the viewpoint of surface properties and film-forming properties. B represents a side chain having at least one amino group, and R ^3a represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. x and y each represent an average degree of polymerization, and are selected so that the kinematic viscosity at 25° C. and amino equivalent of the compound are within the above ranges. R ^1a , R ^2a and R ^3a may be the same or different, and a plurality of R ^2a may be the same or different. ]

In the compound of general formula (a1), x is preferably 10 or more, more preferably 20 or more, still more preferably 30 or more, and preferably 10,000 or less, more preferably from the viewpoint of surface properties and film-forming properties. The number is 5,000 or less, more preferably 3,000 or less. y is preferably 1 or more, and preferably 1,000 or less, more preferably 500 or less, still more preferably 200 or less. The weight average molecular weight of the compound of general formula (a1) is preferably 2,000 or more, more preferably 5,000 or more, still more preferably 8,000 or more, and preferably 1,000,000 or less, more preferably 100,000 or less, more preferably 50,000 or less.

In the general formula (a1), examples of the side chain B having an amino group include the following.
_{-C3H6 - NH2
-C3H6} - _NH - _{C2H4 - NH2}
—C ₃ H ₆ —NH—[C ₂ H ₄ —NH]e—C ₂ H ₄ —NH _{2
-C3H6 -} NH( _CH3 )
_-C3H6 - _NH - _{C2H4 -} NH( _CH3 )
—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
-C3H6 - _{N ( CH3} ) _-C2H4 -N( _CH3 ) 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 from 1 to 30, respectively.)

The amino-modified silicone compound used in the present invention is obtained by, for example, hydrolyzing a hydrolyzate obtained by hydrolyzing an organoalkoxysilane represented by the general formula (a2) with an excess amount of water, and dimethylcyclopolysiloxane with sodium hydroxide. It can be produced by heating to 80 to 110 ° C. to cause an equilibrium reaction using a basic catalyst such as (See JP-A-53-98499).
_H2N ( _CH2 ) _2NH ( _CH2 ) _3Si ( _CH3 )( _OCH3 ) ₂ (a2)

In addition, from the viewpoint of defoaming properties, the amino-modified silicone compound is preferably a monoamino-modified silicone having one amino group in one of the side chains B and two amino groups in one of the side chains B. one or more selected from the group consisting of diamino-modified silicones, more preferably a compound in which the side chain B having an amino group is represented by -C ₃ H ₆ -NH ₂ (hereinafter referred to as component (a1-1) and compounds in which the 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 component (a1-2)]. That's it.

BY16-213 (kinematic viscosity: 55, amino equivalent: 2700) and BY16-853U (kinematic viscosity: 14, amino equivalent: 450) are more preferred as component (a1-1).
(a1-2) components include SF8417 (kinematic viscosity: 1200, amino equivalent: 1700), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), FZ-3760 (kinematic viscosity: 220, amino equivalent: 1600 ) is more preferred.

The average bonding amount of the modifying group in the hydrophobically-modified cellulose fiber (A) is preferably 0.01 mmol/g or more, more preferably 0.05 mmol/g or more per cellulose fiber, from the viewpoint of surface properties and film-forming properties. , more preferably 0.1 mmol/g or more, still more preferably 0.3 mmol/g or more, still more preferably 0.5 mmol/g or more. Further, from the viewpoint of reactivity, it is preferably 3 mmol/g or less, more preferably 2.5 mmol/g or less, still more preferably 2 mmol/g or less, still more preferably 1.8 mmol/g or less. , more preferably 1.5 mmol/g or less. Here, when arbitrary two or more types of modifying groups are simultaneously introduced into the cellulose fiber as modifying groups, the average bonding amount of the modifying groups is such that the total amount of the modified groups introduced is within the above range. preferable.

The introduction rate of the modifying group in the hydrophobically-modified cellulose fiber (A) is preferably 10% or more, more preferably 30% or more, from the viewpoint of surface properties and film-forming properties for any modifying group. It is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, and from the viewpoint of reactivity, preferably 99% or less, more preferably 97% or less, and further It is preferably 95% or less, more preferably 90% or less. Here, when arbitrary two or more types of modifying groups are simultaneously introduced into the cellulose fibers as modifying groups, the total introduction rate is preferably within the above range, as long as the upper limit is not over 100%.

The modifying group may further have a substituent. For example, in the case of a hydrocarbon group, the total number of carbon atoms of the entire modifying group including the substituent is preferably within the above range. Examples of substituents include methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, sec-butoxy, tert-butoxy, pentyloxy, isopentyloxy, and hexyloxy groups. C1-C6 alkoxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl group alkoxy-carbonyl group having 1 to 6 carbon atoms in alkoxy group such as isopentyloxycarbonyl group; halogen atom such as fluorine atom, chlorine atom, bromine atom and iodine atom; acetyl group and propionyl group having 1 carbon atom aralkyl group; aralkyloxy group; alkylamino group having 1 to 6 carbon atoms; and dialkylamino group having alkyl group having 1 to 6 carbon atoms. In addition, the above-described hydrocarbon group itself may be bonded as a substituent.

In the present specification, the average bonding amount and introduction rate of the modifying group in the hydrophobically-modified cellulose fiber (A) can be adjusted by the amount and type of compound added for introducing the modifying group, the reaction temperature, the reaction time, the solvent, and the like. can be done. The average binding amount (mmol/g) and introduction rate (%) of modifying groups refer to the amount and ratio of modifying groups introduced to the anionic groups on the surface of the hydrophobically-modified cellulose fibers (A). The anionic group content of the hydrophobically modified cellulose fiber (A) can be calculated by measuring according to known methods (eg, titration, IR measurement, etc.). The average bonding amount and introduction rate of modifying groups in the hydrophobically-modified cellulose fiber (A) are calculated, for example, by the methods described in Examples.

[Method for producing hydrophobically modified cellulose fiber (A)]
The hydrophobically-modified cellulose fiber (A) used in the present invention can be produced by any known method without particular limitation, as long as the modification group can be introduced into the anion-modified cellulose fiber. The anion-modified cellulose fiber referred to here is subjected to a known method, for example, the method described in Japanese Patent Application Laid-Open No. 2011-140632, and is further subjected to the above-described additional oxidation treatment or reduction treatment to remove aldehyde. can be prepared as oxidized cellulose fibers.

As a specific production method, the following two aspects can be mentioned depending on how the modifying group is introduced into the oxidized cellulose fiber. That is, there are an aspect (aspect A) in which the modifying group is bound to the oxidized cellulose fiber by an ionic bond, and an aspect (aspect B) in which the modifying group is bonded to the oxidized cellulose fiber by a covalent bond. In addition, as a covalent bond, the case of an amide bond is shown below.
[Mode A]
Step (1): Oxidizing natural cellulose fibers in the presence of an N-oxyl compound to obtain oxidized cellulose fibers Step (2A): The oxidized cellulose fibers obtained in Step (1) and for introducing a modifying group A step of mixing with a compound [embodiment B]
Step (1): Oxidizing natural cellulose fibers in the presence of an N-oxyl compound to obtain oxidized cellulose fibers Step (2B): The oxidized cellulose fibers obtained in Step (1) and for introducing a modifying group The step of amidating the compound of

The method for introducing the modifying group can be performed, for example, by referring to the method described in JP-A-2015-143336 for Aspect A and the method described in JP-A-2015-143337 for Aspect B. Further, in the present invention, a method (first production mode) in which the step (2A or 2B) is performed after the step (1) is followed by the step (2A or 2B) by performing the step (1), followed by the step (1) in order. A method of obtaining fine cellulose fibers by performing the step (2A or 2B) and then performing the refining step (second manufacturing mode) may be performed. In addition, the cellulose fiber after the refining treatment may be particularly referred to as "fine cellulose fiber".

Hereinafter, a method for producing fine cellulose fibers will be described based on the first production mode of Mode A.

[Step (1)]
Step (1) is a step of oxidizing natural cellulose fibers in the presence of an N-oxyl compound to obtain oxidized cellulose fibers. Specifically, for natural cellulose fibers, the oxidation treatment step described in JP-A-2015-143336 or JP-A-2015-143337 (for example, 2,2,6,6-tetramethylpiperidine-1-oxyl (Oxidation treatment using TEMPO) and purification step (if necessary), oxidized cellulose fibers having a carboxy group content of preferably 0.1 mmol/g or more can be obtained. By oxidizing cellulose fibers using TEMPO as a catalyst, the hydroxymethyl group (-CH2OH) at the C6 position of the cellulose structural unit is selectively converted to a carboxy group. In particular, this method is advantageous in that it is excellent in the selectivity of the hydroxyl group at the C6 position to be oxidized on the surface of the raw material cellulose fiber and that the reaction conditions are mild.

(Miniaturization process)
Next, a step of refining the oxidized cellulose fibers obtained in step (1) is performed after the purification step (which may be performed if necessary) to obtain fine oxidized cellulose fibers. In the micronization step, it is preferable to disperse the oxidized cellulose fibers that have undergone the refining step in a solvent and perform the micronization treatment.

Solvents as dispersion media include water, alcohols having 1 to 6 carbon atoms, preferably 1 to 3 carbon atoms such as methanol, ethanol and propanol; ketones having 3 to 6 carbon atoms such as acetone, methyl ethyl ketone and methyl isobutyl ketone. linear or branched saturated or unsaturated hydrocarbons having 1 to 6 carbon atoms; aromatic hydrocarbons such as benzene and toluene; halogenated hydrocarbons such as methylene chloride and chloroform; lower hydrocarbons having 2 to 5 carbon atoms Alkyl ethers; polar solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, dimethylsulfoxide, and diesters of succinic acid and triethylene glycol monomethyl ether; These can be used alone or in combination of two or more. A polar solvent such as a lower alkyl ether of 1 to 5, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, or methyl triglycol diester succinate is preferred, and water is more preferred from the viewpoint of reducing environmental load. The amount of the solvent used is not particularly limited as long as it is an effective amount capable of dispersing the oxidized cellulose fibers, but it is preferably 1-fold or more by mass, more preferably 200-fold or more by mass, and preferably 200-fold or more by mass of the oxidized cellulose fibers. is 500 times by mass or less, more preferably 200 times by mass or less.

A well-known dispersing machine is preferably used as a device used in the refining treatment. For example, disaggregator, beater, low pressure homogenizer, high pressure homogenizer, grinder, cutter mill, ball mill, jet mill, short screw extruder, twin screw extruder, pressure kneader, Banbury mixer, Laboplastomill, ultrasonic stirrer, household A juicer mixer or the like can be used. In addition, the solid content of the reactant fiber in the pulverization treatment is preferably 50% by mass or less.

Thus, cellulose fibers can be obtained in which the hydroxyl group at the C6 position of the cellulose fiber constitutional unit is selectively oxidized to a carboxy group via an aldehyde group.

[Step (2A)]
In the first production mode, the step (2A) is a step of mixing the oxidized cellulose fibers obtained through the above steps with a compound for introducing a modifying group to obtain a hydrophobically modified cellulose fiber (A). be. Specifically, oxidized cellulose fibers and a compound for introducing a modifying group may be mixed in a solvent, and can be produced, for example, according to the method described in JP-A-2015-143336.

Examples of the compound for introducing the modifying group used in step (2A) include those described above.

The amount of the compound to be used can be determined according to the desired bonding amount of the modifying group in the hydrophobically modified cellulose fiber (A). However, it is preferably 0.01 mol or more, more preferably 0.1 mol or more, and from the viewpoint of product purity, it is used in an amount that is preferably 50 mol or less, more preferably 20 mol or less, and still more preferably 10 mol or less. In addition, the amount of the compound included in the above range may be subjected to the reaction all at once, or may be divided and subjected to the reaction. When the compound is a monoamine, the above amino group and amine are the same.

As the solvent, it is preferable to select a solvent in which the compound to be used is dissolved. Acetone, ethyl acetate, dimethylformamide, methyl isobutyl ketone, acetonitrile, dimethyl sulfoxide, dimethylacetamide, 1-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, hexane, cyclohexane, cyclohexanone, 1,4- Dioxane, chloroform, dichloromethane, diethyl ether and mixtures thereof.

The temperature during mixing is preferably 0° C. or higher, more preferably 5° C. or higher, and even more preferably 10° C. or higher, from the viewpoint of the reactivity of the raw materials for obtaining the compound. From the viewpoint of product quality such as coloring, the temperature is preferably 50° C. or lower, more preferably 40° C. or lower, and even more preferably 30° C. or lower. The mixing time can be appropriately set according to the type of the compound and solvent used, but from the viewpoint of the reactivity of the raw materials for obtaining the compound, it is preferably 0.01 hour or longer, more preferably 0.1 hour or longer. , more preferably 1 hour or more, preferably 48 hours or less, more preferably 24 hours or less from the viewpoint of productivity.

After the hydrophobically modified cellulose fiber (A) is produced, post-treatment may be carried out as appropriate in order to remove unreacted compounds and the like. As the post-treatment method, for example, filtration, centrifugation, dialysis or the like can be used.

As for the production method of the aspect B, the step (1) can be performed in the same manner as the aspect A, so the step (2B) in the first production mode will be described below. Further, for example, it can be produced by the method described in JP-A-2013-151661.

In both Mode A and Mode B, in the second manufacturing mode, the steps described above are performed in the order of step (1), step (2A) or step (2B), and the miniaturization step. , can be performed in the same manner as in the first manufacturing mode.

Moreover, the hydrophobically-modified cellulose fiber obtained by combining the aspects A and B may be used, that is, the hydrophobically-modified cellulose fiber having a modifying group linked via an ionic bond and a modifying group linked via an amide bond. There may be. In this case, either step (2A) or step (2B) may be performed first.

Thus, hydrophobically modified cellulose fibers can be obtained in which modifying groups are linked to cellulose fibers via ionic and/or covalent bonds.

<Hydrophobic modified cellulose fiber (B) (etherified cellulose fiber)>
The hydrophobically modified cellulose fiber (B) (also referred to as etherified cellulose fiber) in the present invention is characterized in that a modifying group is bonded to the surface of the cellulose fiber via an ether bond, and preferably has a cellulose type I crystal structure. It is. In this specification, the term "bonded via an ether bond" means a state in which a modifying group reacts with a hydroxyl group on the surface of the cellulose fiber to form an ether bond.

The modifying group in the etherified cellulose fiber is preferably a hydrocarbon group which may have a substituent. Here, in the hydrocarbon group which may have a substituent, the hydrocarbon group includes a saturated or unsaturated linear or branched aliphatic hydrocarbon group, an aromatic hydrocarbon group such as a phenyl group, or An alicyclic hydrocarbon group such as a cyclohexyl group can be mentioned. In the hydrocarbon group which may have a substituent in the present invention, examples of the substituent include a halogen atom, an oxyalkylene group such as an oxyethylene group, and a hydroxyl group.

As a preferred embodiment (referred to as "embodiment 1") of such etherified cellulose fibers, for example, a substituent selected from a substituent represented by the following general formula (1) and a substituent represented by the following general formula (2) 1 or 2 or more substituents are bonded to the cellulose fiber via an ether bond and have a cellulose type I crystal structure.
—CH ₂ —CH(R ₀ )—R ₁ (1)
—CH ₂ —CH(R ₀ ) —CH ₂ —(OA) _n —OR ₁ (2)
[Wherein, R ₀ in the general formulas (1) and (2) represents a hydrogen atom or a hydroxyl group, and each R ₁ independently represents a linear or branched alkyl having 3 to 30 carbon atoms, In the general formula (2), n is a number of 0 or more and 50 or less, and A is a linear or branched divalent saturated hydrocarbon group having 1 or more and 6 or less carbon atoms. ]

Specific examples of aspect 1 include etherified cellulose fibers represented by the following general formula (4).

[In the formula, R is the same or different and represents hydrogen or a substituent selected from the substituent represented by the general formula (1) and the substituent represented by the general formula (2), m is 20 Integers of greater than or equal to 3000 and less than or equal to 3000 are preferred, except when all R are hydrogen at the same time]

The etherified cellulose fiber represented by general formula (4) has a repeating structure of cellulose units into which the substituents have been introduced. As the repeating number of the repeating structure, m in the general formula (4) is preferably an integer of 20 or more and 3000 or less from the viewpoint of surface properties and film-forming properties.

(Hydrocarbon group optionally having a substituent)
In the etherified cellulose fiber of aspect 1, one or more substituents selected from the substituents represented by the above general formula (1) and the following general formula (2) are introduced singly or in any combination. be done. Even if the substituent to be introduced is any one of the above substituent groups, the same substituent may be introduced in each substituent group or two or more of them may be introduced in combination.

From the viewpoint of workability and stability, R ₀ in general formulas (1) and (2) is preferably a hydroxyl group.

The number of carbon atoms in R ₁ in general formula (1) is preferably 25 or less from the viewpoint of surface properties and film-forming properties. Specifically, propyl group, butyl group, pentyl group, hexyl group, heptyl group, octyl group, 2-ethylhexyl group, nonyl group, decyl group, undecyl group, dodecyl group, hexadecyl group, octadecyl group, isooctadecyl group, Examples include an icosyl group and a triacontyl group.

The number of carbon atoms in R ₁ in general formula (2) is preferably 4 or more from the viewpoint of surface properties and film-forming properties, and preferably 27 from the viewpoints of improving surface properties, film-forming properties, availability and reactivity. It is below. Specific examples include the same as R ₁ in the general formula (1) described above.

A in general formula (2) forms an oxyalkylene group with an adjacent oxygen atom. The number of carbon atoms in A is preferably 2 or more from the viewpoint of surface property, film formability, availability and cost, and preferably 4 or less from the same viewpoint. Specific examples include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group and the like.

n in the general formula (2) indicates the number of moles of alkylene oxide added. n is preferably 3 or more from the viewpoint of surface properties, film formability, availability and cost, and preferably 40 or less from the same viewpoint.

As the combination of A and n in the general formula (2), from the viewpoint of surface properties and film-forming properties, A is preferably a linear or branched divalent saturated hydrocarbon group having 2 to 3 carbon atoms, n is a combination of numbers of 0 or more and 20 or less.

Specific examples of the substituent represented by the general formula (1) include pentyl group, hexyl group, octyl group, 2-ethylhexyl group, decyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, and isooctadecyl. group, icosyl group, propylhydroxyethyl group, butylhydroxyethyl group, pentylhydroxyethyl group, hexylhydroxyethyl group, heptylhydroxyethyl group, octylhydroxyethyl group, 2-ethylhexylhydroxyethyl group, nonylhydroxyethyl group, decylhydroxyethyl group, undecylhydroxyethyl group, dodecylhydroxyethyl group, hexadecylhydroxyethyl group, octadecylhydroxyethyl group, isooctadecylhydroxyethyl group, icosylhydroxyethyl group, triacontylhydroxyethyl group and the like.

Specific examples of substituents represented by general formula (2) include, for example, 3-butoxy-2-hydroxy-propyl group, 3-hexoxyethylene oxide-2-hydroxy-propyl group, 3-hexyxy-2-hydroxy -propyl group, 3-octoxyethylene oxide-2-hydroxy-propyl group, 3-octoxy-2-hydroxy-propyl group, 6-ethyl-3-hexytoxy-2-hydroxy-propyl group, 6-ethyl-3-hexy Toxyethylene oxide-2-hydroxy-propyl group, 3-Dethoxyethylene oxide-2-hydroxy-propyl group, 3-Dethoxy-2-hydroxy-propyl group, 3-Undethoxyethylene oxide-2-hydroxy-propyl group, 3-Undethoxy -2-hydroxy-propyl group, 3-dodethoxyethylene oxide-2-hydroxy-propyl group, 3-dodethoxy-2-hydroxy-propyl group, 3-hexadethoxyethylene oxide-2-hydroxy-propyl group, 3-hexadethoxy -2-hydroxy-propyl group, 3-octadethoxyethylene oxide-2-hydroxy-propyl group, 3-octadethoxy-2-hydroxy-propyl group and the like. The number of added moles of alkylene oxide may be 0 or more and 50 or less. be done.

(Introduction rate)
In the etherified cellulose fiber, the introduction ratio of the modifying group to 1 mol of the anhydroglucose unit of the cellulose cannot be generally limited depending on the type of the modifying group, but from the viewpoint of the surface properties and film-forming properties, it is preferably 0.0001 mol or more. and has a cellulose type I crystal structure, and is preferably 1.5 mol or less from the viewpoint of surface properties and film-forming properties. Here, when both the substituent represented by the general formula (1) and the substituent represented by the general formula (2) are introduced as the modifying group, it means the total molar ratio of introduction. . In addition, in the present specification, the rate of introduction of the modifying group into the etherified cellulose fiber can be measured according to the following method.

[Introduction rate of modifying group in hydrophobically modified cellulose fiber (B)]
The content % (% by mass) of the modifying group contained in the obtained etherified cellulose fiber is described in Analytical Chemistry, Vol. 51, No. 13, 2172 (1979), the Zeisel method known as a method for analyzing the average number of added moles of alkoxy groups in cellulose ethers, as described in "The Japanese Pharmacopoeia 15th Edition (Section of analytical methods for hydroxypropyl cellulose)". Calculated according to The procedure is shown below.
(i) 0.1 g of n-octadecane is added to a 200 mL volumetric flask, and the volume is increased to the marked line with hexane to prepare an internal standard solution.
(ii) 100 mg of purified and dried etherified cellulose fibers and 100 mg of adipic acid are accurately weighed into a 10 mL vial, 2 mL of hydroiodic acid is added, and the vial is tightly capped.
(iii) The mixture in the vial is heated with a block heater at 160° C. for 1 hour while stirring with a stirrer tip.
(iv) After heating, 3 mL of the internal standard solution and 3 mL of diethyl ether are sequentially injected into the vial and stirred at room temperature for 1 minute.
(v) The upper layer (diethyl ether layer) of the mixture separated into two phases in the vial is analyzed by gas chromatography (manufactured by SHIMADZU, "GC2010Plus"). The analysis conditions are as follows.
Column: DB-5 manufactured by Agilent Technologies (12 m, 0.2 mm × 0.33 μm)
Column temperature: 100°C → 10°C/min → 280°C (10min Hold)
Injector temperature: 300°C, detector temperature: 300°C, injection amount: 1 μL

The content (% by mass) of the modifying group in the etherified cellulose fiber is calculated from the detected amount of the used compound for introducing the modifying group.

From the obtained content of the modifying group, the molar degree of substitution (MS) (molar amount of the modifying group per 1 mol of the anhydroglucose unit) is calculated using the following formula (1).
(Formula 1)
MS = (W1/Mw)/((100-W1)/162.14)
W1: Content of modifying group in etherified cellulose fiber (% by mass)
Mw: the molecular weight (g/mol) of the introduced compound for introducing the modifying group

(average fiber diameter)
The etherified cellulose fiber in the present invention is not particularly limited in average fiber diameter regardless of the type of substituent. For example, an aspect having an average fiber diameter of micro order and an aspect having an average fiber diameter of nano order are exemplified.

The etherified cellulose fiber in micro-order mode preferably has a diameter of 5 μm or more from the viewpoints of surface properties, film formability, handleability, availability and cost. Although the upper limit is not particularly set, it is preferably 100 μm or less from the viewpoint of surface properties, film-forming properties and handling properties. In this specification, the average fiber diameter of micro-order cellulose fibers can be measured by the same method as the average fiber diameter of raw cellulose fibers.

The etherified cellulose fiber in nano-order mode is preferably 1 nm or more from the viewpoint of surface property, film-forming property, handleability, availability and cost, and is preferably 1 nm or more from the viewpoint of surface property, film-forming property and handleability. is 500 nm or less. In this specification, the average fiber diameter of the nano-order cellulose fibers can be measured by the same method as the average fiber diameter of the anion-modified cellulose fibers.

[Method for producing etherified cellulose fiber]
In the etherified cellulose fiber of the present invention, as described above, a modifying group, preferably a hydrocarbon group optionally having a substituent as described above, is bonded to the surface of the cellulose fiber via an ether bond. Introduction of the group can be performed according to a known method without particular limitation. A specific example of the method for producing the etherified cellulose fiber of aspect 1 is described below.
As a specific example of the method for producing etherified cellulose fibers of aspect 1, there is an aspect in which the raw material cellulose fibers are reacted with a specific compound in the presence of a base.

In addition, from the viewpoint of reducing the number of manufacturing steps, cellulose fibers that have been pulverized in advance may be used as raw material cellulose fibers, and in that case, the average fiber diameter is preferably 1 nm or more from the viewpoint of availability and cost. Although the upper limit is not particularly set, it is preferably 500 nm or less from the viewpoint of handleability.

(base)
In this production method, a base is mixed with the cellulose fibers as the raw material.
The base is not particularly limited, but from the viewpoint of promoting the etherification reaction, alkali metal hydroxides, alkaline earth metal hydroxides, primary to tertiary amines, quaternary ammonium salts, imidazole and its derivatives, pyridine. and derivatives thereof, and one or more selected from the group consisting of alkoxides are preferred.

Alkali metal hydroxides and alkaline earth metal hydroxides include sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, barium hydroxide and the like.

Primary to tertiary amines are primary amines, secondary amines and tertiary amines, and specific examples include ethylenediamine, diethylamine, proline, N,N,N',N'-tetramethylethylenediamine, N , N,N′,N′-tetramethyl-1,3-propanediamine, N,N,N′,N′-tetramethyl-1,6-hexanediamine, tris(3-dimethylaminopropyl)amine, N , N-dimethylcyclohexylamine, triethylamine and the like.

The quaternary ammonium salts include tetrabutylammonium hydroxide, tetrabutylammonium chloride, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetraethylammonium hydroxide, tetraethylammonium chloride, tetraethylammonium fluoride, tetraethylammonium bromide, water tetramethylammonium oxide, tetramethylammonium chloride, tetramethylammonium fluoride, tetramethylammonium bromide, and the like.

Imidazole and its derivatives include 1-methylimidazole, 3-aminopropylimidazole, carbonyldiimidazole and the like.
Pyridine and its derivatives include N,N-dimethyl-4-aminopyridine, picoline and the like.

Alkoxides include sodium methoxide, sodium ethoxide, potassium-t-butoxide and the like.

The amount of the base is preferably 0.01 equivalent or more relative to the anhydroglucose unit of the raw material cellulose fiber from the viewpoint of advancing the etherification reaction, and preferably 10 equivalent or less from the viewpoint of production cost.

The mixing of the raw material cellulose fibers and the base may be carried out in the presence of a solvent. The solvent is not particularly limited, and examples include water, isopropanol, t-butanol, dimethylformamide, toluene, methyl isobutyl ketone, acetonitrile, dimethylsulfoxide, dimethylacetamide, 1,3-dimethyl-2-imidazolidinone, hexane, 1,4-dioxane and mixtures thereof.

There are no particular restrictions on the temperature or time for mixing the cellulose fibers as raw materials and the base as long as they can be uniformly mixed.

Next, a compound for introducing a modifying group, preferably a compound for introducing a hydrocarbon group which may have a substituent, is added to the mixture of the raw material cellulose fiber and the base obtained above. to react the raw material cellulose fiber with the compound. Such a compound is preferably one or more selected from the substituents represented by the general formula (1) and the substituents represented by the general formula (2) when reacting with the raw material cellulose fiber. There is no particular limitation as long as the substituent can be bonded via an ether bond, and in the present invention, from the viewpoint of reactive and halogen-free compounds, compounds having a reactive cyclic structural group It is preferable to use, and it is more preferable to use a compound having an epoxy group. Each compound is exemplified below.

Examples of the compound to which the substituent represented by the general formula (1) can be bound via an ether bond include an alkylene oxide compound represented by the following general formula (1A) and an alkyl represented by the general formula (1B). Halides are preferred. Such compounds may be prepared according to known techniques, or may be commercially available products. The total carbon number of the compound is preferably 3 or more from the viewpoint of surface properties and film-forming properties, and preferably 32 or less from the viewpoints of surface properties and film-forming properties.

[In the formula, R ₁ represents a linear or branched alkyl group having 3 to 30 carbon atoms. ]

X—(CH ₂ ) ₂ —R ₁ (1B)
[In the formula, R ₁ represents a linear or branched alkyl group having 3 to 30 carbon atoms, and X is a halogen atom selected from fluorine, chlorine, bromine and iodine. ]

The number of carbon atoms in R ₁ in general formulas (1A) and (1B) is preferably 4 or more from the viewpoint of surface properties and film-forming properties, and preferably 25 or less from the viewpoints of surface properties and film-forming properties. . Specifically, those described in the section for R ₁ in the substituent represented by formula (1) can be mentioned.

Specific examples of the compound represented by formula (1A) include 1,2-epoxyhexane, 1,2-epoxydecane, and 1,2-epoxyoctadecane.
Specific examples of the compound represented by the general formula (1B) include 1-chloropentane, 1-chlorohexane, 1-chlorooctane, 1-chlorodecane, 1-chlorododecane, 1-chlorohexadecane, 1-chlorooctadecane, 1 -bromopentane, 1-bromohexane, 1-bromooctane, 1-bromodecane, 1-bromododecane, 1-bromohexadecane, 1-bromooctadecane, 1-iodopentane, 1-iodohexane, 1-iodooctane, 1- Examples include iododecane, 1-iodododecane, 1-iodohexadecane, and 1-iodooctadecane.

As the compound to which the substituent represented by the general formula (2) can be bound via an ether bond, for example, a glycidyl ether compound represented by the following general formula (2A) is preferable. Such compounds may be prepared according to known techniques, or may be commercially available products. The total carbon number of the compound is preferably 5 or more from the viewpoint of surface properties and film-forming properties, and preferably 100 or less from the viewpoints of surface properties and film-forming properties.

[In the formula, R ₁ is a linear or branched alkyl group having 3 to 30 carbon atoms, A is a linear or branched divalent saturated hydrocarbon group having 1 to 6 carbon atoms, and n is 0 or more. Indicates a number less than or equal to 50. ]

The number of carbon atoms in R ₁ in general formula (2A) is preferably 4 or more from the viewpoint of surface properties and film-forming properties, and preferably 27 or less from the viewpoints of surface properties and film-forming properties. Specifically, those described in the section for R ₁ in the substituent represented by formula (2) can be mentioned.

A in general formula (2A) forms an oxyalkylene group with an adjacent oxygen atom. The carbon number of A is preferably 2 or more from the viewpoint of availability and cost, and preferably 4 or less from the same viewpoint. Specifically, those described in the item A in the substituent represented by the general formula (2) are exemplified. Among them, ethylene group and propylene group are preferable, and ethylene group is more preferable.

n in the general formula (2A) indicates the number of moles of alkylene oxide added. n is preferably 3 or more from the viewpoint of availability and cost, and preferably 40 or less from the same viewpoint.

Specific examples of the compound represented by formula (2A) include butyl glycidyl ether, 2-ethylhexyl glycidyl ether, dodecyl glycidyl ether, stearyl glycidyl ether, isostearyl glycidyl ether and polyoxyalkylene alkyl ether.

The amount of the compound for introducing the modifying group can be determined according to the desired introduction rate of the modifying group in the resulting etherified cellulose fiber. , preferably 0.01 equivalents or more, and preferably 10 equivalents or less from the viewpoint of production cost.

(Etherification reaction)
The etherification reaction between the compound and the raw material cellulose fiber can be carried out by mixing the two in the presence of a solvent. The solvent is not particularly limited, and the solvents exemplified as usable when the base is present can be used.

The amount of the solvent to be used is not generally determined depending on the type of the cellulose fiber as the raw material and the type of the compound for introducing the modifying group, but from the viewpoint of reactivity, it is preferably 30 parts per 100 parts by mass of the cellulose fiber as the raw material. Parts by mass or more, preferably 10,000 parts by mass or less from the viewpoint of productivity.

The mixing conditions are not particularly limited as long as the raw material cellulose fibers and the compound for introducing the modifying group are uniformly mixed and the reaction can proceed sufficiently, and continuous mixing may or may not be performed. good too. When using a relatively large reaction vessel exceeding 1 L, stirring may be performed as appropriate from the viewpoint of controlling the reaction temperature.

The reaction temperature is not unconditionally determined depending on the type of the raw material cellulose fiber, the compound for introducing the modifying group, and the target introduction rate, but from the viewpoint of improving the reactivity, it is preferably 40 ° C. or higher. From the viewpoint of suppressing thermal decomposition, the temperature is preferably 120° C. or less.

The reaction time is not unconditionally determined depending on the type of cellulose fiber as a raw material, the type of compound for introducing the modifying group, and the target introduction rate, but from the viewpoint of reactivity, it is preferably 0.5 hours or more, From the viewpoint of productivity, it is preferably 60 hours or less.

After the reaction, an appropriate post-treatment can be carried out in order to remove unreacted compounds, bases and the like. If desired, further drying (such as vacuum drying) may be performed.
Etherified cellulose fibers are thus obtained.

Regarding both of the above hydrophobically modified cellulose fibers (A) and (B), the obtained hydrophobically modified cellulose fibers can be used in the form of a dispersion after the post-treatment, or can be dried. By removing the solvent from the dispersion liquid by, for example, dry powdery hydrophobically modified cellulose fibers can be obtained and used. The term "powder" as used herein means a powdery form of agglomeration of hydrophobically modified cellulose fibers, and does not mean cellulose particles.

Powdered hydrophobically modified cellulose fibers include, for example, a dried product obtained by drying the cellulose fiber dispersion as it is; a powder obtained by mechanically pulverizing the dried product; and a known spray-drying method for the cellulose fiber dispersion. powdered by a known freeze-drying method; and powdered by a known freeze-drying method. The spray drying method is a method in which the cellulose fiber dispersion is sprayed in the air and dried.

The average fiber diameter of the obtained fine cellulose fibers is preferably 0.1 nm or more, more preferably 0.5 nm or more, still more preferably 1 nm or more, still more preferably 2 nm or more, from the viewpoint of surface properties and film-forming properties. More preferably, it is 3 nm or more. From the same viewpoint, it is preferably 100 nm or less, more preferably 50 nm or less, still more preferably 20 nm or less, even more preferably 10 nm or less, still more preferably 6 nm or less, and even more preferably 5 nm or less.

The length (average fiber length) of the obtained fine cellulose fibers is preferably 150 nm or longer, more preferably 200 nm or longer, from the viewpoint of workability and stability. From the viewpoint of workability and stability, it is preferably 1000 nm or less, more preferably 750 nm or less, even more preferably 500 nm or less, and even more preferably 400 nm or less.

In the present invention, the average fiber diameter and average fiber length of the cellulose fibers are not limited to the ranges described above, and for example, those on the order of micrometers can be used.

In addition, the average aspect ratio (fiber length/fiber diameter) of the obtained fine cellulose fibers is preferably 1 or more, more preferably 10 or more, and still more preferably 10 or more, from the viewpoint of surface property, film formability, workability and stability. is 20 or more, more preferably 40 or more, still more preferably 60 or more, and from the same viewpoint, preferably 260 or less, more preferably 240 or less, still more preferably 220 or less, still more preferably 200 or less, still more preferably 190 180 or less, more preferably 180 or less. Further, when the average aspect ratio is within the above range, the standard deviation of the aspect ratio is preferably 60 or less, more preferably 50 or less, more preferably 50 or less, from the viewpoint of surface property, film formability, workability and stability. is 45 or less, and although the lower limit is not particularly set, it is preferably 4 or more from the viewpoint of economy. The fine cellulose fibers having a low aspect ratio are excellent in heat resistance.

In the defoaming promoting composition of the present invention, from the viewpoint of improving defoaming promoting performance, the component (A) is preferably 1% by mass or more, more preferably 10% by mass or more, and preferably 100% by mass or less. More preferably, the content is 80% by mass or less.

The composition for promoting defoaming of the present invention can contain (B) oil [hereinafter referred to as component (B)]. The component (B) is a preferable component from the viewpoint of improving the coatability (hereinafter also referred to as coatability) when the composition for promoting defoaming of the present invention is applied and used, in addition to promoting defoaming.

Components (B) include squalane, limonene, myrcene, α-pinene, β-pinene, camphene, geraniol, linalool, citronellol, nerol, terpineol, menthol, cineol, ascaridol, borneol, citral, ionone, citronellal, and perillaldehyde. , carvone, dihydrocarvone, piperitone, menthone, camphor, thujone, citronellyl formate, citronellyl acetate, terpinyl acetate, linalyl acetate, geranyl acetate, benzyl acetate, bornyl acetate, farnesol, nerolidol, humulene, caryophyllene, casinool, cadinene, phytol, Terpenoids such as abietic acid; Mineral oils such as paraffinic oils and naphthenic oils; Hydrocarbons such as hexadecane and liquid paraffin; Fatty acids such as oleic acid; Isopropyl myristate, isopropyl palmitate, isopropyl oleate, isononyl isononanoate, isotridecyl isononanoate, 2-ethylhexyl palmitate, cetyl 2-ethylhexanoate, di(2-ethylhexanoic acid) 2,2-dimethyl-1,3 -diisopropyl, 2,2-dimethyl-1,3-diisopropyl dicaprate, 1,2,3-triisopropyl tri(2-ethylhexanoate), 1,2,3-tripropyl tricaprate, dicapric acid Esters such as 1,3-dipropyl and octyldodecyl lactate; Vegetable oils such as evening primrose oil and soybean oil; Fluorocarbon oils such as Fluorinert FC-40, FC-43, FC-72 and FC-770 (manufactured by 3M) silicone oils such as KF-96-1cs and KF-96-10cs (manufactured by Shin-Etsu Chemical Co., Ltd.);

The component (B) is preferably one or more selected from terpenoids and mineral oils from the viewpoint of applicability.

Component (B) has a viscosity at 20° C. of preferably 300 mPa·s or less, more preferably 280 mPa·s or less, even more preferably 260 mPa·s or less, and even more preferably 200 mPa·s or less, from the viewpoint of coating properties. , more preferably 150 mPa·s or less, still more preferably 100 mPa·s or less, and the lower limit may be 10 mPa·s or more. The viscosity of the component (B) was measured with a rheometer Physica MCR301 manufactured by Anton Paar using a plate jig with a diameter of 25 mm, a gap of 0.5 mm, a rotation speed of 3,000 rpm, and 20°C. .

In addition, the molecular weight of component (B) may be, for example, 50 or more, further 100 or more, and 1000 or less, further 500 or less.

From the viewpoint of applicability, the defoaming promoting composition of the present invention preferably contains component (B) in an amount of 10% by mass or more, more preferably 20% by mass or more, and preferably 90% by mass or less, more preferably It contains 80% by mass or less.

From the viewpoint of applicability, the composition for promoting defoaming of the present invention preferably has a mass ratio of (A)/(B) between the content of component (A) and the content of component (B). It is 0.01 or more, more preferably 0.05 or more, still more preferably 0.1 or more, and preferably 1 or less, more preferably 0.9 or less, and still more preferably 0.8 or less.

The composition for promoting defoaming of the present invention can contain (C) a polymer compound other than the component (A) and oil [hereinafter referred to as component (C)]. This oil is the (B) component. Therefore, component (C) is a polymer compound other than components (A) and (B). Component (C) is a preferred component from the viewpoint of film formability and film durability.

Component (C) is more preferably one or more polymer compounds selected from the group consisting of (X) and (Y) below, and the polymer compound (X) is even more preferred. (X) and (Y) may be non-curable polymer compounds. The mass-average molecular weights of (X) and (Y) are preferably 1,000 or more from the viewpoint of film-forming properties and film durability, and preferably 500,000 or less from the same viewpoint.
(X) polymer compound having ester group, amide group, urethane group, amino group, ether group or carbonate group in main chain (Y) methacrylic or acrylic polymer having ester group or amide group in side chain

[Polymer compound of (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 alkenylsuccinic acid, ethylene glycol, Examples include condensates with diols such as propylene glycol and butanediol.

Examples of the polymer compound (X) having an amide 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 alkenylsuccinic acid, ethylenediamine, hexa Examples include condensates with diamines such as aliphatic diamines such as methylenediamine and propylenediamine.

Polymer compounds (X) having urethane groups in the main chain include polymers of diisocyanates such as triresin diisocyanate, diphenylisocyanate, xylylene diisocyanate and hexamethylene diisocyanate and diols such as ethylene glycol, propylene glycol and butanediol. etc.

Polymers of alkylimine such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine, and hexyleneimine are examples of the polymer compound (X) having an amino group in the main chain.

Polymers of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, polymers of formaldehyde, and the like can be mentioned as the polymer compound (X) having an ether group in the main chain.

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, 1,1-bis(4- Condensates of polyols such as hydroxyphenyl)cyclohexane and phosgene.

The polymer compound (X) is preferably one or more polymer compounds selected from the group consisting of the following (a) and (b) from the viewpoint of film-forming properties and film durability, ) is more preferred.
(a) polyamide compound (b) polyalkyleneimine compound

(a) Polyamide compound As the polyamide compound, any polyamide compound having any chemical structure can be used as long as it is a polymer compound having no cellulose structure and having an amide bond (--CONH--). The polyamide compound may be, for example, nylon having a predominantly aliphatic skeleton, or aramid having a predominantly aromatic skeleton. Furthermore, it may have a skeletal structure other than these two. On the other hand, preferred structures include polyamides comprising an amine compound and one or more carboxylic acids selected from the group consisting of monocarboxylic acids, dicarboxylic acids and polymerized fatty acids.

Monocarboxylic acids, dicarboxylic acids, and polymerized fatty acids can be suitably used as the carboxylic acid, which is one of the raw materials.

Amine compounds, which are the other raw materials, include polyamines, aminocarboxylic acids, aminoalcohols, and the like. Polyamines include aliphatic diamines such as ethylenediamine, hexamethylenediamine and propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine, pentaplies Examples include polyalkylenepolyamines such as lenhexamine, aromatic diamines such as (ortho, para or meta)xylenediamine and diphenylmethanediamine, and alicyclic diamines such as piperazine and isophoronediamine. Aminocarboxylic acids include methylglycine, trimethylglycine, 6-aminocaproic acid, δ-aminocaprylic acid, ε-caprolactam and the like. Amino alcohols include ethanolamine, propanolamine, and the like.

Each compound used as these raw materials can be used alone or in combination of two or more.

From the viewpoint of film-forming property and film durability, the amine compound preferably includes an amine component containing polyamine, more preferably the amine compound is a group consisting of diamine, triamine, tetramine, pentamine and hexatetraamine. An amine component used in combination with one or more selected from can be used.

[Polymer compound of (Y)]
Examples of the polymer (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, polybutyl (meth)acrylate, and the like. Alkyl (meth) acrylate, poly (meth) acrylamide, poly N-methyl (meth) acrylamide, poly N, N-dimethyl (meth) acrylamide, poly (meth) acrylamide such as poly N-phenyl (meth) acrylamide, etc. be done.

From the viewpoint of film-forming properties, the composition for promoting defoaming of the present invention may contain a curable resin (hereinafter sometimes referred to as component (C1)) as component (C). Examples of curable resins in the present invention include urethane resins, (meth)acrylic resins, epoxy resins, urea resins, melamine resins, and phenol resins. One or more selected are preferred. A prepolymer can also be used for the (C1) component.

When the curable resin is a urethane resin, the curable monomers include aromatics such as tolylene diisocyanate and diphenylmethane diisocyanate, and aliphatics such as hexamethylene diisocyanate, xylylene diisocyanate, isophorone diisocyanate, and tetramethylxylylene diisocyanate. Polyols such as isocyanate, ethylene glycol, diethylene glycol, butanediol, hexanediol, neopentyldiol, hydroxyethyl acrylate, trimethylolpropane, dimethylolpropionic acid, and isophoronediamine are included. A reaction product of isocyanate and polyol is a urethane resin, but is not limited to this. Oligomers of the listed polyols and polyols such as polyether polyols, polyester polyols and polycarbonate polyols may be used as the curable prepolymer.

When the curable resin is a (meth)acrylic resin, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate, hexyl acrylate, hexyl methacrylate, 2-acrylate Ethylhexyl, 2-ethylhexyl methacrylate, nonanediol diacrylate, phenoxyethyl acrylate, bisphenol A-alkylene oxide adduct (meth)acrylate, epoxy (meth)acrylate (bisphenol A type epoxy (meth)acrylate, novolac type epoxy ( meth) acrylate, etc.), polyester (meth) acrylate (e.g., aliphatic polyester type (meth) acrylate, aromatic polyester type (meth) acrylate, etc.), urethane (meth) acrylate (polyester type urethane (meth) acrylate, polyether type urethane (meth)acrylate, etc.), silicone (meth)acrylate, and those obtained from curable monomers such as mono(meth)acrylates such as cyanoacrylate. Oligomers of curable monomers such as the listed mono(meth)acrylates may also be used as curable prepolymers.

When the curable resin is an epoxy resin, for example, those obtained from curable monomers such as bisphenol A type, phenol novolak type, glycidyl ether type, alicyclic type, glycidyl amine type and glycidyl ester type. Oligomers of the listed curable monomers may also be used as curable prepolymers.

When the curable resin is a urea resin, it includes those obtained from curable monomers such as urea and formaldehyde.
When the curable resin is a melamine resin, it includes those obtained from melamine and curable monomers such as formaldehyde.
When the curable resin is a phenolic resin, it includes those derived from curable monomers such as phenol, cresol, xylenol, resorcinol and formaldehyde.

The weight-average molecular weight of the curable prepolymer is preferably 100 or more, more preferably 500 or more, and still more preferably 1,000 or more from the viewpoint of suppressing cracking during drying of the coating film. From the viewpoint of the dispersibility of the polymer and the solubility of the curable prepolymer in a solvent, the molecular weight is preferably 30,000 or less, more preferably 15,000 or less, and still more preferably 10,000 or less.

A more preferable curable monomer or curable prepolymer in the present invention is a UV curable resin polymerized by a UV curing reaction from the viewpoint of curing speed. Specifically, UV curable resins such as (meth)acrylic resins, curable monomers or curable prepolymers of epoxy resins can be used. Among them, urethane acrylates, polyester (meth)acrylates, and silicone (meth)acrylates are preferred from the viewpoint of strength of interaction with hydrophobically modified cellulose fibers, and bisphenol type and alicyclic acrylates are preferred from the viewpoint of heat resistance. Epoxy resins of the type are preferred. From the viewpoint of film toughness, (meth)acrylic resins and urethane resin monomers or prepolymers are preferred. ) acrylates, silicone (meth)acrylates, aliphatic isocyanates, aromatic isocyanates, polyester polyols, polyether polyols, and polycarbonate polyols.

When using a curable prepolymer of a UV curable resin, it is preferable to further use a photopolymerization initiator as necessary. Such photopolymerization initiators include, for example, acetophenones, benzophenones, ketals, anthraquinones, thioxanthones, azo compounds, peroxides, 2,3-dialkylsion compounds, disulfide compounds, thiuram compounds, fluoroamines. compounds and the like. More specifically, 1-hydroxy-cyclohexyl-phenyl-ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, benzyl methyl ketone, 1-(4- dodecylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-hydroxy-2-methylpropan-1-one, benzophenone and the like.

When the composition for promoting defoaming of the present invention contains component (C), the composition preferably contains component (C) in an amount of 1% by mass or more, more preferably 5% by mass, from the viewpoint of film-forming properties. above, and preferably 75% by mass or less, more preferably 50% by mass or less.

When the composition for promoting defoaming of the present invention contains component (C), from the viewpoint of film-forming properties, the composition preferably contains component (C) in an amount of 1% by mass relative to component (A). Above, more preferably 10% by mass or more, preferably 1000% by mass or less, more preferably 500% by mass or less.

When the composition for promoting defoaming of the present invention contains the component (C1), from the viewpoint of film-forming properties, the composition preferably contains the component (C1) in an amount of 10% by mass or more, more preferably 20% by mass. above, and preferably 50% by mass or less, more preferably 40% by mass or less.

When the composition for promoting defoaming of the present invention contains the component (C1), from the viewpoint of film-forming properties, the composition preferably contains the component (C1) in an amount of 1% by mass relative to the component (A). Above, more preferably 10% by mass or more, preferably 1000% by mass or less, more preferably 500% by mass or less.

The composition for promoting defoaming of the present invention can also contain (D) a curable monomer that becomes a curable resin through a polymerization reaction [hereinafter referred to as component (D)]. The curable monomers listed for the component (C1) can be used as the component (D). When the composition for promoting defoaming of the present invention contains component (D), from the viewpoint of film-forming properties, the composition preferably contains component (D) in an amount of 10% by mass or more, more preferably 20% by mass. above, and preferably 50% by mass or less, more preferably 40% by mass or less.

The form of the composition for promoting defoaming of the present invention may be either solid or liquid.

Next, a method for producing the composition for promoting defoaming of the present invention will be described. The defoaming promoting composition can be produced by stirring a mixture containing component (A) and optional components (B), (C) and (D). Mixing of these components may be performed using a magnetic stirrer, and the conditions in that case are, for example, a rotation speed of 400 rpm or more and 600 rpm or less, a temperature of 15° C. or more and 35° C. or less, and stirring for 6 hours or more and 24 hours or less. Alternatively, the mixture may be stirred at a temperature of 20° C. or higher and 30° C. or lower for 10 hours or longer and 16 hours or shorter.

<Fluid foaming control method>
When the composition for promoting defoaming of the present invention is brought into contact with a fluid containing bubbles, the bubbles of the fluid can be eliminated at the contact site.
The present invention provides a method for controlling foaming of a fluid, comprising contacting a fluid containing bubbles with the composition for promoting defoaming of the present invention and suppressing appearance of bubbles on the surface of the fluid at the contact position.
To the fluid foaming control method of the present invention, the items described in the composition for promoting defoaming of the present invention can be appropriately applied.

In the fluid foam control method of the present invention, said fluid is preferably contacted with a film obtained from said composition. The membrane may be an independent membrane or a membrane formed on the surface of a support. The material of the support is not particularly limited, but may be hard materials such as glass, resin, metal, ceramics or concrete, or soft materials such as fibers and paper. Moreover, the shape of the support is not particularly limited, and examples thereof include a plate shape, a cylindrical shape, a film shape, a combination thereof, and the like.

The thickness of the film of the defoaming promoting composition is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 30 μm or more from the viewpoint of improving defoaming promotion. It is 2,000 μm or less, more preferably 1,500 μm or less, still more preferably 1,200 μm or less.

The film of the composition for promoting defoaming can be formed, for example, by applying the composition for promoting defoaming of the present invention as it is or as a coating solution diluted with an appropriate solvent to a support. The coating method is not particularly limited, but includes, for example, dip coating, spin coating, flow coating, spray coating, roll coating, brush coating and the like. In order to improve the adhesion between the surface of the support and the film, if necessary, a base (lower layer) such as a primer may be previously applied or formed on the surface of the support.

When used as a coating liquid, the coating liquid may contain a dispersion medium such as alcohol, glycol, ether, or carbonyl compound from the viewpoint of coatability. Dispersion media include methanol, ethanol, propanol, isopropanol, butanol, ethylene glycol, diethylene glycol, propylene glycol, diethyl ether, tetrahydrofuran, petroleum ether, acetone, ethyl acetate and the like.

When the coating liquid contains a dispersion medium, the content of the dispersion medium in the coating liquid is preferably 5% by mass or more, more preferably 10% by mass, from the viewpoint of sufficiently dispersing the component (A) and the like. % or more, more preferably 20 mass % or more. From the viewpoint of shortening the film formation time, the content is preferably 90% by mass or less, more preferably 70% by mass or less, and even more preferably 50% by mass or less.

When the coating liquid contains a dispersion medium, it is preferable to carry out a step of removing the dispersion medium from the formed film after coating. A specific method for removing the dispersion medium is not particularly limited, and examples thereof include a method of drying the coating film of the mixture under reduced pressure or normal pressure. The temperature range for drying is preferably 15°C or higher and 75°C or lower. Moreover, as time for drying, 1 hour or more and 24 hours or less are preferable. The dispersion medium does not necessarily have to be completely removed, and may remain in the film to the extent that it does not hinder the performance of the film.

The coating liquid preferably has a viscosity at 20° C. of 400 mPa·s or less, more preferably 350 mPa·s or less, still more preferably 300 mPa·s or less, and even more preferably 250 mPa·s or less, from the viewpoint of coating properties. Yes, and the lower limit may be 10 mPa·s or more. The viscosity of the coating liquid was measured in the same manner as for the component (B).

When the defoaming promoting composition contains the curable monomer (D) component or the curable prepolymer (C1) component, it is preferable to polymerize the curable monomer or curable prepolymer after removing the dispersion medium. The polymerization reaction cures the curable monomer or prepolymer to form a curable resin. The curing method includes known methods such as UV curing, heat curing, moisture curing, etc., and may be appropriately selected depending on the type of resin used. UV curing is preferable from the viewpoint of outflow of an organic medium by heat treatment and the viewpoint of reaction time. Radical UV curing is more preferable than cationic UV curing from the viewpoint of film thickness curability.

Fluids containing air bubbles include curable compositions, resin compositions, ceramic compositions, food compositions, casting compositions, coating compositions, electronic material compositions, ejection compositions, and the like.

In the fluid foam control method of the present invention, the fluid may be a curable composition, such as a hydraulic composition. Hydraulic compositions are a preferred subject of the present invention.

<Method for producing hardened body>
TECHNICAL FIELD The present invention relates to a method for producing a cured body, comprising bringing a curable composition containing air bubbles into contact with a support coated with the composition for promoting defoaming of the present invention and curing the composition. In the present invention, a support having a film of the above composition formed thereon can be used.
To the method for producing a cured product of the present invention, the items described in the composition for promoting defoaming and the method for controlling fluid foaming of the present invention can be appropriately applied. The support, the method of applying the composition, the thickness of the film, etc. are the same as those of the fluid foaming control method of the present invention.

In the method for producing a cured body of the present invention, the support may be a formwork that accommodates the curable composition.
In the method for producing a cured body of the present invention, the support may be separated from the cured body after curing of the curable composition.

By applying the composition for promoting defoaming of the present invention to the surface of the support and further to the surface of the mold as described above, the appearance of the surface of the cured product in contact with the film obtained from the composition for promoting defoaming is improved. be able to. Since the durability of the film itself is excellent and the surface aesthetic effect can be maintained for a long period of time, it can be used for moldings of various uses made of a cured product.

In the method for producing a cured product of the present invention, the curable composition may be a hydraulic composition. Therefore, as a method for producing the cured product of the present invention, the hydraulic composition containing air bubbles is filled in a mold coated with the defoaming promoting composition of the present invention and cured, and then the obtained cured product is placed in a mold. Provided is a method for producing a hardened body of a hydraulic composition that is released from a frame. The hydraulic composition is a composition containing hydraulic powder such as cement, and examples thereof include mortar and concrete. These hydraulic compositions may be known.

In the method for producing a cured body of the present invention, traces of air bubbles on the surface of the cured body can be reduced. That is, for example, by separating the cured body from the mold after curing the curable composition, it is possible to produce a cured body with reduced air bubble marks on the surface. In this way, the curable composition containing air bubbles is cured by contacting it with the coating film obtained from the defoaming promoting composition, and the surface of the cured body is reduced by reducing the bubble marks on the surface of the cured body. Aesthetics can be improved. Therefore, according to the present invention, a curable composition containing air bubbles, for example, a hydraulic composition, is brought into contact with a coating film obtained from the defoaming promoting composition of the present invention to cure the air bubbles on the surface of the cured product. Provided is a method for improving surface aesthetics of a cured body that reduces marks.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples. It should be noted that this example is merely an illustration of the present invention and does not imply any limitation. Parts in the examples are parts by weight unless otherwise specified. In addition, "ordinary pressure" indicates 101.3 kPa, and "ordinary temperature" indicates 25°C.

[Average fiber diameter, average fiber length and average aspect ratio of anion-modified cellulose fibers and hydrophobically-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. An atomic force microscope (AFM) (manufactured by Digital instrument Co., Ltd., Nanoscope IITappingmode AFM; the probe is Nanosensors Co., Ltd., Point Probe (NCH ) is used) to measure the fiber height of the cellulose fibers in the observation sample (difference between the heights where fibers are present and where they are absent). At that time, 100 or more cellulose fibers are extracted from a microscope image in which the cellulose fibers can be confirmed, and the average fiber diameter is calculated from the fiber heights. The average fiber length is calculated from the distance in the fiber direction. The average aspect ratio is calculated from average fiber length/average fiber diameter, and the standard deviation is also calculated. In general, the minimum unit of cellulose nanofibers prepared from higher plants is 6×6 molecular chains packed in a nearly square shape, so the height analyzed in the AFM image can be regarded as the fiber diameter. can.

[Average Fiber Diameter and Average Fiber Length of Raw Material Cellulose Fiber]
Ion-exchanged water is added to the cellulose fibers 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 (manufactured by Jusco International Co., Ltd., trade name: IF-3200), the dispersion is measured using a front lens: 2x, a telecentric zoom lens: 1x, and an image resolution of 0.835 μm/pixel. , syringe inner diameter: 6515 μm, spacer thickness: 500 μm, image recognition mode: ghost, threshold: 8, analysis sample amount: 1 mL, sampling: 15%. 100 or more cellulose fibers are measured, the average ISO fiber diameter is calculated as the average fiber diameter, and the average ISO fiber length is calculated as the average fiber length.

[Anionic group content of anion-modified cellulose fiber and hydrophobically-modified cellulose fiber]
Take 0.5 g of dry mass of cellulose fibers to be measured in a 100 mL beaker, add ion-exchanged 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. A dispersion is prepared. 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 (manufactured by Toa DKK Co., Ltd., AUT-701) to add 0.05 M sodium hydroxide aqueous solution with a waiting time of 60 seconds. is added dropwise to the dispersion under the conditions of , and the conductivity and pH values are measured every minute. The measurement is continued until the pH reaches about 11, and a conductivity curve is obtained. From this conductivity curve, the titration amount of sodium hydroxide 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 titration amount x sodium hydroxide aqueous solution concentration (0.05 M)]/[mass of cellulose fiber to be measured (0.5 g)]

[Aldehyde Group Content of Anion-Modified Cellulose Fiber]
In a beaker, 100.0 g of cellulose fiber to be measured (solid content 1.0% by mass), acetate buffer (pH 4.8), 2-methyl-2-butene 0.33 g, sodium chlorite 0.45 g and stirred at room temperature for 16 hours to oxidize the aldehyde group. After completion of the reaction, the fiber is washed with deionized water to obtain a cellulose fiber to be measured in which the aldehyde group is oxidized. The reaction solution is freeze-dried, and the carboxyl group content of the obtained dried product is measured by the above anionic group content measuring method to calculate the "carboxyl group content of the oxidized anion-modified cellulose fiber". Subsequently, the aldehyde group content of the anion-modified cellulose fiber to be measured is calculated by the following formula.
Aldehyde group content (mmol/g) = (carboxy group content of oxidized anion-modified cellulose fiber) - (carboxy group content of anion-modified cellulose fiber to be measured)

[Solid content in dispersion]
A halogen moisture meter (manufactured by Shimadzu Corporation, trade name: MOC-120H) is used. A 1 g sample is measured at a constant temperature of 150° C. every 30 seconds, and the value at which the mass reduction becomes 0.1% or less is taken as the solid content.

[Average bonding amount and introduction rate (ionic bond) of modifying group of hydrophobically modified cellulose fiber]
The bonding amount of the modifying group is determined by the following IR measurement method, and the average bonding amount and introduction ratio are calculated by the following formula. Specifically, the IR measurement is performed by measuring the dried hydrophobically modified cellulose fiber by the ATR method using an infrared absorption spectrometer (manufactured by Thermo Fisher Scientific, trade name: Nicolet 6700), and calculating the following formula A and From B, the average bonding amount and introduction rate of the modifying group are calculated. Formulas A and B represent the case where the anionic group is a carboxy group, that is, the case of oxidized cellulose fibers. The “1720 cm ⁻¹ peak intensity” below is the peak intensity derived from the carbonyl group. In the case of an anionic group other than the carboxyl group, the peak intensity value may be appropriately changed to calculate the average bonding amount and introduction ratio of the modifying group.

<Formula A>
Average binding amount of modifying group (mmol/g) = a × (b−c) ÷ d
a: Carboxy group content of oxidized cellulose fiber (mmol/g)
b: peak intensity at 1720 cm ⁻¹ of oxidized cellulose fiber c: peak intensity at 1720 cm ⁻¹ of hydrophobically modified cellulose fiber d: peak intensity at 1720 cm ⁻¹ of oxidized cellulose fiber Peak intensity at 1720 cm ⁻¹ : carbonyl group of carboxylic acid Derived peak intensity <Formula B>
Modification group introduction rate (%) = 100 x e/f
e: binding amount of modifying group (mmol/g)
f: carboxyl group content of oxidized cellulose fiber (mmol/g)

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

<Formula C>
Cellulose type I crystallinity (%) = [(I _22.6 -I _18.5 )/I _22.6 ] × 100
[In the formula, I _22.6 is the diffraction intensity of the lattice plane (002 plane) (diffraction angle 2θ = 22.6°) in X-ray diffraction, I _18.5 is the amorphous part (diffraction angle 2θ = 18.5 °) shows the diffraction intensity]

[Cellulose fiber amount (converted amount) in hydrophobically modified cellulose fiber]
The cellulose fiber (converted amount) in the hydrophobically modified cellulose fiber is measured by the following method.
(1) When only one type of "compound for introducing a modifying group" is added The amount of cellulose fibers (converted amount) is calculated by the following formula E.
<Formula E>
Amount of cellulose fiber (converted amount) (g) = Mass of hydrophobically modified cellulose fiber (g)/[1 + Molecular weight of compound for introducing modifying group (g/mol) x Binding amount of modifying group (mmol/g) x 0.001]

(2) When the "compound for introducing the modifying group" to be added is two or more types, the molar ratio of each compound (that is, the molar ratio when the total molar amount of the compounds to be added is 1) is proportionally adjusted. Then, the amount of cellulose fiber (converted amount) is calculated.

Preparation Example 1 (Preparation of anion-modified cellulose fibers)
Bleached coniferous kraft pulp (manufactured by West Fraser, trade name: Hinton) was used as the raw material cellulose fiber. As TEMPO, a commercial product (manufactured by ALDRICH, Free radical, 98% by mass) was used. Commercially available sodium hypochlorite, sodium bromide and sodium hydroxide were used.

First, 10 g of the bleached kraft pulp fibers and 990 g of deionized water were weighed into a 2 L PP beaker equipped with a mechanical stirrer and Teflon (registered trademark) stirring blades, and stirred at normal temperature and 100 rpm for 30 minutes. Thereafter, 0.13 g of TEMPO, 1.3 g of sodium bromide, and 35.5 g of a 10.5% by mass sodium hypochlorite aqueous solution were added in this order to 10 g of the pulp fiber. Using pH stat titration with an automatic titrator (manufactured by DKK Toa, trade name: AUT-701), a 0.5 M sodium hydroxide aqueous solution was added dropwise to maintain the pH at 10.5. After the reaction was carried out at room temperature for 120 minutes at a stirring speed of 100 rpm, the dropwise addition 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 resulting suspension of anion-modified cellulose fibers to adjust the pH to 2, ion-exchanged water was used to filter with a compact electrical conductivity meter (LAQUAtwinEC-33B, manufactured by Horiba, Ltd.). The fibers were thoroughly washed until the electrical conductivity of the liquid was measured to be 200 μs/cm or less, followed by dehydration treatment to obtain anion-modified cellulose fibers. The resulting anion-modified cellulose fibers had a carboxy group content of 1.50 mmol/g and an aldehyde group content of 0.23 mmol/g.

Preparation Example 2 (Preparation of micronized anion-modified cellulose fibers)
100 g of the suspension of the anion-modified cellulose fibers finally obtained in Preparation Example 1 (solid content: 2.0% by mass) was prepared, and 0.5 M sodium hydroxide aqueous solution was added to pH = 8. After adjusting to 200 g in total, ion-exchanged water was added. This suspension was subjected to micronization treatment three times at 150 MPa using a high-pressure homogenizer (manufactured by Yoshida Kikai Co., Ltd., trade name: Nanoveita L-ES), and a dispersion of micronized anion-modified cellulose fibers (containing solid content amount 1.0%). The counter ions of the carboxyl groups of the finely divided anion-modified cellulose fibers are sodium ions, which are abbreviated as "TCNF (Na type)".

Production Example 1 (Production of hydrophobically modified cellulose fiber)
A beaker equipped with a magnetic stirrer and stirrer was charged with 300 g (solid content: 2.0% by mass) of a dispersion obtained by replacing the solvent of the fine anion-modified cellulose fibers obtained in Preparation Example 2 with isopropanol. Subsequently, an amino-modified silicone ("SS-3551" manufactured by Dow Corning Toray Co., Ltd.; abbreviated as "silicone 1") is added to 0.5 mol of an amino group per 1 mol of the carboxy group of the anion-modified cellulose fiber. 100 g of isopropanol was added, and the mixture was stirred at room temperature (25° C.) for 14 hours to react. After the reaction was completed, the cake was washed with isopropanol, stirred at 5000 rpm for 5 minutes with a homogenizer (manufactured by Primix, trade name: TK Robomix), and then stirred with a high-pressure homogenizer (manufactured by Yoshida Kikai Co., Ltd.). (trade name: NanoVita L-ES) was applied at 150 MPa for 10 passes to obtain hydrophobically-modified cellulose fibers in which amino-modified silicone was linked to anion-modified cellulose fibers via ionic bonds. The rate of modification group introduction was 40% of the carboxy groups in the anion-modified cellulose fibers. The hydrophobically modified cellulose fibers had an average fiber diameter of 3.3 nm, an average fiber length of 578 nm, and a crystallinity of 30%.

Examples 1-10 and Comparative Examples 1-5
(1) Component used (A) component Hydrophobic modified cellulose fiber (B) component obtained in Production Example 1 Squalane: Viscosity (20 ° C.) 27.8 mPa s, Fuji Film Wako Pure Chemical Co., Ltd. (mineral oil )
・Paraffin-based raw material oil: Cosmo Pure Spin E, viscosity (20 ° C.) 7.2 mPa s, manufactured by Cosmo Oil Lubricants Co., Ltd. ・ Paraffin-based machine oil (1): Cosmo Pure Safety (grade 22), viscosity (20 ° C.) ) 58.8 mPa s, manufactured by Cosmo Oil Lubricants Co., Ltd. Paraffin-based machine oil (2): Cosmo Pure Safety (grade 32), viscosity (20 ° C.) 92.6 mPa s, manufactured by Cosmo Oil Lubricants Co., Ltd. (C ) Component Polyamide: Polyamide obtained in Production Example 2 below Curable prepolymer: urethane acrylate, Nippon Synthetic Chemical Co., Ltd. "Shikou UV-7000B" (Mw 3500)
(dispersion medium)
・Isopropanol: manufactured by Kanto Chemical Co., Ltd. ・Toluene: manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.

Production Example 2 (production of polyamide)
450 g of a dimer acid having 36 carbon atoms (Halidimer 250K, manufactured by Harima Kasei Co., Ltd., Cas number 61788-89-4, 100% (C36 Dimer acid)) was placed in a 2 L separa flask, heated to 70° C., and then replaced with nitrogen. . Thereafter, 45 g of ethylenediamine and 5 g of diethylenetriamine were gradually added, and after the addition, the temperature was raised until the internal temperature reached 145°C. After stirring at 145° C. for 1 hour, the internal temperature was raised to 210° C. and stirring was performed for 6 hours. Thereafter, while maintaining the internal temperature at 210° C., the pressure was reduced using a vacuum pump until the internal pressure reached 45 KPa, and the mixture was stirred for 0.5 hours to prepare a polyamide. The weight average molecular weight was 33,000. The content of diethylenetriamine in the polyamide was 3.0 mol %. In addition, the molecular weight of polyamide as component (C) was measured by the following method.

*Method for Measuring Molecular Weight of Polyamide The mass average molecular weight (Mw) was measured by gel permeation chromatography (GPC) using Hitachi L-6000 high performance liquid chromatography. Hitachi L-6000 was used as an eluent channel pump, a Shodex RISE-61 differential refractive index detector as a detector, and a GMHHR-H double-connected column as a column. Samples were adjusted to a concentration of 0.5 g/100 mL with eluent and 20 μL was used. A chloroform solution of 1 mmol/L Firmin DM20 (manufactured by Kao Corporation) was used as an eluent. The column temperature was 40° C. and the flow rate was 1.0 mL/min. Polystyrene (manufactured by Tosoh Corporation) was used as a standard polymer for preparing a calibration curve.

(2) Preparation of Defoaming Accelerating Composition Coating Liquid A defoaming promoting composition coating liquid was prepared using the above components in the following manner.
Component (A), component (B) and component (C) as required were sampled so that the mass ratio of the composition shown in Table 2 was obtained, and a dispersion medium was further blended into the screw tube. In Example 6, a 95/5 (mass ratio) mixture of toluene/isopropanol was used as the dispersion medium, and in other examples and Comparative Example 5, isopropanol was used. However, in Comparative Examples 1 to 4, the composition for promoting defoaming was used as the coating liquid without using a dispersion medium. When the curable prepolymer of component (C1) was used, 1-hydroxycyclohexylphenyl ketone as a photopolymerization initiator was further compounded in an amount of 4% by mass based on the curable prepolymer. Then, the contents of the screw tube were stirred for 12 hours at normal temperature (25° C.) with a magnetic stirrer rotating at 500 rpm. Thereafter, the mixture was stirred at 2200 rpm for 2 minutes using an automatic revolution stirrer (Awatori Mixer, manufactured by THINKY Co., Ltd.) to remove bubbles, thereby obtaining a coating liquid of the composition for promoting defoaming. In the coating liquid using the dispersion medium, the total concentration of components (A) to (C) was 3% by mass.

(3) Measurement of coating liquid viscosity The viscosity of the coating liquid prepared by the method of (2) was measured using a plate jig with a diameter of 25 mm using a rheometer Physica MCR301 manufactured by Anton Paar. ,000 rpm and 20°C. Table 2 shows the results. Comparative Examples 1 to 4 are the viscosity of the component (B) itself.

(4) Formwork preparation The obtained defoaming promoting composition coating liquid or the defoaming promoting compositions of Comparative Examples 1 to 4 were applied to a cylindrical steel formwork (height 10 cm, inner diameter 4 cm), It was applied to a thickness (wet thickness) of 1000 μm using a cosmetic handy spray (25 mL, manufactured by Artec Co., Ltd.). Next, the coating liquid of the composition for promoting defoaming was dried at normal temperature and normal pressure for 24 hours. When a dispersion medium was used in the coating liquid, the dispersion medium was volatilized by this operation. Next, only the defoaming promotion composition containing the curable prepolymer was irradiated with a UV irradiation machine (manufactured by FUSION UV SYSTEMS JAPAN, UV-1100-G) at a speed of 15.8 cm/min and an output of 90. %, a lamp height of 67 mm, and 2 passes to polymerize and cure the curable prepolymer. The final coating thickness was 50 μm in all examples.

(5) Preparation of mortar A mortar was prepared according to the composition shown in Table 1. The mortar is prepared by adding an aqueous solution of water, a dispersant and an antifoaming agent to a mixture of cement and sand, and kneading the mortar at 60 rpm for 60 seconds using a mortar mixer specified in JISR 5201. It was prepared by kneading at 120 rpm for 60 seconds. As a dispersant, Mighty 21VS (manufactured by Kao Corporation) is used, and the amount of dispersant added is mortar using a flow cone (upper diameter 70 mm x lower diameter 100 mm x height 60 mm) described in JIS R 5201. The flow was adjusted to 200±10 mm, and the effective solid content was 0.2 parts by mass relative to the powder in any of the examples and comparative examples. Antifoaming agent No. 21 (manufactured by Kao Corporation) is used, and the amount of antifoaming agent added is determined by filling a stainless steel container (inner diameter 7.5 cm, inner height 8.0 cm, weight 1.0 kg) with mortar and removing entrained air. The amount of defoaming agent added was adjusted so that the amount of air measured by the mass method after extraction was 1.0%±0.5%. 007 parts by mass.

The ingredients used to prepare the mortar are as follows.
・ Cement: 1:1 (mass ratio) mixture of ordinary Portland cement manufactured by Taiheiyo Cement Co., Ltd. and ordinary Portland cement manufactured by Sumitomo Osaka Cement Co., Ltd., specific gravity 3.16
・Sand: Surface dry specific gravity 2.50 from Joyo, Kyoto Prefecture
Water: tap water (in Table 1, the water content includes the amount of dispersant and antifoaming agent added)

(6) Evaluation of Surface Appearance of Hardened Mortar The prepared mortar was placed in a cylindrical steel mold (height 10 cm, inner diameter 4 cm) coated with the composition for promoting defoaming shown in Table 2, which was prepared in (4). 30 seconds under vibration of 2500 vpm using a table vibrator (manufactured by Kansai Kiki Seisakusho Co., Ltd.), cured in air at 20° C. for 24 hours, and demolded. The filling of this mortar into the formwork and demolding were carried out twice for each composition for promoting defoaming. The surface of the hardened mortar was photographed with a digital camera after recording the photographing scale, and the photographed image was subjected to image analysis using ImageJ, an image processing open source software. The surface bubble diameter of the photographed image was converted to the actual size with reference to the photographing scale, and the total surface area of cured body surface bubbles per surface area of 10,000 mm ² was calculated. The values in Table 2 are obtained by averaging the measured values obtained by photographing each surface of each two mortar cured bodies. It can be said that the smaller the value of the total bubble surface area on the surface of the cured body is, the more excellent the surface appearance is, which is preferable.

(Discussion)
Compared to the defoaming-promoting composition of the comparative example that does not contain the hydrophobically-modified cellulose fiber of the component (A), the defoaming-promoting composition of the example containing the hydrophobically-modified cellulose fiber of the component (A) has a hardened body surface It can be seen that the value of the total bubble surface area of is small and there are few surface bubble traces, that is, the surface appearance is excellent. In the examples and comparative examples, an antifoaming agent was used, but this was used to adjust the amount of air in the mortar. This evaluation does not contribute to promotion of defoaming. In addition, if a cured product is produced without using a composition for promoting defoaming, demolding becomes difficult, and surface aesthetics (total surface area of cells) cannot be evaluated. Further, for example, when a commercially available release agent is used, the value of the total bubble surface area is equivalent to that of the comparative example.

Claims (17)

(A) A defoaming promoting composition for a hydraulic composition containing hydrophobically modified cellulose fibers [hereinafter referred to as component (A)],
Component (A) is a hydrophobically modified cellulose fiber in which an amino-modified silicone compound is linked via an ionic bond to an anionic group of a cellulose fiber having an anionic group.
A defoaming promoting composition for a hydraulic composition. 2. The defoaming promoting composition for a hydraulic composition according to claim 1, wherein the anionic group is a carboxy group. 3. The defoaming promoting composition for a hydraulic composition according to claim 1, wherein the amino-modified silicone compound as component (a) is a compound represented by the following 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 and a hydrogen atom. R ^2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group and a hydrogen atom. B represents a side chain having at least one amino group, and R ^3a represents an alkyl group having 1 to 3 carbon atoms or a hydrogen atom. x and y each indicate an average degree of polymerization, and the kinematic viscosity at 25° C. of the compound is 10 mm ² /s or more and 20,000 mm ² /s or less, and the amino equivalent is 400 g/mol or more and 8,000 g/mol or less. selected for R ^1a , R ^2a and R ^3a may be the same or different, and a plurality of R ^2a may be the same or different. ] 4. The defoaming promoting composition for a hydraulic composition according to any one of claims 1 to 3, comprising (B) an oil [hereinafter referred to as component (B)]. 5. The defoaming promoting composition for a hydraulic composition according to claim 4, wherein the component (B) has a viscosity at 20[deg.] C. of 300 mPa.s or less. 6. The defoaming promoting composition for a hydraulic composition according to claim 4, wherein the component (B) is one or more selected from terpenoids and mineral oils. (A) / (B), which is the mass ratio of the content of component (A) to the content of component (B), is 0.01 or more and 1 or less, according to any one of claims 4 to 6 A defoaming promoting composition for hydraulic compositions. (C) The defoaming promoting composition for a hydraulic composition according to any one of claims 1 to 7, which contains component (A) and a polymer compound other than oil [hereinafter referred to as component (C)]. thing. 9. The defoaming promoting composition for a hydraulic composition according to claim 8, containing 1% by mass or more and 1000% by mass or less of component (C) relative to component (A). A fluid containing air bubbles is brought into contact with the composition for promoting deaeration of the hydraulic composition according to any one of claims 1 to 9, and suppresses the appearance of air bubbles on the surface of the fluid at the contact position. A method for controlling foaming of a fluid, wherein the fluid is a hydraulic composition. 11. The foam control method of claim 10, wherein the fluid is contacted with a film obtained from the hydraulic composition defoaming promoting composition. A method for producing a cured body, wherein the hydraulic composition containing air bubbles is brought into contact with a support coated with the composition for accelerating defoaming of the hydraulic composition according to any one of claims 1 to 9 and cured. . 13. The method for producing a hardened body according to claim 12, wherein the support is a form for accommodating the hydraulic composition. 14. The method for producing a cured body according to claim 12 or 13, wherein the support is separated from the cured body after curing of the hydraulic composition. The method for producing a cured body according to any one of claims 12 to 14, wherein traces of air bubbles on the surface of the cured body are reduced. The hydraulic composition containing air bubbles is filled into a mold coated with the composition for accelerating defoaming of the hydraulic composition according to any one of claims 1 to 9 and cured, and then the cured body obtained. A method for producing a hardened body of a hydraulic composition, which is removed from the mold. The hydraulic composition containing air bubbles is cured by contacting it with the coating film obtained from the hydraulic composition defoaming promoting composition according to any one of claims 1 to 9, and on the surface of the cured body A method for improving the surface appearance of a cured body, which reduces air bubble marks.