JP7123707B2 - Membrane with hydrophobically modified cellulose fibers and organic medium - Google Patents

Description

The present invention relates to membranes comprising hydrophobically modified cellulose fibers and an organic medium.

Conventionally, in the field of packaging containers for cosmetics, foods, etc., objects that can come into contact with containers, trays, etc. Surface films have been developed to prevent adhesion of fluids such as dirt and stains. Recently, a porous polymer membrane having a network structure in which fibrous polymers are mutually entangled in a three-dimensional direction, and having a continuous pore structure as the voids, and a (Patent Document 1), and Patent Document 1 exemplifies a fluorine-based oil or a silicone oil as the lubricant liquid. (Claim 7). Furthermore, materials using cellulose fibers, which are biomass that exists in large quantities in nature, are also attracting attention. gel films) are disclosed.

JP 2016-011375 A JP 2013-082796 A

However, in the technique of Patent Document 1, an organic medium such as oil that constitutes the surface film migrates to the fluid, and as a result, there is a possibility that the effect of preventing the adhesion of dirt and the like to the surface film is impaired. Such a phenomenon can occur particularly remarkably when the fluid contains liquid organic matter.

Therefore, the inventors investigated a membrane in which the organic medium that constitutes the membrane is less likely to migrate into the fluid, and newly found that a membrane containing a specific hydrophobically modified cellulose fiber and an organic medium is excellent in suppressing the migration of the organic medium. Furthermore, the present inventors further studied and found that even when such an excellent membrane is used repeatedly, the performance (that is, the durability of the membrane) that can maintain its performance can be further improved. Accordingly, the present invention relates to a film that exhibits less migration of an organic medium and is excellent in durability due to repeated use of the film. Further, the present invention relates to a molded article having such a film, which has little migration of an organic medium and has excellent durability. Furthermore, the present invention relates to a method for forming a film on a molded body. Further, the present invention relates to a membrane dispersion suitable for forming such a membrane.

The present invention relates to the following [1] to [4].
[1] Hydrophobic-modified cellulose fibers in which a modifying group is bonded to one or more groups selected from carboxy groups and hydroxyl groups of cellulose fibers, and one or more selected from the group consisting of (X) and (Y) below polymer compound, as well as an organic medium.
(X) a polycondensation polymer having an ester group, an amide group, a urethane group, an imino group, an ether group, or a carbonate group;
(Y) A methacrylic or acrylic polymer having an ester group or an amide group in a side chain [2] A molded article having the film according to [1] above.
[3] Hydrophobically modified cellulose fibers in which a modifying group is bonded to one or more groups selected from carboxy groups and hydroxyl groups of cellulose fibers, and one or more selected from the group consisting of the above (X) and (Y) and a dispersion containing an organic medium, and a step 2 of applying the dispersion prepared in the step 1 to the molded article.
[4] Hydrophobically modified cellulose fibers in which a modifying group is bonded to one or more groups selected from carboxy groups and hydroxyl groups of cellulose fibers, and one or more selected from the group consisting of (X) and (Y) and an organic medium.

The film of the present invention has the effects of less migration of an organic medium and excellent durability due to repeated use of the film. Furthermore, since the molded article of the present invention has such a film, it has the effect of being less susceptible to migration of an organic medium and having excellent durability.

The membrane of the present invention contains a specific hydrophobically modified cellulose fiber, a specific polymer compound and an organic medium.

Although the mechanism by which the membrane of the present invention exerts the effect that the organic medium constituting the membrane is less likely to migrate into the fluid and is excellent in durability is not clear, it is presumed as follows. Organic media, especially organic media with an SP value of 10 or less, are relatively hydrophobic, and thus are thought to have a strong affinity with the hydrophobically modified cellulose fibers. As a result, the organic medium easily separates from the hydrophobically modified cellulose fibers. Therefore, it is presumed that even if the fluid contains an oily component, it will be difficult for it to migrate into the fluid. Furthermore, by adding a specific polymer compound, the strength of the film itself is improved, or the affinity of the film surface with the organic medium is improved, and as a result, the migration of the organic medium is unexpectedly enhanced. It is presumed that the durability of the membrane was improved.

<Hydrophobic modified cellulose fiber>
The hydrophobically-modified cellulose fiber in the present invention is obtained by bonding a modifying group to one or more groups selected from a carboxy group and a hydroxyl group of the cellulose fiber, as long as it exhibits dispersibility in an organic medium. Having dispersibility in an organic medium means, for example, that the viscosity of the mixed liquid of the organic medium and the target hydrophobically modified cellulose fiber is measured with an E-type viscometer (25 ° C., 1 rpm, after 1 minute, standard cone rotor, rotor code : 01) indicates that thickening is observed. For example, as the hydrophobically modified cellulose fiber in the present invention, the viscosity of the dispersion liquid after refining treatment is 50 mPa. s or more is preferable. In addition, the miniaturization treatment can be performed by a method described later.

(cellulose fiber)
The raw cellulose fiber is preferably natural cellulose fiber from an environmental point of view. Examples include wood pulp such as softwood pulp and hardwood pulp; cotton pulp such as cotton linter and cotton lint; straw pulp and bagasse pulp. Non-wood pulp; bacterial cellulose and the like can be mentioned, and one of these can be used alone or two or more of them can be used in combination.
In addition, from the viewpoint of suppressing the migration of the organic medium to the fluid, the cellulose fiber is preferably a cellulose fiber having a carboxy group (hereinafter also referred to as oxidized cellulose fiber), which is obtained by oxidizing the cellulose fiber. be able to.

(oxidized cellulose fiber)
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. A method of oxidation using a bromide of is applicable. 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.

By oxidizing cellulose fibers using TEMPO as a catalyst, the C6-position group (--CH ₂ OH) of the cellulose structural unit is selectively converted to a carboxy group. Therefore, a preferred embodiment of the oxidized cellulose fiber in the present invention is a cellulose fiber having a carboxy group at the C6 position of the cellulose structural unit.

(Carboxy group content)
From the viewpoint of introducing a modifying group, the carboxyl group content of the oxidized cellulose fiber is preferably 0.1 mmol/g or more, more preferably 0.4 mmol/g or more, still more preferably 0.6 mmol/g or more, and still more preferably It is 0.8 mmol/g or more. Also, from the viewpoint of improving handling properties, it is preferably 3 mmol/g or less, more preferably 2 mmol/g or less, and even more preferably 1.8 mmol/g or less. The "carboxy group content" means the total amount of carboxy groups in the cellulose constituting the hydrophobically-modified cellulose fiber or oxidized cellulose fiber, and is specifically measured by the method described in Examples below.

The preferred ranges of the average fiber diameter, average fiber length, and average aspect ratio of the oxidized cellulose fibers are the same as those for the hydrophobically modified cellulose fibers described later, and can be determined by the same measurement methods as for the hydrophobically modified cellulose fibers described later. can be done.

(Modifying group)
As used herein, the bonding of the modifying group in the hydrophobically-modified cellulose fiber means that the modifying group is bonded to one or more groups selected from the group consisting of carboxy groups and hydroxyl groups on the surface of the cellulose fiber, preferably to the carboxy group. / or means a state of being covalently bonded. The mode of binding to the carboxy group includes ionic bond and covalent bond. The covalent bond here includes, for example, an amide bond, an ester bond, and a urethane bond, and among them, an amide bond is preferable from the viewpoint of suppressing migration of the organic medium to the fluid. Moreover, covalent bond is mentioned as a bonding mode to a hydroxyl group, and specifically, ester bond; ether bond such as carboxymethylation and carboxyethylation; and urethane bond. From the viewpoint of suppressing migration of an organic medium into a fluid, the hydrophobically modified cellulose fiber in the present invention includes a compound for introducing a modifying group into the carboxyl group already present on the surface of the cellulose fiber with an ionic bond and/or an amide bond. Preferably, it is 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.

In modification to a hydroxyl group, an ester bond is preferably an acid anhydride, such as acetic anhydride, propionic anhydride, and succinic anhydride. Ether bonds are exemplified by epoxy compounds (eg alkylene oxide and alkyl glycidyl ether), alkyl halides and their derivatives (eg methyl chloride, ethyl chloride and monochloroacetic acid).

A hydrocarbon group or the like can be used as the modifying group in the present invention. 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, it is preferably a chain saturated hydrocarbon group, a cyclic saturated hydrocarbon group, or an aromatic hydrocarbon group.

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, still more preferably 6, from the viewpoint of synovial surface property and suppression of transfer of organic medium to fluid. 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. Hereinafter, the number of carbon atoms in the hydrocarbon group means the total number of carbon atoms of the modifying group as a whole.

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.; From the viewpoint of surface property and suppression of transfer of organic medium to fluid, preferably propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, isobutyl group, pentyl group, tert-pentyl group and 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 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. , a tridecene group, a tetradecene group, and an octadecene group, and from the viewpoint of synovial fluid surface property and suppression of migration of organic media to fluids, preferably an ethylene group, a propylene group, a butene group, an isobutene group, an isoprene group, and a pentene group. , hexene group, heptene group, octene 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 synovial surface property and suppression of transfer of organic medium to fluid, preferably cyclopropane group, cyclobutyl group, cyclopentane group, cyclohexyl group, cycloheptyl group cyclooctyl group, cyclononyl group, cyclodecyl group and 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 number of carbon atoms in the aryl group may be 6 or more, and is preferably 24 or less, more preferably 20 or less, still more preferably 14 or less, from the viewpoint of synovial surface property and suppression of transfer of organic medium to fluid. More preferably 12 or less, more preferably 10 or less.

The total number of carbon atoms in the aralkyl group is 7 or more, preferably 8 or more from the viewpoint of synovial surface property and suppression of transfer of organic medium to fluid, and preferably 24 or less from the same viewpoint. It is more preferably 20 or less, still more preferably 14 or less, still more preferably 13 or less, still more preferably 11 or less.

The aryl group includes, for example, a phenyl group, a naphthyl group, an anthryl group, a phenanthryl group, a biphenyl group, a triphenyl group, a terphenyl group, and groups in which these groups are substituted with the substituents described below. One type alone or two or more types 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 synovial surface property and suppression of transfer of organic medium to fluid.

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 aromatic groups of these groups substituted with substituents described below. groups, etc., and these may be introduced singly or in combination of two or more in an arbitrary ratio. Among them, benzyl group, phenethyl group, phenylpropyl group, phenylpentyl group, phenylhexyl group, and phenylheptyl group are preferable from the viewpoint of synovial surface property and suppression of transfer of organic medium to fluid.

The modifying group may further have a substituent. For example, when the modifying group is a hydrocarbon group, the total carbon number 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. C1-6 alkoxy group; methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, isobutoxycarbonyl group, sec-butoxycarbonyl group, tert-butoxycarbonyl group, pentyloxycarbonyl 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.

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

Specific examples of primary to tertiary amines include ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, butylamine, dibutylamine, hexylamine, dihexylamine, octylamine, dioctylamine, trioctylamine, dodecylamine, didodecylamine, stearylamine, distearylamine, monoethanolamine, diethanolamine, triethanolamine, aniline, benzylamine, amino-modified silicone compounds, and the like. 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, didodecylamine, distearylamine, amino-modified silicone compound, tetraethylammonium hydroxide (TEAH), tetrabutylammonium hydroxide (TBAH), tetrapropylammonium hydroxide (TPAH), aniline, more preferably is propylamine, dodecylamine, amino-modified silicone compound, tetrabutylammonium hydroxide (TBAH), aniline, more preferably amino-modified silicone compound.

Among these compounds, hydrophobically modified cellulose fibers obtained by using an amino-modified silicone compound are particularly useful as raw materials for membranes. Therefore, as one aspect of the hydrophobically modified cellulose fiber, there is provided a hydrophobically modified cellulose fiber in which a modifying group introduced by an amino-modified silicone compound is bonded to one or more groups selected from carboxy groups and hydroxyl groups of the cellulose fiber. be. When such a hydrophobically modified cellulose fiber is used as a membrane, it is possible to exhibit the effects of excellent synovial fluid surface property and suppression of migration of organic medium into fluid.

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

The kinematic viscosity at 25° C. can be determined with an Ostwald viscometer, and is more preferably 200 to 10,000 mm ² /s, still more preferably 200 to 10,000 mm 2 /s, from the viewpoint of the synovial fluid surface property and the suppression of the migration of the organic medium to the fluid. 500 to 5,000 mm ² /s.

In addition, the amino equivalent is preferably 400 to 8,000 g/mol, more preferably 600 to 5,000 g/mol, still more preferably 800 to 8,000 g/mol, from the viewpoint of synovial surface property and suppression of transfer of organic medium to fluid. 3,000 g/mol. 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 improves synovial surface properties and transfer of organic media to fluids. From the viewpoint of suppression, it is preferably a methyl group or a hydroxy group. R ^2a is a group selected from an alkyl group having 1 to 3 carbon atoms, a hydroxy group, or a hydrogen atom, and is preferably a methyl group or a hydroxy group from the viewpoint of synovial fluid surface property and inhibition of migration of an organic medium to a fluid. be. 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 a number of 10 to 10,000, more preferably a number of 20 to 5,000, from the viewpoint of synovial surface property and suppression of migration of organic medium to fluid, More preferably, the number is from 30 to 3,000. y is preferably a number from 1 to 1,000, more preferably a number from 1 to 500, still more preferably a number from 1 to 200. The weight average molecular weight of the compound of general formula (a1) is preferably 2,000 to 1,000,000, more preferably 5,000 to 100,000, still more preferably 8,000 to 50,000.

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} )
-C3H6 _- NH-[ _{C2H4 -} NH] _{f - C2H4 -} NH( _CH3 )
—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} )

The amino-modified silicone compound is preferably a monoamino-modified silicone having one amino group in one of the side chains B and a side chain from the viewpoint of synovial surface property and suppression of transfer of organic medium to fluids. One or more selected from the group consisting of diamino-modified silicones having two amino groups in one of B, more preferably the side chain B having an amino group is represented by -C ₃ H ₆ -NH ₂ a compound [hereinafter referred to as component (a1-1)] and a compound in which side chain B having an amino group is represented by —C ₃ H ₆ —NH—C ₂ H ₄ —NH ₂ [hereinafter referred to as (a1-2) component] is one or more selected from the group consisting of

As the amino-modified silicone compound in the present invention, from the viewpoint of performance, TSF4703 (kinematic viscosity: 1000, amino equivalent: 1600) manufactured by Momentive Performance Materials, TSF4708 (kinematic viscosity: 1000, amino equivalent: 2800), Dow Corning Toray Silicone Co., Ltd. SS-3551 (kinematic viscosity: 1000, amino equivalent: 1600), SF8457C (kinematic viscosity: 1200, amino equivalent: 1800), SF8417 (kinematic viscosity: 1200, amino equivalent: 1700) ), BY16-209 (kinematic viscosity: 500, amino equivalent: 1800), BY16-892 (kinematic viscosity: 1500, amino equivalent: 2000), BY16-898 (kinematic viscosity: 2000, amino equivalent: 2900), FZ-3760 (kinematic viscosity: 220, amino equivalent: 1600), Shin-Etsu Chemical Co., Ltd. KF8002 (kinematic viscosity: 1100, amino equivalent: 1700), KF867 (kinematic viscosity: 1300, amino equivalent: 1700), KF-864 ( Kinematic viscosity: 1700, amino equivalent: 3800), BY16-213 (kinematic viscosity: 55, amino equivalent: 2700), BY16-853U (kinematic viscosity: 14, amino equivalent: 450) are preferred. In ( ), kinematic viscosity is measured at 25° C. (unit: mm ² /s), and the unit of amino equivalent is g/mol.

BY16-213 and BY16-853U are more preferable as the component (a1-1). More preferred components (a1-2) are SF8417, BY16-209, FZ-3760 and SS-3551.

The average binding amount of modifying groups, preferably one or more groups selected from the group consisting of a hydrocarbon group and a silicone group, in the hydrophobically-modified cellulose fibers, per hydrophobically-modified cellulose fibers, improves synovial fluid surface properties and organic medium flow. From the viewpoint of suppressing transfer to animals, preferably 0.01 mmol/g or more, more preferably 0.05 mmol/g or more, still more preferably 0.1 mmol/g or more, still more preferably 0.3 mmol/g or more, and still more preferably is 0.5 mmol/g or more. Further, from the viewpoint of reactivity, 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, still more preferably 1.5 mmol/g g or less. Here, when a hydrocarbon group selected from a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, and a cyclic saturated hydrocarbon group as a modifying group and an aromatic hydrocarbon group are introduced at the same time, Even if there is, the individual average bond amount is preferably within the above range.

In addition, the introduction rate of the modifying group in the hydrophobically-modified cellulose fiber is preferably 5% or more, more preferably 10%, from the viewpoint of synovial fluid surface property and suppression of migration of organic medium to fluid for any modifying group. Above, more preferably 15% or more, preferably 70% or less, more preferably 60% or less, still more preferably 50% or less from the viewpoint of reactivity. Here, when a hydrocarbon group selected from a chain saturated hydrocarbon group, a chain unsaturated hydrocarbon group, and a cyclic saturated hydrocarbon group as a modifying group and an aromatic hydrocarbon group are introduced at the same time, is preferably within the above range as long as the total introduction rate does not exceed the upper limit of 100%.

In the present specification, the average bonding amount of the modifying group is adjusted by the amount of compound added for introducing the modifying group, the type of compound for introducing the modifying group, the reaction temperature, the reaction time, the solvent, and the like. can be done. In addition, the average bonding amount (mmol/g) and the introduction rate (%) of the modifying group in the hydrophobically-modified cellulose fiber refer to the amount and ratio of the modifying group introduced to the carboxyl group or hydroxyl group on the surface of the hydrophobically-modified cellulose fiber. There is, the carboxy group content of the hydrophobically modified cellulose fiber can be calculated according to a known method (e.g., titration, IR measurement, etc.), specifically by measuring by the method described in the examples below. The hydroxyl group content of the modified cellulose fiber can be calculated by measuring according to known methods (eg, titration, IR measurement, etc.).

(Method for producing hydrophobically modified cellulose fiber)
The cellulose fibers used in the present invention can be produced according to known methods without particular limitation, as long as the modifying group can be introduced into the cellulose fibers described above. The cellulose fibers referred to here are oxidized cellulose fibers obtained by a known method, for example, with reference to the explanation of the oxidation reaction step described in JP-A-2011-140632, or are further subjected to additional oxidation treatment or By performing a reduction treatment, oxidized cellulose fibers from which aldehydes have been removed can be prepared.

Specific production methods include an aspect (aspect A) in which the modifying group is bound to the cellulose fiber by ionic bonding, and an aspect (aspect B) in which the modifying group is bonded to the cellulose fiber by covalent bonding. 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

In addition, 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) after the step (1) is performed, and in order from the step (1) 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".

[Step (1)]
In this step, for example, the oxidation treatment step described in JP-A-2015-143336 (for example, 2,2,6,6-tetramethylpiperidine-1-oxyl (TEMPO) was used for natural cellulose fibers. oxidation treatment) and purification step (if necessary), oxidized cellulose fibers having a carboxy group content of preferably 0.1 mmol/g or more can be obtained.

[Step (2A)]
This step is carried out by mixing oxidized cellulose fibers and a compound for introducing a modifying group in a solvent, for example, with reference to the method described in step (B) of JP-A-2015-143336. can be implemented. The "amine having an EO/PO copolymerization moiety" in step (B) of JP-A-2015-143336 corresponds to the "compound for introducing a modifying group" in step (2A) of the present invention.

[Step (2B)]
In this step, the oxidized cellulose fiber and the compound for introducing the modifying group are mixed in the presence of a condensing agent, and the carboxy group contained in the oxidized cellulose fiber and the amino group of the compound for introducing the modifying group are combined. groups to form an amide bond. For example, it can be carried out with reference to the method described in step (B) of JP-A-2015-143337. The "amine having an EO/PO copolymerization moiety or a PO polymerization moiety" in the step (B) of JP-A-2015-143337 is the "compound for introducing a modifying group" in the step (2B) of the present invention. Applicable.

[Miniaturization process]
This step is a step of refining the oxidized cellulose fibers obtained in the previous step (or the oxidized cellulose fibers into which a modifying group has been introduced), and fine oxidized cellulose fibers are obtained. 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. Specifically, it can be carried out with reference to the description of the miniaturization process in Japanese Patent Application Laid-Open No. 2013-151661.

Moreover, the hydrophobic modified cellulose fiber obtained by combining the aspect A and the aspect B may be used. 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.

The average fiber diameter of the obtained hydrophobically modified cellulose fibers is preferably 0.1 nm or more, more preferably 0.5 nm or more, and still more preferably 1 nm, from the viewpoint of synovial surface property and suppression of transfer of organic medium to fluid. Above, more preferably 2 nm or more, still more preferably 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 resulting hydrophobically modified cellulose fibers is preferably 150 nm or longer, more preferably 200 nm or longer, from the viewpoint of synovial surface property and inhibition of transfer of organic medium to fluid. From the same point of view, it is preferably 1000 nm or less, more preferably 750 nm or less, even more preferably 500 nm or less, still more preferably 400 nm or less.

In the present invention, the average fiber diameter and average fiber length of the hydrophobically-modified 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 hydrophobically modified cellulose fibers is preferably 1 or more, more preferably 10 or more, from the viewpoint of synovial surface property and suppression of migration of organic medium to fluid. , More preferably 20 or more, more preferably 40 or more, still more preferably 50 or more, and from the same viewpoint, preferably 150 or less, more preferably 140 or less, still more preferably 130 or less, still more preferably 100 or less, and further It is preferably 95 or less, more preferably 90 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, from the viewpoint of synovial surface property and suppression of migration of organic medium to fluid. It is more preferably 45 or less, and although the lower limit is not particularly set, it is preferably 4 or more from the viewpoint of economy. Since the hydrophobically modified cellulose fibers having a low aspect ratio are excellent in dispersibility in the dispersion, a highly uniform film can be obtained.

<Polymer compound>
The polymer compound constituting the membrane of the present invention is one or more polymer compounds selected from the group consisting of (X) and (Y) below, and suppresses migration of the organic medium into the fluid and prevents the formation of the membrane. From the viewpoint of durability, the polymer compound (X) is preferred.
(X) a polycondensation polymer having an ester group, an amide group, a urethane group, an imino group, an ether group, or a carbonate group;
(Y) Methacrylic or acrylic polymer having an ester group or an amide group in the side chain

The polymer compound preferably contains a polymer component having a molecular weight of 100,000 or more, from the viewpoint of the migration property of the organic medium and the durability of the film. From the same viewpoint, the amount of such a polymer component in the polymer compound is preferably 1% by mass or more, more preferably 5% by mass or more, still more preferably 10% by mass or more, and still more preferably 15% by mass. % or more, and from the same viewpoint, it is preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, and even more preferably 35% by mass or less. The mass-average molecular weight of the polymer compound and the amount of the polymer component having a molecular weight of 100,000 or more in the polymer compound can be measured according to the method described in Examples below.

The mass-average molecular weight of the polymer compound is preferably 1,000 or more from the viewpoint of migration in an organic medium and film durability, and preferably 500,000 or less from the same viewpoint.

The polycondensation polymer (X) having an ester group includes 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.

The polycondensation polymer (X) having an amide group includes 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.

Condensation products of diisocyanates such as triresin diisocyanate, diphenylisocyanate, xylylene diisocyanate and hexamethylene diisocyanate and diols such as ethylene glycol, propylene glycol and butanediol, etc., as the polycondensation polymer (X) having a urethane group. is mentioned.

Condensation products of alkylimine such as ethyleneimine, propyleneimine, butyleneimine, dimethylethyleneimine, pentyleneimine and hexyleneimine, and melamine/formamide condensates are examples of polycondensation polymers (X) having an imino group. mentioned.

Condensation products of alkylene oxides such as ethylene oxide, propylene oxide and butylene oxide, condensates of epichlorohydrin and bisphenol A, condensates of formaldehyde and the like can be mentioned as the polycondensation polymer (X) having an ether group.

The polycondensation polymer (X) having a carbonate group includes 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxy Examples include condensates of polyols such as phenyl)cyclohexane and phosgene.

The polycondensation polymer (X) preferably further contains a tri- or higher functional monomer as a constituent unit from the viewpoints of migration in an organic medium and film durability.

Examples of tri- or higher functional monomers include tri- or higher functional monomers such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine, and pentapentylenehexamine. Tri- or higher functional alcohols such as amines, trimethylol, trimethylolpropane, glycerin, pentaerythritol, ditrimethylolpropane, trimellitic acid, benzophenonetetracarboxylic acid, trimellitic anhydride, pyromellitic acid, pyromellitic anhydride, anhydride Benzophenonetetracarboxylic acid, trimesic acid, ethylene glycol bis(anhydrotrimellitate), glycerol tris(anhydrotrimellitate), and other trifunctional or higher carboxylic acids, which improve the migration of organic media and the durability of membranes. From the viewpoint of functionality, tri- or higher functional amines such as diethylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine, di(methylethylene)triamine, dibutylenetriamine, tributylenetetramine, and pentapentylenehexamine are preferred. is.

The polycondensation polymer (X) further contains tri- or more functional monomers as structural units to form cross-linking points. expected to improve.

The content of the trifunctional or higher monomer in the polycondensation polymer (X) is preferably 0.2 mol % or more, more preferably 0, from the viewpoint of the migration property of the organic medium and the durability of the film. 0.5 mol % or more, more preferably 2.5 mol % or more, and from the viewpoint of migration of the organic medium, preferably 25 mol % or less, more preferably 20 mol % or less, and still more preferably is 15 mol % or less.

The polycondensation polymer (X) is preferably one or more polymer compounds selected from the group consisting of the following (a) and (b) from the viewpoint of the migration property of the organic medium and the durability of the film. Therefore, the polyamide compound (a) is more preferable from the viewpoints of suppression of migration of the organic medium to the fluid and durability of the membrane.
(a) Polyamide compound
(b) polyalkyleneimine compound

(a) Polyamide compound Polyamide compounds having any chemical structure can be used as long as they do not have a cellulose structure and are high molecular compounds 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 composed of diamines and one or more carboxylic acids selected from the group consisting of monocarboxylic acids, dicarboxylic acids and polymerized fatty acids.

The weight average molecular weight of the polyamide compound is preferably 5,000 or more, more preferably 10,000 or more, still more preferably 20,000 or more, and still more preferably 30,000 or more, from the viewpoint of the migration property of the organic medium and the durability of the film. , from the same point of view, it is preferably 500,000 or less, more preferably 250,000 or less, still more preferably 100,000 or less, and even more preferably 50,000 or less.

Polyamide compounds are usually obtained by ring-opening polymerization reaction of cyclic lactams, self-condensation reaction of amino acids and derivatives thereof, condensation polymerization reaction of carboxylic acids and amine compounds, and the like. A polyamide compound obtained by a condensation polymerization reaction of a carboxylic acid and an amine compound can be obtained, for example, by condensation (condensation) reaction of a carboxylic acid and an amine compound.

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

Monocarboxylic acids that can play the role of a polymerization terminator in the reaction in which polyamide compounds are formed, such as acetic acid, propionic acid, butyric acid, valeric acid, lauric acid, palmitic acid, stearic acid, aragidic acid, and behenine. acid and the like. Examples of unsaturated aliphatic monocarboxylic acids include oleic acid, linoleic acid, linolenic acid, eicosenoic acid, erucic acid, mixed fatty acids obtained from natural fats and oils (tall oil fatty acids, rice bran fatty acids, soybean oil fatty acids, beef tallow, fatty acids, etc.), and these may be used alone or in combination of two or more.
The monocarboxylic acid used in the present invention preferably has 8 or more and 24 or less carbon atoms, more preferably 10 or more and 22 or less carbon atoms, from the viewpoint of the migration property of the organic medium and the durability of the film. and more preferably those having 12 or more and 18 or less carbon atoms.

Dicarboxylic acids include, for example, adipic acid, sebacic acid, dodecanedioic acid, phthalic acid, isophthalic acid, terephthalic acid, succinic acid, and alkenylsuccinic acid. As the alkenylsuccinic acid, those having 4 to 20 carbon atoms in the alkenyl group are preferred.

A polymerized fatty acid is a polymer obtained by polymerizing a monobasic fatty acid having an unsaturated bond or a polymer obtained by polymerizing an esterified product of a monobasic fatty acid having an unsaturated bond. Examples of polymerized fatty acids include structures obtained by a dehydration condensation reaction of dimer acids derived from vegetable oils and fats.

As the monobasic fatty acid having an unsaturated bond, an unsaturated fatty acid having 8 to 24 total carbon atoms and having 1 to 3 unsaturated bonds is usually used. These unsaturated fatty acids include, for example, oleic acid, linoleic acid, linolenic acid, natural drying oil fatty acids, natural semi-drying oil fatty acids, and the like. Examples of esters of monobasic fatty acids having unsaturated bonds include esters of monobasic fatty acids having unsaturated bonds and aliphatic alcohols, preferably aliphatic alcohols having 1 to 3 carbon atoms. The polymer obtained by polymerizing the monobasic fatty acid having an unsaturated bond or the polymerized fatty acid obtained by polymerizing the esterified product of the monobasic fatty acid having an unsaturated bond is a dimer. The main component is preferred. For example, as a polymer of an unsaturated fatty acid with 18 carbon atoms, the composition is 0 to 10% by mass of a monobasic acid with 18 carbon atoms (monomer) and 60 to 10% by mass of a dibasic acid with 36 carbon atoms (dimer). A commercially available product containing 99% by mass and 30% by mass or less of an acid (trimer or higher) of tribasic acid having 54 carbon atoms or more.

Furthermore, as the carboxylic acid component, in addition to monocarboxylic acids, dicarboxylic acids and polymerized fatty acids, other carboxylic acids may be added as long as they do not impair the physical properties of the film.

Among these carboxylic acids, a combination of monocarboxylic acid and polymerized fatty acid is particularly preferably used. Incidentally, the carboxylic acid may be an ester with an alcohol having 1 to 3 carbon atoms.

In addition, examples of the amine compound, which is the other raw material for the polycondensation reaction, 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.

In addition, as the amine compound, a monoamine can be used as a role of a polymerization terminator in the reaction in which the polyamide compound is produced.

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

Further, from the viewpoint of the migration property of the organic medium and the durability of the film, the amine compound preferably includes an amine component containing polyamine, and more preferably, the amine compound includes diamine, triamine, tetramine, pentamine and hexatetraamine. An amine component (referred to as "amine component 1") used in combination with one or more selected from the group consisting of diamines or an amine component containing two or more diamines (referred to as "amine component 2") can be used. . From the viewpoint of sliding speed, amine component 1 is more preferable as the amine compound. The mass ratio of each component in the amine component 1 when used in combination is [diamine: one or more selected from the group consisting of triamine, tetramine, pentamine and hexamine] from the viewpoint of the migration property of the organic medium and the durability of the film. , preferably 99.5:0.5 to 50:50, more preferably 99:1 to 60:40, still more preferably 95:5 to 70:30. The mass ratio of the amine component 2 when each component is used in combination is [one diamine: the other diamine], preferably from 99.5:0.5, from the viewpoint of the migration property of the organic medium and the durability of the film. 50:50, more preferably 99:1 to 60:40, still more preferably 95:5 to 64:36. One diamine includes, for example, ethylenediamine, and the other diamine includes, for example, meta-xylenediamine.

(b) Polyalkyleneimine compound A polyalkyleneimine compound is a repeating unit whose main chain consists of an alkylene group and an amino group, and is a polymer having a repeating unit having the structure of the following formula (A) and / or formula (B) is a compound.

In formulas (A) and (B), Q represents an alkylene group. Here, examples of the alkylene group represented by Q include an ethylene group, a propylene group, and a butylene group. Only one type of alkylene group may be used, or two or more types may be used. Among these, the alkylene group is preferably an ethylene group. That is, the polyalkyleneimine is preferably polyethyleneimine.

The weight average molecular weight of the polyalkyleneimine compound is preferably 1,000 or more, more preferably 2,000 or more, still more preferably 5,000 or more, and still more preferably 10,000 or more, from the viewpoint of the migration property of the organic medium and the durability of the film. , from the same point of view, it is preferably 200,000 or less, more preferably 100,000 or less, even more preferably 50,000 or less, still more preferably 20,000 or less.

The polymer (Y), i.e., a methacrylic or acrylic polymer having an ester group or an amide group in the side chain, includes 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.

<Organic medium>
The organic medium used in the present invention may be hydrophilic or hydrophobic, but from the viewpoint of the migration of the organic medium and the durability of the film, it is preferably hydrophobic, for example, having an SP value of 10 or less.

The SP value in the present specification indicates a solubility parameter (unit: (cal/cm ³ ) ^1/2 ) calculated by the Fedors method. Co., 2005), Polymer handbook Third edition (A Wiley-Interscience publication, 1989), and the like.

The mass-average molecular weight of the organic medium used in the present invention is not particularly limited, but is preferably 100 or more, preferably 100,000 or less, more preferably 50,000 or less, and still more preferably 20,000 or less. be.

Hydrophobic organic media used in the present invention include, for example, oleic acid (SP value: 9.2), D-limonene (SP value: 9.4), PEG400 (SP value: 9.4), succinate Dimethyl acid (SP value: 9.9), neopentyl glycol dicaprate (SP value: 8.9), hexyl laurate (SP value: 8.6), isopropyl laurate (SP value: 8.5), myristic acid Isopropyl (SP value: 8.5), Isopropyl palmitate (SP value: 8.5), Isopropyl oleate (SP value: 8.6), Hexadecane (SP value: 8.0), Olive oil (SP value: 9.3 ), jojoba oil (SP value: 8.6), squalane (SP value: 7.9), liquid paraffin (SP value: 7.9), Fluorinert FC-40 (manufactured by 3M, SP value: 6.1) , Fluorinert FC-43 (manufactured by 3M, SP value: 6.1) Fluorinert FC-72 (manufactured by 3M, SP value: 6.1), Fluorinert FC-770 (manufactured by 3M, SP value: 6.1) , KF96-1cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3) KF-96-10cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3), KF-96-50cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3), KF-96-100cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3), KF-96-1000cs (manufactured by Shin-Etsu Chemical Co., SP value: 7.3), and the like. Among these, the SP value of the organic medium is more preferably 9.5 or less, still more preferably 9 or less, from the viewpoint of the migration property of the organic medium and the durability of the film, and examples thereof include squalane.

[film]
The membrane of the present invention contains a specific hydrophobically modified cellulose fiber, a specific polymer compound and an organic medium. Here, the term "film" refers to a film that does not flow at room temperature and retains its shape.
As for the surface hardness of the film, for example, a film having a Martens hardness (HM) of 0.1 (N/mm ² ) or more calculated by the following formula when measured with a microhardness meter is preferable. Specifically, the Martens hardness of the film is measured by the method described in Examples below.
HM=F/(26.43×hmax ² )
F: test force (N)
hmax: maximum value of indentation depth (mm)

The film of the present invention is shown in the literature (Technology of super water-repellent, super oil-repellent, synovial surface / Publisher: Hiroshi Motoki / Publisher: Science & Technology Co., Ltd. / Published January 28, 2016) It preferably exhibits synovial surface properties.

Synovial fluid surface properties can be measured, for example, by the method described in a paper (Nature 2011, vol477, p443-447). Specifically, the synovial surface property was measured by dropping a 2 μL droplet (20° C.) onto the membrane surface at room temperature of 20° C., allowing it to stand for 10 seconds, and then spreading the surface at a rate of 1°/s. It can be evaluated by tilting and measuring the angle at which the droplet starts to flow (hereinafter also referred to as the sliding angle). For example, when dodecane is used as the droplet in the above measurement method, the sliding angle on the film is preferably 80° or less, more preferably 50° or less, and still more preferably 40° or less from the viewpoint of expressing synovial surface property. is.

The arithmetic mean roughness of the membrane of the present invention is not particularly limited, and from the viewpoint of synovial surface property, the thickness of the membrane is preferably 1 μm or more, more preferably 3 μm or more, and still more preferably 5 μm or more. from the point of view, it is preferably 2000 μm or less, more preferably 1200 μm or less, still more preferably 500 μm or less, and even more preferably 100 μm or less.

The membrane of the present invention is, for example, a membrane for modifying the solid surface of a molded article into a synovial fluid surface. By modifying the synovial fluid surface, adhesion of the fluid to the compact can be suppressed compared to the solid surface.

One of the characteristics of the membrane of the present invention is that it is highly effective in suppressing adhesion of fluids that come into contact with the membrane. Specifically, the sliding speed is preferably 1.5 cm/min or more, more preferably 2.0 cm/min or more, and still more preferably 2.5 cm/min or more. Furthermore, from the viewpoint of durability of the effect of suppressing adhesion of the fluid, the sliding speed at the fifth measurement when repeatedly used is preferably 1.5 cm / min or more, more preferably 2.0 cm / min or more, and further It is preferably 2.5 cm/min or more. The sliding speed can be measured according to the method described in Examples below.

One of the characteristics of the membrane of the present invention is that the constituent components of the membrane are less likely to migrate into the fluid of the organic medium. Due to the low migration, the film can be maintained for a longer period of time, and as a result, the anti-adhesion effect is exhibited for a longer period of time. Specifically, the rate at which the organic medium migrates to the fluid (organic medium migration rate) is preferably 10.0% or less, more preferably 7.5% or less, even more preferably 5.0% or less, and even more preferably is 0%. The organic medium migration rate can be measured according to the method described in Examples below.

One of the characteristics of the membrane of the present invention is that there is little adhesion of bacteria to the membrane. Further, the membrane of the present invention is preferably a membrane having an effect of inhibiting adhesion of bacteria, and the membrane of the present invention can be used as a membrane that inhibits adhesion of bacteria.

Although the mechanism by which the film of the present invention exerts the effect of suppressing bacterial adhesion is not clear, the film of the present invention suppresses the adhesion of ions, organic substances, or bacteria themselves that cause the formation of the conditioning film described below. It is considered that such an effect was exhibited even without using an agent or a bacteriostatic agent. As used herein, the term "bacteria" includes bacteria, fungi, algae, protozoa, and various other microorganisms, as well as biofilms, which are viscous substances composed of such microorganisms. According to the literature (Basics and control of biofilm / Publisher: Takashi Yoshida / Publisher: NTS Co., Ltd. / Published on February 4, 2008), the biofilm formation process is (1) to the solid surface (2) adhesion of bacterial cells to the conditioning film, (3) proliferation of adhered cells and production of extracellular polymers (EPS), (4) other bacteria, It is called biofilm growth as a community including microorganisms, and it is presumed that the membrane of the present invention acts particularly effectively on process (1).

One of the characteristics of the film of the present invention is that there is little adhesion of metal to the film. Further, the film of the present invention is preferably a film having an effect of suppressing metal adhesion, and the film of the present invention can be used as a metal adhesion suppressing film.

Although the mechanism by which the film of the present invention exerts the effect of suppressing metal adhesion is not clear, it is thought that such an effect was exhibited because the adhesion of various metal ions was suppressed.

One of the characteristics of the film of the present invention is that it is highly effective in suppressing adhesion of solids such as snow and ice. Further, the film of the present invention is preferably a film having an anti-icing and anti-snow effect, and the film of the present invention can be used as an anti-icing and anti-snow film.

Although the mechanism by which the film of the present invention exerts its anti-icing and snow-preventing effect is not clear, it is believed that such an effect is exhibited because the adhesion between the film of the present invention and ice is low.

Applications of the film of the present invention include, for example, packaging containers for cosmetics, foods, etc., interior materials for transport pipes, ship bottoms, and covering materials for electric wires and the like. Thus, the membranes of the present invention have a wide range of uses, being applicable to a variety of articles such as manufacturing equipment, instruments, buildings, structures, and nonwovens.

The amount of the hydrophobically-modified cellulose fiber in the membrane of the present invention is preferably 1 part by mass or more, more preferably 3 parts by mass with respect to 100 parts by mass of the organic medium, from the viewpoint of migration of the organic medium and durability of the membrane. Above, more preferably 7 parts by mass or more, more preferably 12 parts by mass or more, and from the same viewpoint, preferably 70 parts by mass or less, more preferably 60 parts by mass or less, still more preferably 60 parts by mass or less per 100 parts by mass of the organic medium. is 50 parts by mass or less, more preferably 45 parts by mass or less.

The amount of the polymer compound in the film of the present invention is preferably 5 parts by mass or more, more preferably 10 parts by mass or more with respect to 100 parts by mass of the organic medium, from the viewpoint of the migration property of the organic medium and the durability of the film. , more preferably 15 parts by mass or more, more preferably 20 parts by mass or more, and from the same viewpoint, preferably 50 parts by mass or less, more preferably 45 parts by mass or less, more preferably 45 parts by mass or less per 100 parts by mass of the organic medium 40 parts by mass or less, more preferably 35 parts by mass or less. When two or more polymer compounds are used, the amount of polymer compound is the total amount of each polymer compound.

The amount of the hydrophobically-modified cellulose fibers in the membrane of the present invention is not particularly limited, but from the viewpoint of synovial fluid surface properties and durability of the membrane, it is preferably 1% by mass or more, more preferably 3% by mass or more, and still more preferably. is 6% by mass or more, more preferably 10% by mass or more, and from the same viewpoint, preferably 40% by mass or less, more preferably 35% by mass or less, even more preferably 30% by mass or less, and still more preferably 25% by mass. It is below.

The amount of the polymer compound in the film of the present invention is not particularly limited. It is preferably 12% by mass or more, more preferably 16% by mass or more, and from the same viewpoint, preferably 30% by mass or less, more preferably 27% by mass or less, even more preferably 24% by mass or less, further preferably 22% by mass. % or less. When two or more polymer compounds are used, the amount of polymer compound is the total amount of each polymer compound.

The content of the organic medium in the film of the present invention is not particularly limited. It is preferably 50% by mass or more, more preferably 55% by mass or more. From the same viewpoint, it is preferably 90% by mass or less, more preferably 85% by mass or less, even more preferably 80% by mass or less, and even more preferably 70% by mass or less. When two or more organic media are used, the amount of organic media is the total amount of each organic medium.

<Optional component>
In addition to the components described above, the membrane of the present invention may contain optional components that do not impair the effects of the present invention, such as known antibacterial agents, bacteriostatic agents, antifungal agents, anti-biofouling agents and/or surfactants. may contain. The content of these optional components in the film can be appropriately selected within a range that does not impair the effects of the present invention. For example, it is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, still more preferably 0.5% by mass or more, preferably 10% by mass or less, more preferably 5% by mass or less in the film. , more preferably 3% by mass or less, more preferably 2% by mass or less, still more preferably 1% by mass or less. When there are two or more optional ingredients, the amount of optional ingredients is the total amount of each optional ingredient.

<Fluid>
The fluid in the present invention means an object exhibiting fluidity that can come into contact with the "formed body" defined later, for example, in the case of cosmetics, the cosmetics themselves held in a container, and in the case of foods, the food itself on a tray or Food wrapped with resin film itself, liquids, powders or gases transported in pipes for transportation, water and seawater that may come in contact with the bottom of a ship, blood in the case of medical equipment and non-woven fabric, and In the electric wire, it is rainwater, snow, etc., which may come into contact with the electric wire, and furthermore, it is a dirt exhibiting fluidity. If the fluid adheres to the surface of the molded product for a long period of time, not only will the appearance of the product look poor, but it may also cause adverse effects such as clogging of pipes, deterioration of fuel consumption of ships, and disconnection of electric wires. From the viewpoint that the effect of the present invention is easily exhibited, the viscosity of the fluid, for example, when it is liquid at about room temperature, is preferably 0.1 mPa·s or more, more preferably 0.5 mPa·s or more, and still more preferably 0.5 mPa·s or more. It is 8 mPa·s or more, and from the same viewpoint, it is preferably 100,000 mPa·s or less, more preferably 80,000 mPa·s or less, and still more preferably 50,000 mPa·s or less. The viscosity of such a liquid fluid can be measured with an E-type viscometer (25° C., 1 rpm, after 1 minute, standard cone rotor, rotor code: 01).

In addition, from the viewpoint that the effects of the present invention are easily exhibited, the surface tension of the fluid is preferably 15 mN/m or more, more preferably 18 mN/m or more, and still more preferably 20 mN/m when it is liquid at about room temperature. From the same point of view, it is preferably 75 mN/m or less. The surface tension of such liquid fluid can be measured by a plate method (Wilhelmy method).

[Method of Forming Film on Mold]
The method of forming a film on a molded body of the present invention includes step 1 of preparing a dispersion containing a hydrophobically modified cellulose fiber, a polymer compound and an organic medium, and applying the dispersion prepared in step 1 to a molded body. It has the process 2 to carry out.

<Step 1>
A dispersion containing hydrophobically modified cellulose fibers, a polymer compound and an organic medium can be prepared by mixing these ingredients with a solvent.

Examples of solvents include isopropanol, ethanol, methyl ethyl ketone and the like.

Mixing of these components may be performed using a magnetic stirrer, and the conditions in that case are, for example, conditions of stirring at a rotation speed of 400 to 600 rpm and a temperature of 15 to 35° C. for 6 to 24 hours. More preferably, the rotation speed is about 500 rpm, the temperature is 20 to 30° C., and the stirring is performed for 10 to 16 hours.

<Step 2>
The dispersion obtained in step 1 is applied to a shaped body having a solid surface. Examples of the coating method include a method of coating using an applicator, bar coder, spin coater, or the like. The thickness of the coating film is preferably 10 μm or more, more preferably 20 μm or more, and still more preferably 30 μm or more from the viewpoint of synovial fluid speed and durability, and is preferably 2000 μm or less, more preferably 2000 μm or more from the viewpoint of coatability. It is 1500 μm or less, more preferably 1200 μm or less.

The coating is then dried. The drying conditions may be under reduced pressure or normal pressure, and the temperature range is preferably 15 to 75°C. Moreover, the time for drying is preferably 1 to 24 hours.

In this manner, a film is formed, and a compact having the film is obtained.

[Molded body]
A molded article having a film can be produced as described above, and the molded article having the aforementioned film is included in the present invention. As used herein, the term "molded body" refers to an object having a hard surface made of glass, resin, metal, ceramics, concrete, or the like, or a solid surface such as a fiber surface, and the film of the present invention is formed on the solid surface. It is an object to be formed. The shape of the molded body is not particularly limited, and examples thereof include plate-shaped, (hollow) cylindrical and film-shaped, and those formed by further processing these molded bodies into predetermined shapes such as trays and ship bottoms.

By applying the membrane of the present invention to a solid surface as described above, the solid surface can be modified into a synovial fluid surface. Accordingly, the present invention includes the aforementioned membrane for modifying a solid surface into a synovial fluid surface. The film of the present invention not only has a high effect of preventing adhesion of fluids, but also has excellent durability of the film itself, so that the effect can be maintained for a long period of time. As an interior material for packaging containers such as blister packs, trays, and lunch box lids, food containers, industrial trays and pipes used for transporting and protecting industrial parts, and coating materials for ship bottoms and electric wires. It can be used preferably.

Specific examples of molded articles include, but are not limited to, pipes, piping, tanks, electric wires, wire ropes, sign plates, snow cover plates, mirrors, shelters, lamps, fences, traffic lights, and guards. Outdoor equipment such as ventilation fans, drains, packing, washstands, toilets, bathroom interiors, washing machines, air conditioners, sinks, kitchens, etc., and buildings such as roofs, walls, windows, tunnels, bridges, storerooms, etc. , endoscopes, hemodialysis machines, catheters, dentures, medical equipment such as denture fixing equipment, metal processing equipment, metal processing equipment, machine tool parts, tableware, washbasins and other equipment, ships ( Ship bottoms), vehicles such as automobiles, airplanes, and trains, and containers such as bottles, bottles, pouches, film containers, jars, bags, trays, blister packs, cans, paper packs, pumps, dispensers, drums, cartridges, etc. and nonwoven fabrics such as clothes, sanitary goods, and diapers.

[Membrane Dispersion]
As one aspect of the present invention, there is provided a dispersion for membrane comprising hydrophobically modified cellulose fibers in which a modifying group is bonded to one or more groups selected from carboxy groups and hydroxyl groups of cellulose fibers, a polymer compound, and an organic medium. be. Such a film-forming dispersion can be provided as a coating liquid for forming a film. Such a film-forming dispersion may contain the solvent and other components listed in the above [Method for forming a film on a molded article], if necessary.

The content of the hydrophobically-modified cellulose fiber in the membrane dispersion is preferably 0.1% by mass or more, more preferably 0.3% by mass or more, and still more preferably 0.3% by mass or more, from the viewpoints of suppression of migration of the organic medium and durability. It is 6% by mass or more, more preferably 1.0% by mass or more. From the same viewpoint, it is preferably 4.0% by mass or less, more preferably 3.5% by mass or less, even more preferably 3.0% by mass or less, and even more preferably 2.5% by mass or less.

The content of the polymer compound in the dispersion for membrane is preferably 0.4% by mass or more, more preferably 0.8% by mass or more, and still more preferably 1.2% by mass, from the viewpoints of suppression of migration of the organic medium and durability. It is at least 1.6% by mass, more preferably at least 1.6% by mass. From the same viewpoint, it is preferably 3.0% by mass or less, more preferably 2.7% by mass or less, even more preferably 2.4% by mass or less, and even more preferably 2.2% by mass or less.

The content of the organic medium in the film-forming dispersion is preferably 4.0% by mass or more, more preferably 4.5% by mass or more, and still more preferably 5.0% by mass, from the viewpoints of suppression of migration of the organic medium and durability. % or more, more preferably 6.0 mass % or more. From the same point of view, it is preferably 9.0% by mass or less, more preferably 8.5% by mass or less, even more preferably 8.0% by mass or less, and even more preferably 7.0% by mass or less.

The content of the solvent in the membrane dispersion is preferably 80.0% by mass or more, more preferably 85.0% by mass or more, and still more preferably 88.0% by mass, from the viewpoint of sufficiently dispersing the hydrophobically modified cellulose fibers and the like. % or more. From the viewpoint of shortening the film formation time, the content is preferably 92.8% by mass or less, more preferably 91.7% by mass or less, and even more preferably 90.6% by mass or less.

Specific examples of film dispersions are not limited to the items listed, but include coating liquids, paints, coating agents, varnishes, paints, lacquers, glazes, glazes, surface treatment agents, and surface modifiers. , cleaning agents, functionalizing agents, antifouling agents, and the like. Here, the coating method of the film dispersion is not particularly limited, but includes dip coating, spin coating, flow coating, spray coating, roll coating, brush coating, and the like.

EXAMPLES Hereinafter, the present invention will be specifically described with reference to Examples and the like. 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. "Atmospheric pressure" means 101.3 kPa, and "room temperature" means 25°C.

[Average fiber diameter, average fiber length and average aspect ratio of cellulose fibers and hydrophobically modified cellulose fibers]
Water is added to cellulose fibers or hydrophobically modified cellulose fibers to prepare a dispersion having a concentration of 0.0001% by mass, and the dispersion is dropped onto mica (mica) and dried. Using a force microscope (AFM) (manufactured by Digital Instruments: Nanoscope III Tapping mode AFM, using Point Probe (NCH) manufactured by Nanosensors), the cellulose fibers or hydrophobically modified cellulose fibers in the observation sample Measure the fiber height. 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.

[Carboxy group content of oxidized cellulose fiber and hydrophobically modified cellulose fiber]
Take 0.5 g of dry mass of oxidized cellulose fiber or hydrophobically modified cellulose fiber 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 there. is added to prepare a dispersion, and the dispersion is stirred until the oxidized cellulose fibers or hydrophobically modified cellulose fibers are well 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., trade name "AUT-710") to add 0.05 M sodium hydroxide aqueous solution. The solution is added dropwise to the dispersion with a waiting time of 60 seconds, and the conductivity and pH values are measured every minute until the pH reaches about 11 to obtain a conductivity curve. From this conductivity curve, the titration amount of sodium hydroxide is determined, and the carboxyl group content of the oxidized cellulose fiber or hydrophobically modified cellulose fiber is calculated according to the following formula.
Carboxy group content (mmol/g) = sodium hydroxide titration amount x sodium hydroxide aqueous solution concentration (0.05 M)/mass of oxidized cellulose fiber or hydrophobically modified cellulose fiber (0.5 g)

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

[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 (IR) Nicolet 6700 (manufactured by Thermo Fisher Scientific), and modifying according to the following formula. Calculate the average amount of bonding and introduction rate of the group.
Average binding amount of modifying group (mmol/g)=[Carboxy group content of cellulose fiber (mmol/g)]×[(Peak intensity of cellulose fiber at 1720 cm ⁻¹ −Peak intensity of hydrophobically modified cellulose fiber at 1720 cm ⁻¹ ) ÷ 1720 cm ⁻¹ peak intensity of cellulose fibers]
Peak intensity at 1720 cm ⁻¹ : peak intensity derived from carbonyl group of carboxylic acid Modification group introduction rate (%) = {binding amount of modification group (mmol/g) / carboxy group content in cellulose fiber before introduction ( mmol/g)}×100

[Average bond amount and introduction ratio (amide bond) of modifying group of hydrophobically modified cellulose fiber]
The average bonding amount of the modifying group is calculated by the following formula.
Average bonding amount of modifying group (mmol/g) = carboxy group content in cellulose fiber before modification group introduction (mmol/g) - carboxy group content in cellulose fiber after modification group introduction (mmol/g)
Modification group introduction rate (%) = {average bonding amount of modification group (mmol/g)/carboxy group content in cellulose fiber before introduction (mmol/g)} x 100

[Measurement of arithmetic mean roughness of film]
The arithmetic mean roughness of the film is measured as follows. The arithmetic mean roughness of the film is measured under the following measurement conditions using a laser microscope "VK-9710" manufactured by Keyence Corporation. The measurement conditions are: objective lens: 10 times, light amount: 3%, brightness: 1548, Z pitch: 0.5 μm. The surface arithmetic average roughness is measured at 5 points using built-in image processing software, and the average value is used.

[Preparation of oxidized cellulose fiber dispersion]
Preparation Example 1 (Dispersion of oxidized cellulose fibers obtained by reacting natural cellulose fibers with an N-oxyl compound)
Bleached kraft pulp of softwood (manufactured by Fletcher Challenge Canada, trade name "Machenzie", 650 ml of CSF) was used as the natural cellulose fiber. As TEMPO, a commercial product (manufactured by ALDRICH, Free radical, 98% by mass) was used. As sodium hypochlorite, a commercial product (manufactured by Wako Pure Chemical Industries, Ltd.) was used. As sodium bromide, a commercial product (manufactured by Wako Pure Chemical Industries, Ltd.) was used.

First, 100 g of bleached softwood kraft pulp fiber is sufficiently stirred with 9900 g of ion-exchanged water, and then 1.25% by mass of TEMPO, 12.5% by mass of sodium bromide, and 28% by mass of sodium hypochlorite are added to 100 g of the pulp mass. .4% by weight were added in this order. Using a pH stud, the pH was maintained at 10.5 by dropwise addition of 0.5M sodium hydroxide. After the reaction was carried out for 120 minutes (20° C.), the dropwise addition of sodium hydroxide was stopped to obtain oxidized pulp. The obtained oxidized pulp was thoroughly washed with deionized water and then dehydrated. After that, 3.9 g of oxidized pulp and 296.1 g of ion-exchanged water are subjected to refining treatment twice at 245 MPa using a high-pressure homogenizer (manufactured by Sugino Machine Co., Ltd., Starburst Lab HJP-2 5005), and the oxidized cellulose fiber dispersion ( solid concentration of 1.3% by mass) was obtained. The oxidized cellulose fibers had an average fiber diameter of 3.3 nm and a carboxy group content of 1.62 mmol/g.

Preparation Example 2 (dispersion of oxidized cellulose fibers with aldehyde groups reduced)
3846.15 g of the oxidized cellulose fiber dispersion obtained in Preparation Example 1 (solid content concentration: 1.3% by mass) was put into a beaker, and 1M aqueous sodium hydroxide solution was added thereto to adjust the pH to about 10, and then sodium borohydride. (manufactured by Wako Pure Chemical Industries, Ltd., purity 95% by mass) was charged in an amount of 2.63 g, and reacted at room temperature for 3 hours for aldehyde reduction treatment. After completion of the reaction, 405 g of 1M hydrochloric acid aqueous solution and 4286 g of ion-exchanged water are added to make a 0.7% by mass aqueous solution, which is allowed to react at room temperature for 1 hour for protonation. After completion of the reaction, it is washed with ion-exchanged water to remove hydrochloric acid and salts. Removed. Finally, the solvent was replaced with isopropanol to obtain an oxidized cellulose fiber dispersion in which aldehyde groups were reduced. The obtained oxidized cellulose fiber dispersion (solid concentration: 2.0% by mass) in which aldehyde groups were reduced had an average fiber diameter of 3.3 nm and a carboxy group content of 1.62 mmol/g.

[Preparation of Hydrophobic Modified Cellulose Fiber]
Production example 1
A beaker equipped with a magnetic stirrer and a stirrer was charged with 300 g of the oxidized cellulose fiber dispersion obtained in Preparation Example 2 (solid concentration: 2.0% by mass). Subsequently, amino-modified silicone (manufactured by Dow Corning Toray Co., Ltd.: BY16-209) was added in an amount corresponding to the number of moles (0.5 mol) of amino groups shown in Table 2 with respect to 1 mol of carboxy groups of the oxidized cellulose fiber. was charged, 100 g of isopropanol was added, and the mixture was allowed to react at room temperature (25° C.) for 14 hours. After completion of the reaction, the mixture was filtered, washed with isopropanol, stirred for 2 minutes with an ultrasonic homogenizer (manufactured by Nippon Seiki Seisakusho: US-300E), and placed in a high-pressure homogenizer (manufactured by Sugino Machine: Starburst Lab HJP-2 5005). Hydrophobic-modified cellulose with an average fiber diameter of 3.3 nm and an average fiber length of 578 nm, in which the amino-modified silicone is linked to the oxidized cellulose fibers via ionic bonds, is finely treated at 100 MPa for 1 pass and at 150 MPa for 9 passes. fiber was obtained.

Production example 2
Hydrophobic-modified cellulose fibers were obtained in the same manner as in Production Example 1, except that the amount of amino-modified silicone charged was changed to 0.25 mol as shown in Table 2. The obtained hydrophobically modified cellulose fibers had an average fiber diameter of 3.3 nm and an average fiber length of 578 nm.

[Preparation of membrane]
Examples 1 to 6, Comparative Example 1
In Examples 1, 2, 4 to 6 and Comparative Example 1, the hydrophobically modified cellulose fibers obtained in Production Example 1 were used, and in Example 3, the hydrophobically modified cellulose fibers obtained in Production Example 2 were used. A membrane was prepared as follows. That is, hydrophobically-modified cellulose fibers, a polymer compound, an organic medium (squalane) and a solvent (isopropanol) were introduced into a screw tube so that the solvent accounted for 90% by mass of the entire dispersion and the mass ratio shown in Table 2. was blended with Then, the contents of the screw tube were stirred at room temperature (25° C.) for 12 hours with a magnetic stirrer rotating at 500 rpm. After that, the mixture was stirred at 2200 rpm for 2 minutes using an automatic revolution stirrer, Awatori Mixer (manufactured by Thinky Co.), and deaerated to obtain a dispersion for a coating film. The obtained dispersion for coating film was coated on a glass substrate (Micro Slide Glass S2112 manufactured by MATSUNAMI Co., Ltd.) as a model molded body using an applicator (manufactured by Tester Sangyo Co., Ltd.) so as to have a thickness of 400 μm. The isopropanol was volatilized by drying at 50° C. under vacuum for 12 hours to obtain a film with a thickness of 40 μm.

Method for Measuring Molecular Weight of Polymer Compound 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 the eluent channel pump, Shodex RI SE-61 differential refractive index detector as the detector, and GMHHR-H double connected column as the 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.

From the chart obtained by GPC measurement, the component amount of the polymer component having a molecular weight of 100,000 or more in the polymer compound was calculated according to the following formula.
Amount of component with molecular weight of 100,000 or more = (area of molecular weight of 100,000 or more) / (total area)

The details of the organic medium used above are as follows.
Squalane (manufactured by Wako Pure Chemical Industries, SP value: 7.9)
The details of the polymer compounds used above are as follows.
Polyamides 1 to 3: Polyamides synthesized using raw materials in the proportions shown in Table 1 Polyalkyleneimine: Epomin P-1000 (manufactured by Nippon Shokubai Co., Ltd.)

Method for Synthesizing Polyamide 1 Halidimer 250K: 450 g was placed in a 2 L Separat flask, heated to 70° C. and then purged 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. After that, while keeping 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 produce Polyamide 1.

Method for Synthesizing Polyamides 2 to 3 Polyamides 2 to 3 were also produced using raw materials shown in Table 1 in the same manner as polyamide 1.

The compositions of the raw materials used above are as follows.
Halidimer 250K (manufactured by Harima Kasei Co., Ltd.): Cas number 61788-89-4: 100% (C36 Dimer acid)
Tsuno Dime 205 (manufactured by Tsuno Food Industry Co., Ltd.): Cas number 61788-89-4: 70% (C36 Dimer acid), Cas number 68937-90-6: 18% (TRILINOLEIC ACID) and Cas number 68955-98-6 : 12% (Fatty acids, c16-18 and c18-unsatd., branched and linear) mixture

[Membrane performance test]
The following tests were performed at room temperature. The details of the fluid A used in the test are as follows.
Cortamine E-80K (manufactured by Kao Corporation): 3% by mass
Propylene glycol (manufactured by Wako Pure Chemical Industries, Ltd.): 1% by mass
Deionized water: balance

Test Example 1 (Sliding speed measurement test)
50 mg of the fluid A was placed on the film prepared in each example or comparative example, the substrate was tilted at 90°, and the distance the fluid A slides down per minute was measured. This test was performed 5 times. Table 2 shows the first sliding speed and the fifth sliding speed.

Test Example 2 (organic medium migration test)
Fluid A was applied on the film prepared in each example or comparative example in an amount 100 times the mass of the organic medium. After 72 hours, the fluid A was sampled to evaluate the transferability of the organic medium to the fluid A. The migration property was evaluated by the amount (% by mass) of the organic medium contained in the sampled fluid A. Squalane in the sampled fluid A was measured using GC under the following conditions.

<GC method>
In the following measurement method, the transfer rate was measured from the peak area derived from squalane detected at 18.9 minutes.

Equipment: Agilent 6850 series II
Column: DB-5 (Agilent), 12 m x 200 µm x 0.33 µm
Method: Hold at 100°C for 3 minutes → Heat up from 100°C to 320°C at 10°C/min → Hold at 320°C for 15 minutes Detector: 330° _C (FID), H2: 30 mL/min, Air: 400 mL/min, He: 30 mL/min Carrier gas: He
Injection volume: 1 μL
Sample: solution diluted 100 times with isopropanol after sampling

Table 2 shows the results.

Test Example 3 (sliding angle measurement test)
At a room temperature of 20° C., a 2 μL droplet of dodecane (20° C.) is dropped onto the membrane, left to stand for 10 seconds, and then the membrane surface is tilted at a speed of 1°/s to determine the angle at which the droplet starts to flow. It was measured. As a representative example, the sliding angle of the membrane of Example 1 was 7°.

Test Example 4 (hardness measurement test)
The surface hardness (Martens hardness) of each film was measured using a hardness tester DUH-211 (manufactured by Shimadzu Science Co., Ltd.) under the following conditions. Table 2 shows the results.
Test force: 0.1mN
Load holding time: 5 (s)
Unloading retention time: 1 (s)

The table above reveals the following.
It was found that the membranes of each example had a high slide-down speed, a small migration rate to organic medium, and excellent durability in which the performance did not deteriorate even after repeated synovial fluid tests. Furthermore, it was also confirmed that the larger the amount of the specific polymer compound, the larger the value of the surface hardness of the film.
On the other hand, in Comparative Example 1, which does not contain a polymer compound, the slide-down speed is remarkably lowered in the repeated synovial fluid test, indicating that the durability is low.

Example 7 and Comparative Example 2
One side of an HAp substrate (manufactured by Cosmo Bio, apatite pellets (square), product number: APP-100, 1 cm square) was mirror-polished using abrasive paper of 40 μm, 12 μm, and 3 μm, and then immersed in 1N HCl for 1 minute. Acid deashing treatment was applied. After the treatment, the HAp substrates were washed with deionized water and dried to obtain treated substrates for Examples, Comparative Examples and Controls according to the following method.

Using the hydrophobically modified cellulose fibers obtained in Production Example 1, the dispersion for a coating film having the same composition as in Example 2 was applied on the treated substrate in the same manner and then dried to obtain a film having a thickness of 40 μm. got The substrate on which the film was formed was used as the substrate of Example 7.

On the other hand, the above treated substrate is placed in the wells of a 24-well plate, and 1 mL of a diluted solution obtained by diluting a commercially available dentifrice containing a bactericide (Colgate Total ORIGINAL Lot. CP (L) 5139PL1111) 4-fold with ion-exchanged water is added. soaked for a minute. Thereafter, the substrate was transferred to another well containing 1 mL of ion-exchanged water, rinsed with ion-exchanged water for 30 seconds, and dried.

[Evaluation of biofilm formation inhibitory effect 1]
Test example 5
1) Collection of stimulated saliva Healthy men in their 20s and 30s were asked to chew gum pellets contained in Dent Buff Strips (OralCare Inc.), and saliva collected in their mouths was collected each time. Saliva was collected in Falcon tubes by having them expectorate into the Falcon tubes. Since there are individual differences in bacteria in saliva, a biofilm formation suppression test was performed for all examples and comparative examples using the saliva of one healthy male.

2) Formation of Model Dental Plaque Saliva collected in a Falcon tube was centrifuged at 3000 rpm/rt/10 min. Using the separated supernatant saliva, sucrose was added to make a 5% by mass solution, and then stirred using a stirring device (Voltex, manufactured by Nippon Genetics Co., Ltd.) to prepare a dental plaque model test solution.
Next, the substrate of Example 7 or the substrate of Comparative Example 2 was placed in the wells of the 24-well plate. After adding 1 mL of the dental plaque model test solution to each well in which the substrate was placed, this was stored in a plastic case together with a CO ₂ pack under anaerobic conditions, cultured at 37 ° C. for 24 hours, and placed on the substrate. A model dental plaque was formed as a biofilm.

3) Evaluation of biofilm formation inhibitory effect Using a vacuum pump, the dental plaque model test solution in the well was sucked up, 1 mL of ion-exchanged water was added to the well, and the well was shaken for 5 minutes. Next, water was sucked up using a pump, and 750 μL of 0.1 mass % crystal violet (CV) solution was added and shaken for 15 minutes.

Further, the CV solution was sucked up with a pump, and 1 mL of ion-exchanged water was added to the well and shaken for 5 minutes. Next, the water was sucked up with a pump, and 1 mL of ion-exchanged water was added to the well and shaken for 5 minutes. Then, the water is sucked with a pump, 500 μL of ethanol is added to the well and pipetted, the CV attached to the biofilm is extracted, the extract is diluted 10-fold with ion-exchanged water, and a microplate recorder (manufactured by TECAN, wavelength The absorbance OD _{595 nm} was measured with a variable absorbance microplate reader (Sunrise Rainbow Thermo).

As a control, the treated substrate was used as it was instead of the substrate of Example 7 or the substrate of Comparative Example 2, and the above 2) and 3) were performed to form a model dental plaque on the substrate, with an OD of _{595 nm} . (control) was measured. The biofilm formation rate (%) was calculated according to the following formula. In addition, it means that the biofilm formation inhibitory effect is so high that the value of the obtained biofilm formation rate is small.

Biofilm formation rate (%) = {OD _{595 nm} /OD ₅₉₅ nm of substrate of example or comparative example (control)} × 100

Table 3 shows the results.

From Table 3, it can be seen that the membranes of the present invention, despite the fact that they do not contain bactericides or bacteriostats, have a lower biofilm formation rate than when treated with a commercial dentifrice containing a bactericide. From this, it was shown that the membrane of the present invention can be used as a bacteria adhesion inhibitory membrane.

Example 8 and Comparative Example 3
The hydrophobically modified cellulose fiber obtained in Production Example 1 was used on a SUS substrate (40 mm × 200 mm), and the dispersion for a coating film having the same composition as in Example 2 was applied in the same manner and then dried. A 40 μm membrane was obtained. The SUS substrate on which the film was formed was used as the substrate of Example 8. A SUS substrate on which no film was formed was used as a substrate of Comparative Example 3.

[Evaluation of metal adhesion suppression effect]
Test example 6
After each of the substrate of Example 8 and the substrate of Comparative Example 3 was immersed in industrial water for two weeks, the solid substance formed on the substrate surface of the substrate of Comparative Example 3 was removed, and the substrate of Example 8 was removed together with the film. After scraping and pretreating the scraped sample by the method shown below, the amount of metal was quantified.

Pretreatment method (wet decomposition method)
The total amount of each scraped sample was placed in a separate digestion vessel for wet digestion. Both samples were approximately 10 mg. 2 mL of Conc sulfuric acid and 4 mL of Conc nitric acid were added thereto, and the container was placed on a hot plate heated to 220° C. for 3 hours to perform wet decomposition treatment. After cooling, ultrapure water was used to quantitatively transfer the residue in the container to a 25mL volumetric flask, and then filled up to 25mL with ultrapure water to obtain a measurement sample.

The amount of metal was quantified using the following analyzer and conditions.
Analyzer: iCAP 6500Duo manufactured by Thermo Fisher Scientific
RF power: 1150W
Coolant gas flow rate: 12L/min
Nebulizer flow rate: 0.50 L/min
Auxiliary gas: 1.0 L/min
Pump flow rate: 50rpm
Measurement wavelength: Wavelength according to each element

The metal adhesion amount was calculated as the metal mass contained per 1 g of the scraped sample. Since the mass of the collected samples was the same, each value shown in Table 4 can be compared as the amount of metal adhesion in the same area on the SUS substrate.

From Table 4, it was found that the film of the present invention can suppress metal adhesion with respect to all measured metal species. From this, it was shown that the film of the present invention can be used as a metal adhesion suppressing film.

Example 9 and Comparative Example 4
The hydrophobically modified cellulose fiber obtained in Production Example 1 was used on a glass substrate (Micro Slide Glass S2112 manufactured by MATSUNAMI), and the coating film dispersion having the same composition as in Example 2 was applied in the same manner. After drying, a film with a thickness of 40 μm was obtained. The substrate on which the film was formed was used as the substrate of Example 9.

A glass substrate (Micro Slide Glass S2112 manufactured by MATSUNAMI) was immersed in an ethanol solution of 10 ppm 4,4'-dichloro-2-hydroxydiphenyl ether (common name: diclosan) for 3 minutes, then immersed in ethanol for 30 seconds and rinsed. , the ethanol was dried to obtain a diclosan-treated substrate. A substrate of Comparative Example 4 was used as the substrate to be treated.
[Evaluation of biofilm formation inhibitory effect 2]
Test example 7
1) Preparation of bacterial solution Staphylococcus aureus NBRC13276, Escherichia coli NBRC3972, and Pseudomonas aeruginosa NBRC13275 were each treated with Soybean-Casein Digest Agar (manufactured by Nihon Pharmaceutical Co., Ltd.: SCD agar medium "Daigo ”) was used for pre-culture at 30° C. for 24 hours.

Put 3 mL of Soybean-Casein Digest (manufactured by Nihon Pharmaceutical Co., Ltd.: SCD medium "Daigo") in a 10 mL culture test tube, inoculate 1 platinum loop of a colony prepared by preculture there, and incubate at 30 ° C. / 200 rpm / 24 hours. It was cultured under shaking conditions.

The absorbance (OD _600nm ) at a wavelength of 600 nm was measured for the cultured bacterial solution using a spectrophotometer, and the following values were obtained. Staphylococcus aureus: 0.4, E. coli: 0.8, Pseudomonas aeruginosa: 0.4. The OD _{600 nm} combined bacterial solutions were each diluted 100-fold with SCD medium to prepare bacterial solutions for evaluation.

2) Evaluation of biofilm formation inhibitory effect The substrate of Example 9 and the substrate of Comparative Example 4 were irradiated with UV for 1 minute to sterilize the substrate surface. A sterilized substrate was placed in a rectangular 4-well (manufactured by AS ONE Co., Ltd.: multi-dish for floating cells 267061), 6 mL each of the previously prepared bacterial solution was added, and cultured at 30 ° C. for 24 hours. A biofilm of the fungal species was allowed to form.

Using a vacuum pump, the bacterial liquid in the well was sucked out, and 6 mL of physiological saline was added to the well and shaken. Next, the physiological saline was sucked up with a pump, and 6 mL of physiological saline was added to the well and shaken. Then, the solution was sucked up with a physiological saline pump, 6 mL of a 0.1% by mass crystal violet (CV) solution was added, and the solution was allowed to stand for 30 minutes.

The CV solution was sucked up, and 6 mL of physiological saline was added to the well and shaken. Next, the physiological saline was sucked up with a pump, and 6 mL of physiological saline was added to the well and shaken. Next, the physiological saline pump was aspirated, and 6 mL of ethanol was added to the wells and pipetted to extract CVs adhering to the biofilm. The extract was diluted 10-fold with ethanol, and absorbance OD _{595 nm} was measured with a microplate reader (VERSA max microplate reader manufactured by Molecular Devices Japan).

As a control, a glass substrate was used as it was instead of the substrate of Example 9 or the substrate of Comparative Example 4, and the above operation was performed to form a biofilm on the substrate, and OD _{595 nm} (control) was measured. A higher OD _{595 nm} value indicates a higher amount of biofilm.

The obtained measured values were calculated according to the following formula to calculate the biofilm formation rate (%). In addition, it means that the biofilm formation inhibitory effect is so high that the value of the obtained biofilm formation rate is small.

Biofilm formation rate (%) = {OD _{595 nm} /OD ₅₉₅ nm of substrate of example or comparative example (control)} × 100

Table 5 shows the results.

OD _595nm is the absorbance measurement at 595nm and is proportional to the number of bacteria. From Table 5, although the amount of biofilm formation on the glass substrate differs depending on the bacterial species, the film containing the hydrophobically modified cellulose fibers and the organic medium exhibits a high biofilm formation inhibitory effect against all bacterial species. rice field.

[Evaluation of anti-icing effect]
<Preparation of evaluation board>
Comparative example 5
Using a bar coater (OSG System Products, OSP-13) on a glass substrate (MATSUNAMI: Micro Slide Glass S2112), an antifouling paint (Mitsubishi Materials Trading: E-Frontier ^TM antifouling paint) is applied. worked. This substrate was designated as Comparative Example 5.
On the other hand, a substrate having the film of the present invention produced by the same method as in Example 2 was prepared.

<Ice sliding test>
Using a micropipette (M&S: Pipetman), 100 μl of ion-exchanged water was dropped onto SUS304 placed on dry ice in a constant temperature room at 2° C., and allowed to stand for 10 minutes to prepare ice. Place the ice on each surface of the substrate of Example 2 and the substrate of Comparative Example 5 in a temperature-controlled room at 2° C., allow to stand for 1 minute, tilt from 0° to 90°, and evaluate whether the ice slides down. did.

With the substrate of Example 2, it was confirmed that the ice slid down while being tilted up to 90°. On the other hand, with the substrate of Comparative Example 5, it was confirmed that even if the substrate was tilted up to 90°, the ice stuck to the surface of the substrate and did not slide down. In other words, it was confirmed that the film of the present invention has a high ice sliding effect.

[Evaluation of Fluid Adhesion Suppression Effect]
<Preparation of evaluation container>
Example 10
<Preparation of Lower Layer>
Essential conditioner before bag making Moist glossy hair Mask the heat-sealed part of the refill container (manufactured by Kao Corporation: Raku-raku eco pack for refill), and use a bar coater (OSG System Products, OSP-13) to coat the lower layer. A water-based acrylic emulsion (manufactured by DSM, NeoCryl A-1127) was applied as a body-forming coating liquid to the inner surface of the container. It was dried at room temperature (25° C.) for 24 hours to volatilize the solvent to obtain a laminated structure.

<Fabrication of upper layer>
Using the hydrophobically modified cellulose fibers obtained in Production Example 1, an upper layer was produced on the surface of the laminate structure on the lower layer side in the following manner. hydrophobically modified cellulose fibers in a weight ratio of cellulose fiber: squalane (lubricating oil):polyamide 1 of 1:3:1 and the solvent is 97% of the total dispersion, Squalane, polyamide 1 and a solvent (isopropanol:toluene=100:5 mixed solvent) were blended and stirred in a screw tube at room temperature for 24 hours. Using the obtained dispersion for forming the upper layer as a coating film sample, an applicator (manufactured by Tester Sangyo Co., Ltd.) was applied to the surface of the lower layer of the laminated structure so that the thickness of the sample liquid for coating film became 1800 μm. It was coated as The solvent was volatilized by drying at room temperature (25° C.) for 12 hours to obtain a laminate of the upper layer, the lower layer, and the substrate, in which the upper layer had a thickness of about 50 μm. A container was produced by heat-sealing the obtained laminate.

Comparative example 6
Essential Conditioner Moist Shiny Hair Before Making Bag A container for refilling (manufactured by Kao Corporation: Rakuraku eco pack for refilling) was heat-sealed to prepare a container, which was designated as Comparative Example 6.

<Remaining amount evaluation>
The containers of Example 10 and Comparative Example 6 were filled with 340 g of the contents of Essential Conditioner Moist Shiny Hair (manufactured by Kao Corporation). It was set in a smart holder (manufactured by Kao Corporation) and ejected at 25° C. at 1 Push/second until ejection became impossible. After discharge, the pump was removed and the remaining amount of contents in the container was measured.

As a result, the remaining amount in Example 10 was 2.2 g, while the remaining amount in Comparative Example 6 was 3 g. As described above, when the membrane of the present invention is applied to an actual container, the container of Example 10 having the membrane can reduce the remaining amount of contents more than the container of Comparative Example 6 which does not have such a membrane. Do you get it.

INDUSTRIAL APPLICABILITY The film of the present invention can be used in the field of interior materials for packaging containers for cosmetics and foods, and in the field of various transportation pipes.

Claims (7)

A hydrophobically-modified cellulose fiber obtained by bonding a modifying group introduced by an amino-modified silicone compound to at least one group selected from a carboxy group and a hydroxyl group of the cellulose fiber, from the group consisting of (X) and (Y) below. A film comprising one or more selected polymer compounds and an organic medium having an SP value of 10 or less .
(X) one or more polymer compounds selected from the group consisting of (a) polyamide compounds and (b) polyalkyleneimine compounds
(Y) Polyalkyl (meth)acrylate 2. The membrane according to claim 1, wherein the polymer compound contains a polymer component having a molecular weight of 100,000 or more. 3. The membrane according to claim 1 or 2, wherein the polymer compound is polymer compound (X). The membrane according to any one of claims 1 to 3 , wherein the hydrophobically-modified cellulose fiber is obtained by bonding a modifying group to the carboxyl group of the cellulose fiber. A molded article having the film according to any one of claims 1 to 4 . A hydrophobically-modified cellulose fiber obtained by bonding a modifying group introduced by an amino-modified silicone compound to at least one group selected from a carboxy group and a hydroxyl group of the cellulose fiber, from the group consisting of (X) and (Y) below. Step 1 of preparing a dispersion containing one or more selected polymer compounds and an organic medium having an SP value of 10 or less , and Step 2 of applying the dispersion prepared in Step 1 to a molded body. and a method for forming a film on a molded body.
(X) one or more polymer compounds selected from the group consisting of (a) polyamide compounds and (b) polyalkyleneimine compounds
(Y) Polyalkyl (meth)acrylate A hydrophobically-modified cellulose fiber obtained by bonding a modifying group introduced by an amino-modified silicone compound to at least one group selected from a carboxy group and a hydroxyl group of the cellulose fiber, from the group consisting of (X) and (Y) below. A film dispersion containing one or more selected polymer compounds and an organic medium having an SP value of 10 or less .
(X) one or more polymer compounds selected from the group consisting of (a) polyamide compounds and (b) polyalkyleneimine compounds
(Y) Polyalkyl (meth)acrylate