JP2010077202A - Moisture-permeable film, coating agent, filler for coating film, and coated sheet - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a moisture-permeable film having extremely excellent moisture permeability; a coating agent, a filler for a coating film, and a coated sheet having high antimicrobial and antifungal properties. <P>SOLUTION: This moisture-permeable film contains a matrix resin, and collagen powders comprising a crosslinked regenerated collagen, wherein a communication degree of the collagen powders is 1-95%. The coating agent contains a matrix resin and a filler, wherein the filler is a powdered filler containing an organic resin and an aluminum salt, the aluminum salt being chemically bonded to the organic resin. The coated sheet is obtained by applying the coating agent onto a base fabric sheet. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a coating agent, a coating film filler, a paint sheet, and a moisture-permeable film having phosphorus adsorptive properties, antibacterial properties, and anti-wrinkle properties.

  Conventionally, by attaching an appropriate resin to a clothing material such as cloth, the waterproofness and heat retention of the clothing are improved, the moisture permeability is improved, the skin is prevented from being peeled, and the comfort is improved. . This is a so-called moisture-permeable waterproof cloth. As such an example, a moisture-permeable waterproof film using a polyurethane resin or a moisture-permeable waterproof cloth in which the film is laminated on a base cloth is known, such as synthetic leather, sports clothing, etc. It is used for.

  Polyurethane resins have excellent mechanical strength and elasticity, so they are also used in various applications such as coating agents, molding materials, surface treatment agents, paints, etc. However, moisture-permeable waterproof fabrics coated with ordinary polyurethane resins are transparent. Since it was inferior in wetness, there was a drawback that it was steamed when worn. In order to solve this problem, a method has been proposed in which a polyurethane resin solution is wet-solidified to become porous (Patent Document 1). However, the processing steps are complicated and the film strength is inferior. In addition, a method of introducing hydrophilic polyoxyethylene glycol into the main chain as a polyol component of a polyurethane resin has been proposed (Patent Document 2). However, the obtained polyurethane resin generally has low water resistance and solvent resistance, and has a problem of poor durability. Moreover, in the case of polyurethane-based resins, there is a sticky feeling peculiar to urethane, and in particular, there is a large stickiness feeling when contacting with sweaty skin. Therefore, a method has been proposed in which a hygroscopic powder such as natural collagen is mixed and applied in a polyurethane resin solution (Patent Document 3). However, although the functions of surface touch and moisture permeability are satisfied, the heat resistance of natural collagen is low, and it has the disadvantage that it becomes sticky when heat-processed at high temperature or when it is gelatinized by wet heat deterioration. Had.

There have been many proposals for antibacterial and antifungal coatings. For example, a proposal to add hinokitiol to a paint to make an antibacterial paint (Patent Document 4), a proposal to use an antibacterial silicic acid containing magadiite or kenyaite into which quaternary ammonium ions or tertiary ions are introduced by ion exchange (Patent Document 5) ), Proposal to mix tea husk into paint and apply to cardboard (Patent Document 6), proposal to use silver-containing aluminum sulfate hydroxide particles as antibacterial agent (Patent Document 7), coordinate copper or zinc to carbonyl compound There is a proposal (patent document 8) etc. which mix | blends the metal complex with the coating material.
JP-A-11-269773 Japanese Patent Laid-Open No. 7-3148 JP-A-4-82974 JP 2007-126602 A JP 2007-106737 A JP 2007-46182 A JP 2007-39444 A JP 2006-282647 A

  In order to improve the above-mentioned conventional problems, the present invention has a coating agent, a coating film filler, a coated sheet, and a moisture-permeable permeability that have high antibacterial and antifungal properties, high moisture absorption and release properties, and good touch. It is to provide a wet film.

As a result of intensive studies to solve the above problems, the present invention has been completed. That is, the present invention relates to a moisture permeable film comprising a matrix resin and a collagen powder comprising crosslinked regenerated collagen, wherein the degree of communication with the collagen powder is 1 to 95%. .
As a preferred embodiment, there is a moisture-permeable film characterized in that the crosslinked regenerated collagen is crosslinked with a treatment liquid containing an organic compound and / or a metal salt.
In a preferred embodiment, the organic compound is a monofunctional epoxy compound, and the following general formula (1):

（式中、Ｒは、Ｒ₁−、Ｒ₂−Ｏ−ＣＨ₂−またはＲ₂−ＣＯＯ−ＣＨ₂−で表される置換基を示し、Ｒ₁は炭素数２以上の炭化水素基またはＣＨ₂Ｃｌであり、Ｒ₂は炭素数４以上の炭化水素基を示す。）で表される化合物であることを特徴とする透湿性フィルムがある。
好適な実施態様としては、金属塩が次の式で表される塩基性塩化アルミニウム又は塩基性硫酸アルミニウムである透湿性フィルムがある。
Ａｌ（ＯＨ）_n Ｃｌ_3-n、又はＡｌ₂ （ＯＨ）_2n（ＳＯ₄ ）_3-n
（式中、ｎは０．５〜２．５である）
好適な実施態様としては、マトリックス樹脂が、ポリウレタン系樹脂であることを特徴とする透湿性フィルムがある。
また、本発明のコーティング剤は、マトリックス樹脂と、フィラーを含むコーティング剤であって、前記フィラーは、有機樹脂とアルミニウム塩を含み、前記アルミニウム塩は、前記有機樹脂に化学的に結合され、粉末化されたフィラーであることを特徴とする。

(In the formula, R represents a substituent represented by R ₁ —, R ₂ —O—CH ₂ — or R ₂ —COO—CH ₂ —, and R ₁ represents a hydrocarbon group having 2 or more carbon atoms or CH. ₂ Cl and R ₂ represents a hydrocarbon group having 4 or more carbon atoms.) There is a moisture-permeable film characterized by being a compound represented by
In a preferred embodiment, there is a moisture permeable film in which the metal salt is basic aluminum chloride or basic aluminum sulfate represented by the following formula.
Al (OH) _n Cl _3-n or Al ₂ (OH) _2n (SO ₄ ) _3-n
(Where n is 0.5 to 2.5)
As a preferred embodiment, there is a moisture permeable film characterized in that the matrix resin is a polyurethane resin.
The coating agent of the present invention is a coating agent containing a matrix resin and a filler, wherein the filler contains an organic resin and an aluminum salt, and the aluminum salt is chemically bonded to the organic resin and powder The filler is characterized in that it is a filler.

  The filler for a coating film of the present invention contains an organic resin and an aluminum salt, and the aluminum salt is a powder that is chemically bonded to the organic resin and pulverized, and the average particle size of the filler is 10 μm or less, And 95 weight% of particle | grains are the particle diameters of 50 micrometers or less, It is characterized by the above-mentioned.

  The coated sheet of the present invention is obtained by painting the above coating agent on a base fabric sheet.

  The moisture-permeable film of the present invention is excellent in moisture permeability, and has a smooth and comfortable touch feeling similar to that of synthetic leather, and resistance to discoloration due to heating and ultraviolet rays.

In addition, the coating film filler of the present invention, the coating agent containing the same, and the coating sheet take away phosphorus, which is a nutrient of bacteria, due to high phosphorus adsorption ability, and exhibit antibacterial and antifungal properties. Furthermore, it has a smooth, smooth and pleasant feel similar to that of synthetic leather, and resistance to discoloration caused by heating and ultraviolet rays.
In addition, since the coating film filler of the present invention has a particle size in a specific range, it can provide a coating agent with high moisture absorption and desorption and good touch. Furthermore, it has a smooth, smooth and pleasant feel similar to that of synthetic leather, and resistance to discoloration caused by heating and ultraviolet rays.

  Further, the moisture-permeable film, the coating filler, the coating agent containing the same, and the regenerated collagen powder used in the coating sheet are excellent in dispersibility and properties as a modifying additive.

  The present invention is described in detail below.

  The moisture-permeable film of the present invention is a moisture-permeable film containing a matrix resin and collagen powder made of crosslinked regenerated collagen, and the degree of communication with the collagen powder is 1 to 95%.

The regenerated collagen powder of the present invention will be described below.
The regenerated collagen of the present invention is produced by producing a solubilized collagen solution from the skin, bone, tendon, etc. of animals such as cattle, pigs, horses, deer, sharks, birds, fish, etc. It is possible to provide a novel collagen powder that can solve the quality problem of the powder. Furthermore, by spinning a solubilized collagen aqueous solution into regenerated collagen fibers, a completely new collagen powder can be provided by thoroughly purifying the collagen and carrying out precise crosslinking in the fiberizing process by spinning.

  As a method for producing the regenerated collagen, for example, as disclosed in Japanese Patent Application Laid-Open No. 2002-249882, it is preferable to use a portion of the floor skin as a raw material. The floor skin is obtained from, for example, fresh floor skin obtained from animals such as cows, pigs, horses, deer, sea breams, birds, fish, and salted raw skin. Most of these skins are made of insoluble collagen fibers, but are usually used after removing the meaty portion adhering to the net and removing the salt used to prevent spoilage and alteration. In addition, other materials such as bones and tendons of the animals can be used in the same manner.

  The insoluble collagen fibers contain impurities such as lipids such as glyceride, phospholipids and free fatty acids, proteins other than collagen such as glycoproteins and albumin. These impurities have a great influence on quality such as gloss and strength, odor and the like when powdered. Therefore, for example, lime pickled to hydrolyze the fat in insoluble collagen fibers, unraveling the collagen fibers, and then subjected to leather treatments such as acid / alkali treatment, enzyme treatment, solvent treatment, etc. It is preferable to remove these impurities in advance.

  The insoluble collagen that has been treated as described above is subjected to a solubilization treatment in order to cleave the cross-linked peptide portion. As the solubilization method, a publicly-known publicly known alkali solubilization method or enzyme solubilization method can be applied. When applying the alkali solubilization method, it is preferable to neutralize with an acid such as hydrochloric acid. In addition, you may use the method described in Japanese Patent Publication No.46-15033 as an improved method of the conventionally known alkali solubilization method.

  The enzyme solubilization method has an advantage that regenerated collagen having a uniform molecular weight can be obtained, and can be suitably employed in the present invention. As such an enzyme solubilization method, methods described in, for example, Japanese Patent Publication No. 43-25829 and Japanese Patent Publication No. 43-27513 can be employed. Further, the alkali solubilization method and the enzyme solubilization method may be used in combination.

  When the solubilized collagen is further subjected to operations such as pH adjustment, salting out, washing with water and solvent treatment, it is possible to obtain regenerated collagen with excellent quality and so on. It is preferable to perform the treatment. The solubilized collagen obtained has an acidity adjusted to pH 2 to 4.5 with an acid such as hydrochloric acid, acetic acid or lactic acid so as to be a stock solution having a predetermined concentration of, for example, 1 to 15% by weight, preferably about 2 to 10% by weight. Dissolved using solution. The obtained aqueous collagen solution may be defoamed with stirring under reduced pressure as necessary, and may be filtered to remove fine dust that is a water-insoluble matter. In the solubilized collagen aqueous solution obtained, if necessary, for example, a stabilizer for the purpose of improving mechanical strength, improving water resistance / heat resistance, improving gloss, improving spinnability, preventing coloring, preserving, etc. An appropriate amount of an additive such as a water-soluble polymer compound may be blended.

  Regenerated collagen is formed by discharging the solubilized collagen aqueous solution into the inorganic salt aqueous solution through, for example, a spinning nozzle or a slit. As the inorganic salt aqueous solution, for example, an aqueous solution of a water-soluble inorganic salt such as sodium sulfate, sodium chloride, or ammonium sulfate is used, and the concentration of these inorganic salts is usually adjusted to 10 to 40% by weight. The pH of the inorganic salt aqueous solution is usually 2 to 13, preferably 4 to 12, by adding a metal salt such as sodium borate or sodium acetate, hydrochloric acid, boric acid, acetic acid, sodium hydroxide, or the like. It is preferable to adjust. When the pH is less than 2 or exceeds 13, the peptide bond of collagen tends to be subject to hydrolysis, and the target collagen powder tends to be difficult to obtain. Further, the temperature of the inorganic salt aqueous solution is not particularly limited, but it is usually preferably 35 ° C. or lower. When the temperature is higher than 35 ° C., the soluble collagen is denatured, so that the strength is lowered and stable production becomes difficult. In addition, although the minimum of temperature is not specifically limited, Usually, it can adjust suitably according to the solubility of inorganic salt.

  The free amino group of the collagen is modified with an alkyl group having 2 to 20 carbon atoms and having a hydroxyl group or an alkoxy group at the β-position or γ-position. The carbon number main chain indicates a continuous carbon chain of an alkyl group bonded to an amino group, and the number of carbons existing through other atoms is not considered. As a reaction for modifying a free amino group, a conventionally known alkylation reaction of an amino group can be used. In view of reactivity, ease of treatment after the reaction, etc., the alkyl group having 2 to 20 carbon atoms having a hydroxyl group or an alkoxy group at the β-position is preferably a compound represented by the following general formula (2).

—CH ₂ —CH (OX) —R (2)
(In the formula, R represents a substituent represented by R ₁ —, R ₂ —O—CH ₂ — or R ₂ —COO—CH ₂ —, and R _{1 in the} substituent is a carbon atom having 2 or more carbon atoms. A hydrogen group or CH ₂ Cl, R 2 represents a hydrocarbon group having 4 or more carbon atoms, and X represents hydrogen or a hydrocarbon group.)

  Preferable examples of the general formula (2) include a glycidyl group, a 1-chloro-2-hydroxypropyl group, and a 1,2-dihydroxypropyl group. In addition, a structure in which a glycidyl group is added to a free amino group in collagen can be mentioned. Furthermore, a structure in which the epoxy compound used is subjected to ring-opening addition and / or ring-opening polymerization starting from the hydroxyl group contained in the alkyl group described in the above-mentioned preferred group can be mentioned. Examples of the terminal structure include those having the aforementioned alkyl group structure.

  Examples of amino acids constituting the free amino group of the regenerated collagen include lysine and hydroxylysine. Furthermore, although the amino acid that originally constitutes collagen is arginine, the amino group of ornithine, which is produced by partial hydrolysis during hydrolysis under alkaline conditions to obtain the regenerated collagen, is also present. Alkylation reaction is performed. In addition, in the present invention, the reaction proceeds also in the secondary amine contained in histidine.

  The modification rate of the free amino group can be measured by amino acid analysis, and calculated based on the amino acid analysis value of the regenerated collagen fiber before the alkylation reaction or the known composition of the free amino acid constituting the collagen used as the raw material Is done. In the modification of the amino group in the present invention, the structure modified with an alkyl group having 2 or more carbon atoms having a hydroxyl group or an alkoxy group at the β-position or γ-position may be 50% or more of the free amino group. The other part may be a free amino group or a structure modified with another substituent. The modification rate of the free amino acid in the regenerated collagen needs to be 50% or more, more preferably 65% or more, and still more preferably 80% or more. When the reaction rate is low, good characteristics cannot be obtained due to heat resistance.

  Here, in the modification of a free amino group, one molecule of an alkylating agent usually reacts per one free amino group, but two or more molecules may react. Furthermore, a cross-linking reaction may be present in the molecule or between the molecules via a hydroxyl group, an alkoxy group or other functional group present in the β-position or γ-position of the alkyl group bonded to the free amino group. . Specific examples of the alkylation reaction include an addition reaction of an epoxy compound, an addition reaction of a hydroxyl group at the α-position or β-position or an aldehyde compound having this derivative, and a subsequent reduction reaction, a hydroxyl group at the β-position or γ-position. Alternatively, a substitution reaction such as a halogenated compound having 2 or more carbon atoms having an alkoxy group, an alcohol, and an amine is exemplified, but the invention is not limited thereto.

  In the present invention, aldehydes, epoxies, phenol derivatives, and the like are listed as organic compounds that can be used as an alkylating reagent, but the modification reaction with an epoxy compound has excellent characteristics because of its reactivity and ease of processing. Are preferable, and monofunctional epoxy compounds are particularly preferable.

  Specific examples of the monofunctional epoxy compound used here include, for example, ethylene oxide, propylene oxide, butylene oxide, isobutylene oxide, octene oxide, styrene oxide, methyl styrene oxide, epichlorohydrin, epibromohydrin, glycidol and the like. Olefin oxides, glycidyl methyl ether, butyl glycidyl ether, octyl glycidyl ether, nonyl glycidyl ether, undecyl glycidyl ether, tridecyl glycidyl ether, pentadecyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, phenyl glycidyl ether , Cresyl glycidyl ether, t-butylphenyl glycidyl ether, dibromophenyl glycidyl ether, benzyl glycidyl ether Glycidyl ethers such as polyethylene oxide glycidyl ether, glycidyl formate, glycidyl acetate, glycidyl acrylate, glycidyl methacrylate, glycidyl benzoate and the like, glycidyl amides, etc. It is not a thing.

Among monofunctional epoxy compounds, since the water absorption rate of regenerated collagen decreases, it is preferable to treat with a monofunctional epoxy compound represented by the following general formula (1). In the formula, R represents a substituent represented by R ₁ —, R ₂ —O—CH ₂ — or R ₂ —COO—CH ₂ —, and R ₁ represents a hydrocarbon group having 2 or more carbon atoms or CH ₂ Cl and R ₂ represents a hydrocarbon group having 4 or more carbon atoms.

  The regenerated collagen thus obtained is swollen with water or an aqueous solution of an inorganic salt. The swollen body preferably contains 4 to 15 times the weight of regenerated collagen and contains an aqueous solution of water or an inorganic salt. If the content of the aqueous solution of water or inorganic salt is 4 times or more, the aluminum salt content in the regenerated collagen is large, so the water resistance is sufficient. Moreover, if it is 15 times or less, intensity | strength does not fall and handleability is favorable.

The swollen regenerated collagen is then immersed in an aqueous solution of an aluminum salt. As an aluminum salt of this aluminum salt aqueous solution, the following formula Al (OH) _n Cl _3-n or Al ₂ (OH) _2n (SO ₄ ) _3-n
(Where n is 0.5 to 2.5)
The basic aluminum chloride or basic aluminum sulfate represented by these is preferable. Specifically, for example, aluminum sulfate, aluminum chloride, alum or the like is used. These aluminum can be used individually or in mixture of 2 or more types. The aluminum salt concentration of the aluminum salt aqueous solution is preferably 0.3 to 5% by weight in terms of aluminum oxide. When the concentration of the aluminum salt is 0.3% by weight or more, the aluminum salt content in the regenerated collagen fiber is high, and the water resistance is sufficient. Moreover, if it is 5 weight% or less, it will not be so hard after a process, and handleability will be favorable.

  The pH of the aluminum salt aqueous solution is usually adjusted to 2.5 to 5 using, for example, hydrochloric acid, sulfuric acid, acetic acid, sodium hydroxide, sodium carbonate or the like. If this pH is 2.5 or more, the structure of collagen can be maintained well. If pH is 5 or less, precipitation of aluminum salt does not occur, and it becomes easy to penetrate uniformly. This pH is first adjusted to 2.2 to 3.5, and the aluminum salt aqueous solution is sufficiently infiltrated into the regenerated collagen. Thereafter, for example, sodium hydroxide, sodium carbonate or the like is added to 3.5 to 5 It is preferable to complete the treatment by adjusting to. When a highly basic aluminum salt is used, only the first pH adjustment of 2.5 to 5 may be used. Moreover, the liquid temperature of this aluminum salt aqueous solution is although it does not specifically limit, 50 degrees C or less is preferable. If the liquid temperature is 50 ° C. or lower, the regenerated collagen is hardly denatured or altered.

  The time for immersing the regenerated collagen in this aluminum salt aqueous solution is 3 hours or more, preferably 6 to 25 hours. If this immersion time is 3 hours or more, the reaction of the aluminum salt proceeds, and the water resistance of the regenerated collagen becomes sufficient. Moreover, although there is no restriction | limiting in particular in the upper limit of immersion time, reaction of aluminum salt will fully advance within 25 hours, and water resistance will also become favorable. It should be noted that an inorganic salt such as sodium chloride, sodium sulfate, potassium chloride or the like may be appropriately added to the aqueous solution of the aluminum salt so that the aluminum salt is not rapidly absorbed into the regenerated collagen and uneven concentration occurs.

  The crosslinked regenerated collagen thus treated with the aluminum salt is then washed, oiled and dried. The regenerated collagen fiber thus obtained has almost no coloration treated with a conventional chromium salt and has excellent water resistance. In order to prevent collagen denaturation (gelatinization), attention should be paid to the temperature history during processing. In order to prevent denaturation even after cross-linking, it is necessary to keep the moisture and temperature control during production, powdering processing and product storage below the denaturation conditions of regenerated collagen. Since most of the gelatinized materials have changed characteristics, it is difficult to express the characteristics of the target collagen. It is advantageous to use the regenerated collagen in terms of preventing denaturation.

  In the case of spinning from a collagen solution, it is easy to mix and color a pigment or dye in the solution or immediately before spinning by a known method. The pigments and dyes to be used can be selected according to the purpose, without any elution separation in the spinning process or powdering process, and according to the required quality of the product used. Moreover, a filler, an anti-aging agent, a flame retardant, an antioxidant, etc. can also be added as needed. It can replace with such a collagen fiber manufacturing process, can manufacture a film by the same method using a slit nozzle, and can also pulverize this.

  In the present invention, the regenerated collagen obtained by the above-described method can be made into a collagen powder (regenerated collagen powder) comprising regenerated collagen crosslinked by pulverization. When the regenerated collagen is a fiber or film, it is cut into a fiber length or size suitable for pulverization, further pulverized, or directly pulverized into a regenerated collagen powder. be able to. There is no particular limitation on the cutter that can be used to produce the regenerated collagen powder. For example, it is cut to about 0.1 mm to several mm with a rotary blade cutter, a belt cutter, a shearing machine, a cutter mill or the like usually used for cutting fibers. In addition, this cut cotton can be crushed in roller mills, rod mills, ball mills (dry, wet), jet mills, pin mills, vibration mills, centrifugal (CF) mills, planetary ball mills, shearing mills such as grinder mills, etc. And then finely pulverized using a medium stirring type ultrafine pulverizer or the like. By using a hard ball such as a zirconia ball, it can be preferably used from the viewpoint of preventing the ball material from being mixed into the powder and grinding efficiency. Balls of other materials such as alumina balls can also be used. As another pulverization method, freeze pulverization can also be used. The regenerated collagen powder thus obtained preferably has an average particle size of 0.01 to 80 μm.

  It is also possible to appropriately adjust the particle size of the regenerated collagen powder obtained depending on the type of pulverizer and the pulverization time. For example, when a vibration mill is used, an average particle size of about 5 to 80 μm is obtained in 1 hour to several tens of hours, but when an average particle size of 0.01 to 5 μm is obtained, crushed regeneration It is obtained by classifying collagen powder. Classification may be wind classification or classification in water.

  Moreover, the content of aluminum converted as a single metal of the regenerated collagen powder is preferably in the range of 0.1 to 70% by weight. A more preferred range is 0.2 to 50% by weight, and a particularly preferred range is 1 to 40% by weight.

  Although it is possible to appropriately adjust the particle size of the regenerated collagen powder obtained depending on the type of pulverizer and the pulverization time, for example, when a vibration mill is used, the average particle size is 5 to 1 hour to several tens of hours. Although a thing about 80 micrometers is obtained, when obtaining a thing with an average particle diameter of 0.01-5 micrometers, it is obtained by classifying the crushed regenerated collagen powder.

  The average particle size of the regenerated collagen powder is preferably 0.01 to 80 μm, and more preferably 1 to 20 μm. When the thickness is 0.01 μm or more and 80 μm or less, the surface feel after the film is formed and the dispersibility in organic solvents and polyurethane paints is good, which is preferable. The average particle diameter can be determined by, for example, a microtrack method, which is one of laser diffraction methods.

  In the case of a moisture permeable film, as the matrix resin, polyurethane resin, polyvinyl chloride resin, polyolefin resin, olefin thermoplastic elastomer (TPO), styrene thermoplastic elastomer (TPS), synthetic rubber, etc. should be used. Can do. Of these, polyurethane resins are preferred in terms of mechanical strength, flexibility, scratch resistance, and the like. Examples of the polyurethane resins include polycarbonate urethane resins, polyester urethane resins, polyether urethane resins, silicone modified urethane resins, fluorine modified urethane resins, and polyamino acid urethane resins. Among these, polycarbonate urethane resin, polyester urethane resin, and polyether urethane resin are preferable from the balance between strength and moisture permeability. As the polyurethane resin, a commercially available polyurethane paint can be used. A thermoplastic polyurethane resin can also be used.

  The composition ratio of the matrix resin and the regenerated collagen powder is preferably 95: 5 to 30:70 (weight ratio) and 90:10 to 50:50 (weight ratio) from the viewpoint of moisture permeability and membrane strength. It is more preferable. If the regenerated collagen powder is added to the above range or more, the film strength is lowered, which is not preferable. If blended below the above range, sufficient moisture permeability is not exhibited, which is not preferable.

  The degree of communication is the content of the communication structure. Since the regenerated collagen powder of the present invention has an irregular particle shape, when dispersed in a matrix resin, the particles easily form contact points with each other, and thus has a communication structure, and therefore has extremely excellent moisture permeability. ing. In particular, regenerated collagen powder produced using a CF mill is preferable because it has a strong needle shape and can easily come into contact with each other. An outline of the communication structure is shown in FIG.

  The degree of communication can be measured and calculated with an electron microscope. The microtome cut surface of the film is observed with a scanning electron microscope, and 10 views of 2300 times magnification images are randomly acquired. Next, for each of the images, the ratio of the portion where the powder protrudes in the length of 100 microns in the center of the surface portion on the film upper surface side (cast upper surface side) is calculated. The average of the ratio of the powder protrusion calculated for each of these 10 visual fields is defined as the degree of communication.

The degree of communication is preferably 1 to 95%, and more preferably 10 to 90%. If the degree of communication is less than 1%, sufficient moisture permeability cannot be exhibited, which is not preferable. In order to make the degree of communication 95% or more, it is necessary to add a large amount of regenerated collagen, which is not preferable because the strength of the film is remarkably lowered.
The thickness of the moisture-permeable film of the present invention is usually preferably from 5 to 30 μm, more preferably from 10 to 20 μm, from the viewpoint of moisture permeability and film strength. If the thickness is 30 μm or more, the moisture permeability decreases, which is not preferable. When the thickness is 5 μm or less, the film strength is undesirably lowered.

The moisture permeability is a property that allows moisture (water vapor) to pass through, and the moisture permeability can be measured by, for example, the JIS L 1099-1985 A-1 method (calcium chloride method). Moisture permeability is preferably at 300g / m ² / 24h or more, it is 500g / m ² / 24h or more, more preferably. With regard to synthetic leather and sports clothing, if the moisture permeability is high, it is possible to prevent peeling during sweating and to obtain comfort.

  In the range which does not impair moisture permeability, the moisture-permeable film of this invention can laminate | stack films other than this invention, and can be set as a laminated film in order to provide intensity | strength. Such a laminated film may be a two-layer film or a multilayer film. Examples of the film other than the present invention include a film made of polyurethane-based resin, and the film may be nonporous or porous. Moreover, the moisture-permeable film of this invention from which content of reproduction | regeneration collagen powder differs can also be laminated | stacked.

  The moisture-permeable film of the present invention can be produced using a known method such as dry film formation, wet film formation, and extrusion molding. Among these, it is preferable to produce by a dry film forming method. Dry film formation is performed by casting the resin solution and evaporating the solvent. Preferably, the resin solution is applied on the release paper to a uniform thickness using a comma coater, knife coater, reverse coater, etc., and then dried. The film is formed by peeling the release paper. In the resin film, a colorant (pigment), a stabilizer, a filler, and other additives may be added. Further, the solution viscosity may be adjusted by diluting with an organic solvent. As the organic solvent, N, N-dimethylformamide, 2-butanone (methyl ethyl ketone), isopropanol, toluene and the like alone or a mixture thereof can be used.

  As a method for forming the moisture permeable film of the present invention on a base fabric by dry and wet film formation to form a moisture permeable waterproof fabric, spray coating, gravure coating, knife coating, roll coating, release paper were used. A known method such as a laminating method can be employed. As the base fabric, fibers such as nylon, polyester, polyacrylonitrile, cotton, rayon or the like, or a woven fabric, a knitted fabric, or a nonwoven fabric made of a mixed fiber thereof may be used.

  The moisture-permeable waterproof film obtained in this way has a surface feel that does not feel uncomfortable when a person comes into contact with the skin, has no stickiness, and has excellent moisture permeability.

  Since the moisture-permeable film of the present invention is excellent in moisture permeability, it can be suitably used for synthetic leather, artificial leather, shoes, sports clothing, sauna suits, windbreakers, raincoats, winter clothes, and the like.

  The regenerated collagen powder of the present invention has moisture absorption / release properties, touch and coolness, which are characteristics derived from natural leather, and antibacterial and anti-elastogenic properties derived from aluminum cross-linking. Therefore, the moisture-permeable film of the present invention has these characteristics. To demonstrate.

  In the case of a coating agent, a filler for a coating film, and a coated sheet, the regenerated collagen powder used in the present invention exhibits antibacterial properties even when the particle diameter is about 0.1 to several mm, but the average particle diameter is 0.01. Antibacterial properties are improved by fine pulverization to ˜80 μm. Moreover, from a viewpoint of a touch, 1-20 micrometers is preferable and, as for an average particle diameter, 1-10 micrometers is more preferable. If the average particle size is larger than the above range, the coated surface after applying the coating agent has a rough feel, which is not preferable. Moreover, handling property is favorable in it being 1 micrometer or more.

  The average particle size of the filler after classification is preferably 10 μm or less, and 95% by weight of the particles preferably have a particle size of 50 μm or less. More preferably, the average particle size is 5 μm or less, and 95% by weight of the particles have a particle size of 20 μm or less. If it is the said range, the tactile sensation of a coated material can exhibit a smooth feeling, and moisture absorption / release property is also suitable.

  The regenerated collagen powder of the present invention is excellent in the feeling of contact cold and warm. The feeling of cold contact is a sensitivity factor (tactile sensation) that indicates the warmth (coldness) of the material, and surface differential heat (Qmax) is usually used as an index. In PVC leather, Qmax is large, that is, heat transfer is large and a cold tactile sensation is obtained. This skin has a small Qmax and a warm feel. Since the sheet coated with the regenerated collagen powder of the present invention contains collagen, which is the same component as the main skin, the surface differential heat (Qmax) is lower than PVC leather, and a “warm” tactile sensation closer to the main skin is obtained. be able to.

  The collagen powder of the present invention is excellent in whiteness. Since the collagen powder of the present invention is sufficiently purified and impurities are removed at the production stage of collagen fibers, it has high whiteness and little yellowness.

  The particle distribution and average particle diameter can be measured with a commercially available particle size distribution meter. For example, it can be measured using a microtrack particle size distribution measuring apparatus (“MT3300” manufactured by Nikkiso Co., Ltd.) by a laser diffraction scattering method. For example, methanol is used as the dispersion medium. The particle refractive index is 1.44 which is the refractive index of collagen.

  The regenerated collagen powder of the present invention has phosphorus adsorption ability. The phosphorus to be adsorbed is not particularly limited as long as it contains phosphorus element or a phosphorus compound. For example, a phosphate structure can be adsorbed. Here, the phosphoric acid structure refers to a substance having a phosphoric acid skeleton such as phosphoric acid, phosphate, and phosphate ester. In general, phosphorus element is generally present in the form of a phosphoric acid structure in nature, and the preferred method for adsorbing phosphorus by the phosphorus adsorbent of the present invention is simply an aqueous solution containing phosphorus and regenerated collagen powder that is a phosphorus adsorbent. Or a phosphorus adsorbent that is a mixture with the support. For more efficient adsorption, it is desirable to disperse the phosphorus adsorbent or adsorbent as uniformly as possible in the solution.

In the coating agent composition of the present invention, the regenerated collagen powder is preferably added in an amount of 0.1 to 70% by weight. More preferably, it is 2 to 60% by weight, and particularly preferably 5 to 60% by weight. Effective antibacterial properties are observed when the content is 0.1% by weight or more. If it is 70 weight% or less, there exists fluidity | liquidity preferable as a coating agent.

Next, carboxymethyl cellulose and polyvinyl alcohol of the present invention will be described.
In the present invention, carboxymethyl cellulose and polyvinyl alcohol can also be used as the organic resin powder. Carboxymethylcellulose and polyvinyl alcohol are also matrix resin gel components that are soluble in water before crosslinking, and are crosslinked by contacting an aluminum salt. The aluminum salt is chemically bonded to the gel component of the resin to form a water-insoluble resin. can do. That is, since carboxymethyl cellulose has a —COOH group and a —OH group, it can be crosslinked with an aluminum salt. Moreover, since polyvinyl alcohol has an —OH group, it can be crosslinked with an aluminum salt. Polyvinyl alcohol having a -COOH group introduced may be used. The amount of —COOH group introduced can be, for example, about 0.1 to 5 mol%.

  An example of carboxymethylcellulose is “carboxymethylcellulose sodium salt” manufactured by SIGMA. As polyvinyl alcohol, for example, “Anion-modified PVA (A series)” grade: AF17 manufactured by Nippon Vineyard PVA is available.

1. Filler made of organic resin powder In the present specification, a powdered filler containing an organic resin and an aluminum salt is referred to as “filler made of organic resin powder” or simply “organic filler”.

2. Matrix resin As the matrix resin material, any resin may be used as long as it is a resin used for general paints. For example, selected from the group consisting of polyamide resin, vinyl chloride resin, polyurethane resin, polyester resin, acrylic resin, styrene resin, acrylic silicone resin, epoxy ester resin, fluorine resin, polyolefin elastomer, polyester elastomer, styrene elastomer It is preferable to use a composition containing at least one kind of resin that can be used in combination as long as the moisture absorption / release properties and chemical substance adsorption properties that are the characteristics of the regenerated collagen powder are not impaired. Among these, polyurethane resins are preferable in terms of wear resistance, cold resistance, flex resistance, oil resistance, and the like. When polyurethane resin / regenerated collagen powder is used as a coating agent, the moisture absorption and release characteristics and leather-like feel, particularly “smooth” feel, which are characteristic of the regenerated collagen powder, are obtained, and there is no stickiness and the tactile feeling is good. Furthermore, by blending silica fine powder, it becomes “moist touch” and a high-class feeling can be exhibited. Examples of the polyurethane resin include polycarbonate polyurethane resin, polyester urethane resin, polyether polyurethane resin, polycaprolactone polyurethane resin, silicone copolymer type, and water polyurethane resin.

3. Coating Agent The coating agent of the present invention contains an organic filler such as a matrix resin and regenerated collagen powder. Moreover, an organic solvent or water, inorganic fillers, such as a silica powder, a coloring agent (pigment), a plasticizer, an anti-aging agent, etc. can also be added as needed. The mixing conditions may be known conditions and are not particularly limited.

  Although it does not specifically limit as an organic solvent, For example, in the case of a polyurethane-type resin, organic solvents, such as a dimethylformamide (DMF), methyl ethyl ketone (MEK), toluene, isopropanol, are preferable from the solubility of resin. These solvents may be used alone or in combination of two or more. In recent years, water-based polyurethane resins and water-based acrylic resins have attracted attention due to problems of environmental impact and VOC, or costs and labor related to solvent recovery / disposal, and these water-based resins can also be used.

By mixing the regenerated collagen powder thus obtained and the matrix resin material, a coating agent composition having excellent antibacterial or antifungal properties can be obtained. In addition, the coating agent of the present invention is excellent in terms of water resistance, formaldehyde adsorption, moisture absorption / release properties, wettability, matting and the like.

  The coating agent of the present invention may be applied to a fixed object such as a wall or ceiling, or may be a coated sheet coated on a base fabric sheet. Examples of the coated sheet include wallpaper, cloth, synthetic leather, polyvinyl chloride leather, artificial leather, or a synthetic resin molded product. The coating method is not particularly limited, and for example, a gravure printer method, a spray method, a roll coater method, a reverse coater method, a doctor knife method, a brush coating method, a dipping method, or the like can be used.

  The coating agent of the present invention is economically inexpensive because it does not require the addition of another antibacterial agent or antifungal agent, for example, a composition or compound containing Ag, or a pyridine compound. Of course, it may be used in combination with other antibacterial agents or antiepileptic agents.

4). Although fungi are classified into bacteria and fungi, there are few materials that are usually effective in any of these, and those having such functions are desired. In general, the bacteria are roughly classified into Gram-positive bacteria having a large amount of peptidoglycan on the cell wall, Gram-negative bacteria having lipopolysaccharide, and other bacteria as shown below. Gram-positive bacteria are further roughly classified into Gram-positive cocci and Gram-positive rods.

  Gram-positive cocci include facultative anaerobic and aerobic cocci, and the genera include Micrococcus, Staphylococcus, Streptococcus and Streptococcus and Enterococcus, Staphylococcus aureus As methicillin-resistant Staphylococcus aureus (MRSA) and Streptococcus, Streptococcus pyogenes, Group B Streptococcus, Streptococcus pneumoniae, and Streptococcus pneumoniae are known as pathogens.

  Gram-positive rods are classified into Corynebacterium, Listeria, Eridiperrostrix, Bacillus, and Mycobacterium, and the pathogens are Corynebacterium diphtheria and Listeria monocytogenes. The main ones are the erythrosperix genus swine venom, Bacillus anthrax, Bacillus cereus, and Mycobacterium tuberculosis.

  The gram-negative bacterium is mainly gram-negative bacilli.

  Examples of gram-negative bacilli include aerobic gram-negative bacilli and gram-negative facultative anaerobes.

  Pseudomonas, Burkholderia, Rastonia, Legionella, Brucella, Bordetella, Alcaligenes, Francisella etc. are mentioned as the main genus of aerobic gram-negative bacilli. Pseudomonas genus Pseudomonas aeruginosa, Legionella genus Legionella pneumophila, Brucella genus Thermophilus, bovine abortion thermophile, swine abortion bacteria and the like are known as those having pathogenicity.

Gram-negative facultative anaerobes are classified as Enterobacteriaceae, Vibrioaceae, Pasteurellaceae, and Enterobacteriaceae are further classified as Escherichia, Klebsiella, Serratia, Proteus, Yersinia and As E. coli, E. coli such as O157, Salmonella, Shigella, Klebsiella, Klebsiella pneumoniae, Serratia, spirits, Proteus, Proteus mirabilis, and Yersinia, plague bacteria are known. Vibrioaceae is known as Vibrio cholera, Pasteurellae is Pasteurella multicida is known as a pathogenic bacterium.

  As other bacteria, there are obligate anaerobic bacteria and spiral fungal groups as gram positive and negative bacterial groups, and the following bacteria are known.

  The obligate anaerobic bacteria are classified into obligate spore-forming bacteria, obligate anaerobic gram-positive sporeless bacillus, obligately anaerobic gram-negative arbuscular gonococci, anaerobic gram-positive cocci, and anaerobic gram-negative cocci. These include obligate spore-forming bacteria such as tetanus, Clostridium botulinum, Clostridium perfringens, and difficile.

  As the spiral fungus group, C. pylori of Campylobacter genus. fetus, C.I. jejuni, C.I. colit is known as a pathogen.

  The above bacteria are known in various pathogens. In particular, it can be said that Escherichia coli, Staphylococcus aureus, Pseudomonas aeruginosa, MRSA, Bacillus cereus, and Klebsiella pneumoniae, which are often detected in food poisoning and hospital infections, are extremely important as antimicrobial agents.

5). Fungi (yeast and sputum)
Next, fungi are roughly classified into yeast and cocoon.

  Spiders are classified into Aspergillus genus, Penicillium genus, Cladosporium genus, Alternaria genus, Fusarium genus, Aureobasidium genus, Trichoderma genus, Chaetomium genus. Examples of target moths are those listed in JIS Z 2911. For example, (Group 1) Aspergillus niger, Aspergillus tereus, Eurotium Tonohirum, (Group 2) Penicillinium citrinum, Penicillinium funiculosum, (Group 3) Group) Rhizopus oryzae, (Group 4) Cladosporium cladosporioides (Kurokawa 黴), Aureobasidium pullulans, Gliocladium bilens, (Group 5) Ketomium globosum, Fusarium moniliforme, Milotesium・ Spots such as Belcaria are considered.

  Yeast is classified into the genus Candida, the genus Rhodotorula, and the genus Saccharomyces.

  The coating agent of the present invention has a growth inhibitory effect on the bacteria and fungi corresponding to the yeast.

  In addition, the anti-epileptic agent of the present invention has a growth inhibitory effect against fungi corresponding to the above-mentioned moth.

  The present invention relates to an antibacterial agent or an antiepileptic agent, but it does not deny the case of having both performances, and may be compatible.

  The amount of aluminum as a metal simple substance of the coating agent of the present invention is measured by atomic absorption spectrometry after wet oxidative decomposition of the powder. The coating film can also be measured by the same method as described above. In addition, aluminum as a metal simple substance shows only an aluminum atom and its associated body.

Hereinafter, the present invention will be described more specifically with reference to examples. In addition, this invention is not limited at all by these Examples. In the following examples, “%” simply means “wt%”.

Example 1
(1) Preparation of regenerated collagen powder 30 kg of hydrogen peroxide aqueous solution diluted to 30% by weight was added to 1200 kg of skin sliced with collagen (180 kg of collagen) made from cow's floor skin, and then dissolved in lactic acid aqueous solution. A stock solution adjusted to pH 3.5 and a solid content of 7.5% by weight was prepared. The stock solution was subjected to stirring and defoaming treatment with a stirring deaerator (manufactured by Dalton Co., Ltd., 8DMV type) under reduced pressure, transferred to a piston-type spinning stock solution tank, and further allowed to stand under reduced pressure for defoaming. This stock solution is extruded by a piston, and then a fixed amount is fed by a gear pump, filtered through a sintered filter having a pore diameter of 10 μm, passed through a spinning nozzle having a pore diameter of 0.275 mm, a hole length of 0.5 mm, and a hole number of 300, and sodium sulfate is 20 weight. % Was discharged at a spinning speed of 5 m / min into a 25 ° C. coagulation bath (adjusted to pH 11 with boric acid and sodium hydroxide).

  Next, the obtained regenerated collagen fibers (300 fibers, 20 m) were added to 1.32 kg of an aqueous solution containing 1.7% by weight of epichlorohydrin, 0.0246% by weight of sodium hydroxide, and 17% by weight of sodium sulfate. After soaking at 25 ° C. for 4 hours, the temperature of the reaction solution was further raised to 43 ° C. and impregnated for 2 hours.

  After completion of the reaction, the reaction solution was removed, and then washed with batch water three times using 1.32 kg of 25 ° C. water in a fluid type apparatus. Thereafter, 1.32 kg of an aqueous solution containing 5% by weight of aluminum sulfate, 0.9% by weight of trisodium citrate salt and 1.2% by weight of sodium hydroxide was impregnated at 30 ° C., and 2 hours after the start of the reaction, After 5 hours and 4 hours, 13.2 g of a 5% by weight aqueous sodium hydroxide solution was added to the reaction solution and reacted for a total of 6 hours. After completion of the reaction, the reaction solution was removed, and then washed with batch water three times using 1.32 kg of 25 ° C. water in a fluid type apparatus.

  Next, a part of the prepared fiber was immersed in a bath filled with an oil agent comprising an amino-modified silicone emulsion and a pluronic polyether-based antistatic agent to adhere the oil agent. One end of the fiber bundle is fixed inside a hot air convection dryer set to 50 ° C., and a weight of 2.8 g is hung from one fiber on the other end and dried under tension for 2 hours. 60 deci tex Regenerated collagen fibers were obtained.

  The obtained regenerated collagen fiber was physically pulverized. That is, first, 2 kg of regenerated collagen fibers were shredded to a length of about 1 mm with a cutter mill SF-8 (manufactured by Sanriki Seisakusho) and recovered with a Cyclone CYC-600 model manufactured by the same company. This shredded product was used for the antibacterial test of Staphylococcus aureus in Example 1 described later. Next, it grind | pulverized using the vibration mill (made by Token Co., Ltd.). As the grinding conditions, the same alumina balls (diameter 19 mm) are filled in an alumina container having a capacity of 4 L at a filling capacity of 80%, and the chopped collagen fibers are filled in a filling capacity of 40% (500 g) for 4 to 12 hours. Carried out. As a result, it was possible to obtain a powder having an average particle size of 33 μm by pulverization for 4 hours and an average particle size of 10 μm by pulverization for 15 hours. The powder having an average particle size of 10 μm was classified, and coarse particles having a size of 20 μm or more were cut. As a result, the average particle size was 8.8 μm.

(2) Preparation and Coating of Coating Agent Composition Using the regenerated collagen powder obtained above and “Nipporan 5199” (solid content 30 wt%) manufactured by Nippon Polyurethane as a polycarbonate-based polyurethane resin, N, N— Dimethylformamide (DMF) was weighed and mixed as shown in Table 1 to obtain a coating composition. This coating agent composition was coated on a soft polyvinyl chloride (PVC) sheet using a film applicator and then dried at 100 ° C. for 5 minutes. The film thickness after drying was 30 μm.

(3) Antibacterial test The obtained coating was subjected to an antibacterial test. The test sample was cut into a plate of 5 cm × 5 cm and used for an antibacterial test. In the test, Escherichia coli IFO3972 was cultured with shaking in 5 ml of normal bouillon medium (Eiken Chemical Co., Ltd.) at 27 ° C. overnight, and then sterilized physiological saline containing normal bouillon medium at a final concentration of 1/500. Dilute with (0.85 wt% NaCl). 0.4 ml of this bacterial suspension was placed in a resin petri dish (manufactured by Seibu Co., Ltd.), and a sample was placed on the bacterial solution with the test surface down, covered and left at 30 ° C. This bacterial suspension was recovered in 4.5 ml of sterile physiological saline at the time of inoculation and 24 hours later, diluted 10-fold in 5 steps, and the number of viable bacteria in 0.5 ml of these bacterial suspensions was measured. In addition, the control used the polyethylene sheet instead of the sample, and performed the same operation. The number of viable bacteria is measured by hygiene test method, comment (2005) 1.2.1.1 General test method for bacteria 3) Bacteria measurement (1) Pour plate culture method (p.59)
). However, SCDLP agar medium “DAIGO” (manufactured by Nippon Pharmaceutical Co., Ltd.) was used for culturing the microorganisms and cultured at 37 ° C. for 24 hours. The viable cell count was converted to the viable cell count concentration in the bacterial suspension inoculated into the sample. The detection limit of the viable cell count was 10 2 cells / ml or less.

  The above conditions and results are shown in Table 1.

As is clear from Table 1, in Experiment 2, the number of E. coli cells was reduced by half compared to Experiment 1 (Comparative Example). The amount of regenerated collagen powder in Experiment 2 was about 0.1 wt% in terms of dry weight. Moreover, in the regenerated collagen powder 5-30 wt% of Experiments 3-6, the viable count of E. coli was greatly reduced.

(Example 2)
A coating composition was prepared in the same manner as in Example 1, coated on PVC, and anti-epileptic properties were carried out by using the Kurokawa strain, as follows.

That is, the regenerated collagen powder was added to the dried coating film so as to have a concentration of 0 wt%, 0.1 wt%, 1 wt%, 5 wt%, 10 wt%, and 30 wt%. Each sample coated with a coating agent is added to an agar-containing medium (Sabouraud agar medium manufactured by Eiken Chemical Co., Ltd.) kept at 50 ° C., and after mixing well, this is dispensed into a petri dish and solidified to obtain a measurement plate. Was made. Next, each test strain was adjusted to a growth medium (Kurokawa potato; Potato Dextose Agar manufactured by Difco) at 25 ° C. for 10 days, adjusted to 10 6 / ml (Kurokawa potato is the number of spores), and smeared on a plate. And cultured after culturing at 25 ° C. for 7 days. Determination was made into the minimum growth inhibitory concentration with the lowest density | concentration by which the growth of the microbe was inhibited.

  From the above results, it was confirmed that the coating agent of this example has anti-eating properties.

(Examples 3-1 to 3-9, Comparative Examples 1-2)
Regenerated collagen powder was prepared in the same manner as in Example 1, classified after pulverization, coarse particles of 20 μm or more were cut, and the coating agent was adjusted and coated in the same manner as in Example 1. Table 3 shows the additives and blending amounts, coating conditions, and evaluation results. In Table 3, the additives are as follows.

(1) Polyurethane “Niporan 5199”: Polycarbonate polyurethane, solid content 30 wt%, manufactured by Nippon Polyurethane Co., Ltd. (2) Polyurethane “Chrisbon 3354”: Polyester polyurethane, solid content 20 wt%, manufactured by Dainippon Ink Co., Ltd. (3) Regenerated collagen Powder CFM-R1: Average particle size 8.8 μm
(4) Regenerated collagen powder VMS: Average particle size 10.0 μm
(5) Silicone oil TSF451-100CS: manufactured by GE Toshiba Silicone Corp. (6) Silica powder ACEMATT TS-100: average particle size 4 μm, manufactured by Tegusa Japan (7) silica powder ACEMATT OK 412: average particle size 3 μm, manufactured by Tegusa Japan (8 ) Solvent DMF: N, N-dimethylformamide (9) Solvent MEK: Methyl ethyl ketone

In Table 3, the evaluation result “tactile sensation” was as follows. Ten evaluators were allowed to touch the painted product by hand, and the evaluation of the touch at that time was expressed as an average score. The evaluation criteria for the feel was based on whether or not it approximates to synthetic leather.
5 points: Very good touch and close to synthetic leather.
4 points: Good touch feeling, similar to synthetic leather.
3 points: Normal 2 points: Touch feeling is not so good.
1 point: Touch feeling is bad.

  As described above, the examples of the present invention were evaluated to be more than normal.

Example 4
Insolubilized carboxymethylcellulose (CMC) powder was prepared as follows. A 1 wt% aqueous solution of carboxymethylcellulose sodium salt (CMC; manufactured by Sigma) was prepared, and the solution was dropped into an aluminum sulfate solution for aluminum crosslinking to form an insoluble material. The insoluble material was collected, dried, and pulverized in a mortar to obtain fine particles. The fine particles were classified to cut particles of 20 μm or more, and the average particle size was 12 μm. This insolubilized carboxymethyl cellulose (CMC) powder was added to “Nipporan 5199” (solid content 30 wt%) manufactured by Nippon Polyurethane Co., Ltd. so as to have a dry weight of 10 wt%. I got a thing. This coating agent composition was coated on a soft polyvinyl chloride (PVC) sheet using a film applicator and then dried at 100 ° C. for 5 minutes. The film thickness after drying was 30 μm. Antibacterial evaluation of the obtained coating was performed in the same manner as in Example 1. As a result, the viable cell count was not detected. From the above results, antibacterial properties were recognized.

(Example 5)
Insolubilized PVA powder was prepared as follows. A 10% (W / V) aqueous solution of anion-modified polyvinyl alcohol (trade name “AF-17” manufactured by Nippon Vinegar Poval Co., Ltd.) is prepared, and the solution is added dropwise to an aluminum sulfate solution for aluminum cross-linking so as to be insoluble. Formed. The insoluble material was collected, dried, and pulverized in a mortar to obtain fine particles. The fine particles were classified to cut particles of 20 μm or more, and the average particle size was 11 μm. This insolubilized PVA powder was added to “Nippolan 5199” (solid content: 30 wt%) manufactured by Nippon Polyurethane Co., Ltd. so as to have a dry weight of 10 wt%, and the coating agent composition was obtained in the same manner as in Example 1 except for the other conditions. . This coating agent composition was coated on a soft polyvinyl chloride (PVC) sheet using a film applicator and then dried at 100 ° C. for 5 minutes. The film thickness after drying was 30 μm. Antibacterial evaluation of the obtained coating was performed in the same manner as in Example 1. As a result, the viable cell count was not detected. From the above results, antibacterial properties were recognized.

(Example 6)
The powder obtained by pulverizing the regenerated collagen fiber obtained in Example 1 was classified by wind. As the classifier, “Micron Separator MS-1H” manufactured by Hosokawa Micron and “Pulse Jet Collector CP-16-6” manufactured by the same company were used. As a result, a filler having a particle size shown in Table 4 was obtained. Experiment No. shown in Table 4 For the particle distribution of the fillers 1 to 4, a micro-track particle size distribution measuring device ("MT3300" manufactured by Nikkiso Co., Ltd.) by a laser diffraction scattering method is used, methanol is used as the dispersion medium, and the particle refractive index is the refractive index of collagen. 1.44 was used. FIG. 1 shows experiment No. 1 of this example. It is a graph which shows the particle distribution of the filler of 1-4.

(2) Preparation and coating of coating agent composition 20 parts by weight of the regenerated collagen powder obtained above and 100 parts by weight of “Nipporan 5199” (solid content 30 wt%) manufactured by Nippon Polyurethane as a polycarbonate-based polyurethane resin, as a solvent 20 parts by weight of N, N-dimethylformamide (DMF) was weighed and mixed to obtain a coating composition. This coating agent composition was coated on a polyethylene terephthalate (PET) film having a thickness of 50 μm using a film applicator, and then dried at 100 ° C. for 5 minutes. The film thickness after drying was 30 μm. Table 4 shows the evaluation results of the obtained coated sheet.

  From the results shown in Table 4, the average particle size of the regenerated collagen filler was 10 μm or less, and 95% by weight of the particles had a particle size of 50 μm or less. It was confirmed that 1-2 was preferable in the tactile sensation and the sensory test.

(Example 7)
Experiment No. 6 in Example 6 Weighed 1 to 2 fillers, 100 parts by weight of Nippon Polyurethane “Nipporan 5199” (solid content 30 wt%) as a polycarbonate-based polyurethane resin, and 20 parts by weight of N, N-dimethylformamide (DMF) as a solvent. And mixed to obtain a coating composition. This coating agent composition was coated on a soft polyvinyl chloride (PVC) sheet using a film applicator and then dried at 100 ° C. for 5 minutes. The film thickness after drying was 40 μm.

  The resulting coated sheet was examined for hygroscopicity and moisture release. The coated sheet is cut into a size of 5 cm in length and 7 cm in width, and is kept in a constant temperature and humidity chamber at a temperature of 30 ° C. and a temperature relative humidity of 30% for the first 4 days, and then at a temperature of 30 ° C. and a temperature relative humidity of 80%. Move to a constant temperature and humidity chamber, measure the mass after 1, 2 and 3 hours, then transfer to a constant temperature and humidity chamber with a temperature of 30 ° C. and a relative humidity of 30%, after 1, 2, 3 hours The mass was measured. The result is shown in FIG. From FIG. 2, it was confirmed that the coated sheet of this example had higher moisture absorption and desorption than the PVC sheet of the comparative example.

(Production Example 1) Method for Producing Regenerated Collagen Fiber After adding 30 g of hydrogen peroxide aqueous solution diluted to 30% by weight to 1200 kg (collagen content: 180 kg) of cow's floor skin as raw material, lactic acid aqueous solution To prepare a stock solution adjusted to pH 3.5 and a solid content of 7.5% by weight. The stock solution was stirred and defoamed with a stirring defoamer (Dalton Co., Ltd., 8DMV type) under reduced pressure, transferred to a piston-type spinning stock solution tank, and allowed to stand under reduced pressure for defoaming. The stock solution was extruded with a piston, then metered into a gear pump, filtered through a sintered filter with a pore size of 10 μm, passed through a spinning nozzle with a pore size of 0.275 mm, a hole length of 0.5 mm, and a number of holes of 300, and 20% by weight of sodium sulfate. Was discharged at a spinning speed of 5 m / min into a 25 ° C. coagulation bath (adjusted to pH 11 with boric acid and sodium hydroxide).

  Next, the obtained regenerated collagen fibers (300 fibers, 20 m) were added to 1.32 kg of an aqueous solution containing 1.7% by weight of epichlorohydrin, 0.0246% by weight of sodium hydroxide, and 17% by weight of sodium sulfate. After soaking at 25 ° C. for 4 hours, the temperature of the reaction solution was further raised to 43 ° C. and impregnated for 2 hours.

  After the reaction was completed, the reaction solution was removed, and then washed with water three times using 1.32 kg of 25 ° C. water in a fluid type apparatus. Thereafter, it was impregnated with 1.32 kg of an aqueous solution containing 5% by weight of aluminum sulfate, 0.9% by weight of trisodium citrate, and 1.2% by weight of sodium hydroxide at 30 ° C. After 5 hours and 4 hours, 13.2 g of a 5% by weight aqueous sodium hydroxide solution was added to the reaction solution and reacted for a total of 6 hours. After the reaction was completed, the reaction solution was removed, and then washed with water three times using 1.32 kg of 25 ° C. water in a fluid type apparatus.

Next, a part of the prepared fiber was immersed in a bath filled with an oil agent comprising an amino-modified silicone emulsion and a pluronic polyether-based antistatic agent to adhere the oil agent.
One end of the fiber bundle was fixed inside a hot air convection dryer set at 50 ° C., and a weight of 2.8 g was suspended from one fiber on the other end and dried under tension for 2 hours. Regenerated collagen fibers were obtained.

Production Example 2 Production Method of Regenerated Collagen Powder-A Regenerated collagen powder-A was prepared by physically pulverizing the regenerated collagen fiber shown in Production Example 1. That is, first, 30 kg of regenerated collagen fibers were shredded to a length of about 1 mm with a cutter mill SF-8 (manufactured by Riki Seisakusho Co., Ltd.) and recovered with a Cyclone CYC-600 model manufactured by the same company. Next, grinding was performed using a vibration mill FV-100 (manufactured by Chuo Kako Co., Ltd.). As the pulverization conditions, the same alumina balls (diameter 20 mm) were filled in an alumina container having a capacity of 283 L with a filling capacity of 80%, and the chopped collagen fibers were filled in 50 kg as the filling capacity, and pulverization was performed for 24 hours. As a result, a powder having an average particle diameter of 11.0 μm could be obtained by grinding for 24 hours. The powder having an average particle diameter of 11.0 μm was dry classified. Using a dry classifier micron separator MS-1H (manufactured by Hosokawa Micron Co., Ltd.) and a pulse jet type dust collector CP-16-6 (manufactured by Hosokawa Micron Co., Ltd.), the air volume is 12 m ³ / min (secondary air volume ³ m ³ / min), and the rotational speed. It was set to 5000 rpm. As a result, a powder having an average particle size of 5.0 μm (hereinafter referred to as regenerated collagen powder-A) was obtained. The particle size of the powder was measured by a wet laser diffraction / scattering method. Microtrac MT3300 (manufactured by Nikkiso Co., Ltd.) was used, and methanol was used as a dispersion medium.

Production Example 3 Production Method of Regenerated Collagen Powder-B Regenerated collagen powder-B was prepared by physically pulverizing the regenerated collagen fiber shown in Production Example 1. That is, first, 2 kg of regenerated collagen fibers were shredded to a length of about 1 mm with a cutter mill SF-8 (manufactured by Sanriki Co., Ltd.) and recovered with a Cyclone CYC-600 model manufactured by the same company. Next, it grind | pulverized using CF mill CF-630 (made by Ube Industries, Ltd.). As pulverization conditions, 40 kg of the same zirconia balls (diameter 6 mm) were placed in a zirconia container, the separator rotation speed was 1400 rpm, the mill rotation speed was 1000 rpm, and the supply rate was 1.8 kg / h. As a result, a powder having an average particle size of 13 μm (hereinafter referred to as regenerated collagen powder-B) was obtained. The regenerated collagen powder-B had a larger average particle size than the regenerated collagen powder-A, and as a result of observation with an electron microscope, the regenerated collagen powder-B was a powder having a strong needle shape.

(Example 8)
A coating composition having the following formulation was applied to the release paper with a uniform thickness using a film applicator (clearance: 200 μm). The film was dried at room temperature for 30 minutes and further dried at 100 ° C. for 10 minutes, and the release paper was peeled off to obtain a moisture-permeable film having a thickness of 29 μm.
Nipponran 5199 (polycarbonate polyurethane resin, solid content 30 wt%) 100 parts by weight (manufactured by Nippon Polyurethane Industry Co., Ltd.)
Regenerated collagen powder-A 5 parts by weight 2-butanone (methyl ethyl ketone) 25 parts by weight

Example 9
The following coating composition was subjected to the same operation as in Example 8 to obtain a moisture-permeable film having a thickness of 30 μm.
Nipponran 5199 (polycarbonate polyurethane resin, solid content 30 wt%) 100 parts by weight (manufactured by Nippon Polyurethane Industry Co., Ltd.)
Regenerated collagen powder-A 30 parts by weight 2-butanone (methyl ethyl ketone) 80 parts by weight

(Example 10)
The following coating composition was subjected to the same operation as in Example 8 to obtain a moisture-permeable film having a thickness of 32 μm.
Nipponran 5199 (polycarbonate polyurethane resin, solid content 30 wt%) 100 parts by weight (manufactured by Nippon Polyurethane Industry Co., Ltd.)
Regenerated collagen powder-A 60 parts by weight 2-butanone (methyl ethyl ketone) 150 parts by weight

(Example 11)
The following coating composition was subjected to the same operation as in Example 8 to obtain a moisture-permeable film having a thickness of 32 μm.
Nipponran 5199 (polycarbonate polyurethane resin, solid content 30 wt%) 100 parts by weight (manufactured by Nippon Polyurethane Industry Co., Ltd.)
Regenerated collagen powder-B 5 parts by weight 2-butanone (methyl ethyl ketone) 25 parts by weight

(Comparative Example 4)
The following coating composition containing no regenerated collagen powder was subjected to the same operation as in Example 8 to obtain a moisture-permeable film having a thickness of 32 μm.
Nipponran 5199 (polycarbonate polyurethane resin, solid content 30 wt%) 100 parts by weight (manufactured by Nippon Polyurethane Industry Co., Ltd.)
2-butanone (methyl ethyl ketone) 15 parts by weight

(1) Moisture permeability The moisture permeability was measured by JIS L 1099-1985 A-1 method (calcium chloride method).

(2) Communication structure The degree of communication of the film was measured and calculated by the following method. That is, first, the microtome cut surfaces of the films produced in Examples 8 to 11 and Comparative Example 4 were observed with a scanning electron microscope JSM-6060LA (manufactured by JEOL Ltd.), and 10 views of 2300 times magnification images were randomly selected. I got it. For each of these images, the ratio of the portion where the powder protruded in the length of the center of the surface portion on the upper surface side (cast upper surface side) of 100 microns was calculated. The average of the ratio of the powder protrusion calculated for each of these 10 fields of view was defined as the degree of communication shown in Table 5.

  In Examples 8 to 11, regenerated collagen powder was contained, and in the polyurethane resin which is a matrix resin, extremely good moisture permeability was exhibited due to the powder particles having a communication structure. Moreover, in Example 11, since the regenerated collagen powder-B having a strong needle shape and a large average particle diameter is used, it is higher than Example 1 using the regenerated collagen powder-A. The moisture permeability was shown. Since Comparative Example 4 is a film made of only a polyurethane resin containing no regenerated collagen powder, the moisture permeability was insufficient.

(Example 12) Ultraviolet light resistance test of regenerated collagen powder using a carbon arc lamp The collagen powder was placed in a tablet forming apparatus (iron cylinder of φ44 mm), and press-molded at 100 MPa for 1 minute. Further, as a surface treatment, sandpaper # A sample for irradiation was prepared by lightly polishing several times at 1200 times. The conditions for carbon arc lamp irradiation (FAL-SP type manufactured by Suga Test Instruments Co., Ltd.) were in accordance with JIS L0842. The black panel temperature was 63 ° C., the discharge voltage current was 125-145 V, 15-17 A, and the irradiation time was 20 hours. The surface measurement method was in accordance with powder colorimetry.

  As a result, as shown in Table 6, it was found that the regenerated collagen powder had ultraviolet light resistance.

Example 13 Discoloration Test by Heating Regenerated Collagen Powder 1 g of regenerated collagen powder was placed in an aluminum container and allowed to stand in a thermostatic device at 120 ° C., and the discoloration degree of the sample was observed with the naked eye over time. After standing at 120 ° C., the discoloration at each time point of 1 hour, 3 hours, 6 hours, and 24 hours was visually evaluated.
As a result, any time was not different from that before heating.

(Example 14) Dispersibility 1 g of regenerated collagen powder was added to 10 g of acetone or 10 g of water and stirred. In the evaluation of the dispersion state, it was determined that it was satisfactory when aggregated particles having a size that can be easily detected visually were not observed. When aggregated particles having a size that can be easily detected are observed, the dispersion state is considered to be poor.

  As a result, as a result of evaluating the dispersibility, the regenerated collagen powder had a good dispersibility in acetone and water. When it was left overnight and shaken again, the dispersibility was good as well.

(Example 15) About deodorizing property Regenerated collagen powder or silk powder and 3 L of nitrogen were put into a 5 L Tedlar bag and heat-sealed. For example, in the case of ammonia, various malodorous components were added so as to have an initial concentration of 30 ppm, and the malodorous component concentration remaining after 3 hours was measured using a gas detector tube (manufactured by Gastec Co., Ltd.). The sample charge (g) and the initial concentration (ppm) of malodorous substances were as shown in Table 7.

  As a result, as shown in Table 7, the ammonia concentration after 3 hours was 100%. The regenerated collagen powder was found to be excellent in deodorizing properties of ammonia, trimethylamine, acetic acid, isovaleric acid, and formaldehyde.

(Example 16)
Recycled collagen powder or silk powder and 3 L of nitrogen were placed in a 5 L Tedlar bag and heat sealed. For example, in the case of ammonia, various malodorous components were added so that the initial concentration was 30 ppm, and the concentration of the malodorous component remaining after 24 hours was measured using a gas detector tube (manufactured by Gastec Co., Ltd.). The sample charge (g) and the initial concentration (ppm) of malodorous substances were as shown in Table 8.

  As a result, as shown in Table 8, the regenerated collagen powder had excellent odor (not detected) concentrations of various malodorous components after 24 hours. Further, formaldehyde adsorptivity was as shown in FIG. Similarly, when added so as to be 20 ppm of trimethylamine, 12 ppm of acetic acid, and 13 ppm of isovaleric acid, the residual concentration of each malodorous component after 24 hours was ND (undetected). When acetaldehyde was added to 22 ppm, the residual acetaldehyde concentration after 24 hours was 17 ppm. When pyridine was added to 20 ppm, the residual pyridine concentration after 24 h was 9 ppm.

(Example 17)
A 5 L Tedlar bag was charged with 0.5 g of regenerated collagen powder or silk powder and 3 L of nitrogen and heat sealed. The initial concentration of ammonia was added to 30 ppm, and the malodorous component concentration remaining after 5 minutes, 10 minutes, 20 minutes, and 30 minutes was measured using a gas detector tube (manufactured by Gastec Co., Ltd.).

  As a result, as shown in FIG. 5, in the case of the regenerated collagen powder, it became ND (not detected) after 5 minutes, and an immediate effect was confirmed.

(Example 18)
A 5 L Tedlar bag was charged with 0.5 g of regenerated collagen powder or silk powder and 3 L of nitrogen and heat sealed. The initial ammonia concentration was added to 70 ppm, and the remaining ammonia concentration was measured after 2 hours using a gas detector tube (manufactured by Gastec Co., Ltd.) (first cycle). Once the inside of the Tedlar bag was emptied, 3 L of nitrogen and 70 ppm of ammonia were newly added, and the remaining ammonia concentration was measured after 2 hours (second cycle). The same operation was repeated.

As a result, as shown in FIG. 6, it was confirmed that the regenerated collagen powder hardly reduced the ammonia deodorization rate. In the table, the deodorization rate was defined by the following formula (3).
Formula (3)
Deodorization rate (%) = (1-N / Nb) × 100 (3)
N: Ammonia concentration after 2 hours, Nb: Initial concentration of ammonia (Example 19) Moisture absorption / release and tactile sensation

1. Preparation and Coating of Coating Agent Composition Using 2 g of the regenerated collagen powder obtained above and 10 g of “Nipporan 5199 (solid content 30 wt%) manufactured by Nippon Polyurethane Co., Ltd. as a polycarbonate polyurethane resin, and N, N-dimethylformamide as a solvent 6 g of (DMF) was weighed and mixed to obtain a coating composition, which was coated on a soft polyvinyl chloride (PVC) sheet using a film applicator and then at 100 ° C. The film was dried for 5 minutes, and the film thickness after drying was 30 μm.

In the evaluation method, 10 evaluators were allowed to touch the painted product by hand, and the evaluation of the touch at that time was expressed as an average score. The evaluation criteria for the feel was based on whether or not it approximates to synthetic leather.
5 points: Very good touch and close to synthetic leather.
4 points: Good touch and similar to synthetic leather.
3 points: Normal 2 points: Touch is not very good.
1 point: The touch feeling was bad. As a result, the touch feeling of the obtained coating sheet was as good as 4 points, and it was “smooth” and “feeling smooth”.

  As a place where the coating agent of the present invention is applied or a paint sheet is pasted, hospitals, nursing homes, nursing homes, schools, kindergartens, public halls, gymnasiums, stations, houses, apartment buildings, automobiles, vehicles, ships, airplanes, etc. It is suitable for interiors or interiors, baths, toilets, etc. In particular, it is suitable for parts that require antibacterial and antifungal properties such as walls, handrails, ceilings, and doors. Other examples include notebooks, writing utensils, bags, clothing, gloves, shoes, sports shoes, furniture such as sofas and chairs, synthetic leather used for automobile seats, artificial leather, surfaces such as PVC leather, or Car interior materials, home furnishings, electrical appliances, mobile phones, curtains, shower curtains, slippers, headphones, sports equipment, golf club grips, wheelchair grips, stair railings, desk mats, mouse pads, mice, etc. Can be mentioned.

1 shows the experiment No. 6 in Example 6. FIG. It is a graph which shows the particle distribution of the filler of 1-4. FIG. 2 is a graph showing the moisture absorption / release properties of the coated sheet of Example 7. FIG. 3 is a conceptual diagram of the moisture-permeable film of the present invention. FIG. 4 shows the results of an odor catching test. FIG. 5 shows the results of an ammonia deodorization immediate effect test. FIG. 6 shows the results of the cycle deodorization test.

Explanation of symbols

1 Regenerated collagen powder 2 Matrix resin

Claims (17)

  A moisture-permeable film comprising a matrix resin and a collagen powder comprising crosslinked regenerated collagen, wherein the degree of communication is 1 to 95%.   2. The moisture permeable film according to claim 1, wherein the crosslinked regenerated collagen is crosslinked with a treatment solution containing an organic compound and / or a metal salt. The organic compound is a monofunctional epoxy compound, and the following general formula (1):

(In the formula, R represents a substituent represented by R ₁ —, R ₂ —O—CH ₂ — or R ₂ —COO—CH ₂ —, and R ₁ represents a hydrocarbon group having 2 or more carbon atoms or CH. _{2. The} moisture-permeable film according to claim 1, wherein R ₂ is a compound represented by the following formula: R ₂ is a hydrocarbon group having 4 or more carbon atoms. The moisture-permeable film according to any one of claims 1 to 3, wherein the metal salt is basic aluminum chloride or basic aluminum sulfate represented by the following formula.
Al (OH) _n Cl _3-n or Al ₂ (OH) _2n (SO ₄ ) _3-n
(Where n is 0.5 to 2.5)   The moisture-permeable film according to claim 1, wherein the matrix resin is a polyurethane resin. A coating agent containing a matrix resin and a filler,
The filler includes an organic resin and an aluminum salt, and the aluminum salt is a powdered filler chemically bonded to the organic resin.   The coating agent according to claim 6, wherein the organic resin is at least one organic resin selected from regenerated collagen, polyvinyl alcohol, and carboxymethylcellulose.   The coating agent according to claim 6 or 7, wherein the organic resin is crosslinked with the aluminum salt. The coating agent according to claim 8, wherein the organic resin further includes a crosslinking component composed of an organic compound, and the crosslinking component is a monofunctional epoxy compound represented by the following general formula (1).

(In the formula, R represents a substituent represented by R ₁ —, R ₂ —O—CH ₂ — or R ₂ —COO—CH ₂ —, and R ₁ represents a hydrocarbon group having 2 or more carbon atoms or CH. ₂ Cl and R ₂ represents a hydrocarbon group having 4 or more carbon atoms.) The coating agent according to claim 6 or 8, wherein the aluminum salt is basic aluminum chloride or basic aluminum sulfate represented by the following formula.
Al (OH) _n Cl _3-n or Al ₂ (OH) _2n (SO ₄ ) _3-n
(Where n is 0.5 to 2.5)   The coating agent according to any one of claims 6 to 10, wherein an average particle size of the organic resin powder is 0.01 to 80 µm.   The said organic resin powder is a coating agent in any one of Claims 6-11 which has phosphorus adsorption capacity.   The coating agent according to any one of claims 6 to 12, wherein the matrix resin is a polyurethane-based resin.   The coating agent according to any one of claims 6 to 13, wherein 0.1 to 70% by weight of the regenerated collagen powder is added to the coating agent.   The average particle diameter of the said filler is 10 micrometers or less, and 95 weight% of particle | grains are particle diameters of 50 micrometers or less, The coating agent in any one of Claims 6-14. A coating film filler,
The filler includes an organic resin and an aluminum salt, and the aluminum salt is a powdered filler that is chemically bonded to the organic resin,
An average particle size of the filler is 10 μm or less, and 95% by weight of the particles have a particle size of 50 μm or less.   A coated sheet obtained by coating the base fabric sheet with the coating agent according to claim 6.

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