JP2011026358A - Moisture permeable film - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a moisture permeable film extremely excellent in moisture permeability. <P>SOLUTION: The moisture permeable film includes a matrix resin and a collagen powder comprising a crosslinked regenerated collagen, and is characterized in that the communication degree by the collagen powder is 1-95%. In the moisture permeable film, the collagen powder comprising the crosslinked regenerated collagen is dispersed into the matrix resin to constitute the film. The collagen powders are contacted with each other, and the collagen powder is communicated from one surface of the film to the other surface. Thus, the extremely excellent moisture permeability is exhibited. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a moisture permeable film containing regenerated collagen powder.

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.
JP-A-11-269773 JP 7-3148 A JP-A-4-82974

  That is, the problem to be solved by the present invention is to provide a moisture permeable film excellent in moisture permeability.

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、Ｒ_１−、Ｒ₂−Ｏ−ＣＨ₂−またはＲ₂−ＣＯＯ−ＣＨ₂−で表される置換基を示し、Ｒ_１は炭素数２以上の炭化水素基またはＣＨ_２Ｃｌであり、Ｒ_２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。

(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.)
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 moisture permeable film of the present invention is excellent in moisture permeability.

  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, lactic acid or the like 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 the hydrolysis under alkaline conditions in order 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 conditions. 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, 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 is the same as described above.

このようにして得られた再生コラーゲンは、水又は無機塩の水溶液で膨潤した状態になっている。この膨潤は再生コラーゲンの重量に対して４〜１５倍の水又は無機塩の水溶液を含有した状態が良い。水又は無機塩の水溶液の含有量が４倍未満では再生コラーゲン中のアルミニウム塩含有量が少なく、耐水性が不充分であり、また１５倍を越える場合には強度が弱くなって取扱いが困難である。

The regenerated collagen thus obtained is swollen with water or an aqueous solution of an inorganic salt. This swelling is preferably in a state containing water or an aqueous solution of an inorganic salt 4 to 15 times the weight of regenerated collagen. If the content of the aqueous solution of water or inorganic salt is less than 4 times, the content of aluminum salt in the regenerated collagen is small and the water resistance is insufficient, and if it exceeds 15 times, the strength becomes weak and handling is difficult. is there.

The swollen regenerated collagen is then immersed in an aqueous solution of an aluminum salt. As the aluminum salt aqueous aluminum salt solution, the following _{formula, Al (OH) n Cl 3} -n, or _{Al 2 (OH) 2n (SO} 4) in _3-n (wherein, n is 0.5 to 2. 5). Basic aluminum chloride or basic aluminum sulfate represented by formula (5) is preferred. 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. If the concentration of the aluminum salt is less than 0.3% by weight, the content of the aluminum salt in the regenerated collagen fiber is small and the water resistance is insufficient, and if it exceeds 5% by weight, it becomes hard after the treatment. It will be damaged.

  The pH of the aqueous aluminum salt 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 the pH is less than 2.5, the collagen structure tends to be destroyed and denatured. If the pH is more than 5, precipitation of aluminum salt occurs, making it difficult to penetrate. 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 pH 1, but 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. When the liquid temperature exceeds 50 ° C., the regenerated collagen tends to be denatured.

  The time for immersing the regenerated collagen in this aluminum salt aqueous solution is 3 hours or more, preferably 6 to 25 hours. If the immersion time is less than 3 hours, the reaction of the aluminum salt is difficult to proceed, and the water resistance of the regenerated collagen becomes insufficient. Moreover, although there is no restriction | limiting in particular in the upper limit of immersion time, the reaction of aluminum salt will fully advance within 25 hours, and water resistance will also become favorable. In addition, an inorganic salt such as sodium chloride, sodium sulfate, or potassium chloride 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 obtained in this way has almost no coloration treated with a conventional chromium salt and is excellent in water resistance, so it is clear that the advantages of the present invention are great. In order to prevent collagen denaturation (gelatinization), attention should be paid to the temperature history during processing. In order to prevent denaturation even after crosslinking, it is essential to maintain the moisture and temperature control during production, powdering and product storage at or 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. In such a collagen fiber manufacturing process, a film can be manufactured by the same method using a slit nozzle, and this can be pulverized.

  In the present invention, the regenerated collagen obtained by the above method can be made into a collagen powder (regenerated collagen powder) composed of regenerated collagen crosslinked by pulverization. However, when the regenerated collagen is a fiber or film, Can be made into a regenerated collagen powder by cutting to a fiber length or size suitable for pulverization, further pulverizing the cut, or directly pulverizing the fiber or film. The cutter that can be used in the production of the regenerated collagen powder in the present invention is not particularly limited, but is cut to about 0.1 mm to several mm with a rotary blade cutter, belt cutter, shearing machine, cutter mill, etc., which are usually used for cutting fibers. To do. 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 from the viewpoint of grinding efficiency, but it is also possible to use a ball of another material such as an alumina ball. it can.

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 80 μm or more, the surface texture after forming the film becomes rough, which is not preferable. If it is 0.01 μm or less, the dispersibility in an organic solvent or polyurethane paint is poor, which is not preferable. The average particle diameter can be determined by, for example, a microtrack method, which is one of laser diffraction methods.
As the matrix resin, polyurethane resin, polyvinyl chloride resin, polyolefin resin, olefin thermoplastic elastomer (TPO), styrene thermoplastic elastomer (TPS), synthetic rubber, or the like can be used. 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 a woven fabric, a knitted fabric, or a nonwoven fabric made of a mixed fiber thereof may be used, and a raising treatment may be performed as necessary.

  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.

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.
(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 1
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 2)
The following coating composition was subjected to the same operation as in Example 1 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 3)
The following coating composition was subjected to the same operation as in Example 1 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 4)
The following coating composition was subjected to the same operation as in Example 1 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 1)
The following coating composition containing no regenerated collagen powder was subjected to the same operation as in Example 1 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) Water vapor transmission rate The water vapor transmission rate was measured by the 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 prepared in Examples 1 to 4 and Comparative Example 1 were observed with a scanning electron microscope JSM-6060LA (manufactured by JEOL Ltd.), and 10 images were randomly obtained at a magnification of 2300 times. 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 1.

実施例１〜４では、再生コラーゲン粉末を含有し、マトリックス樹脂であるポリウレタン樹脂中で、粉末の粒子同士が連通構造をとることに起因して、極めて良好な透湿性を示した。また、実施例４では、針状形状の強い粒子形状で、平均粒径の大きな再生コラーゲン粉末−Ｂを使用しているため、再生コラーゲン粉末−Ａを使用している実施例１よりも、高い透湿度を示した。比較例１は、再生コラーゲン粉末を含有しないポリウレタン樹脂のみのフィルムであるため、透湿性が不十分であった。

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

Conceptual diagram of moisture-permeable film of the present invention

Explanation of symbols

1 Regenerated collagen powder 2 Matrix resin

Claims (5)

  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 _{3. The} moisture-permeable film according to claim 1, wherein R ₂ is a compound represented by: 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.

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