JP4999367B2 - Waterproof sheet and manufacturing method thereof - Google Patents

Description

The present invention relates to a waterproof fabric that is durable against an organic solvent and a method for producing the waterproof fabric.

Waterproof fabrics are used in a variety of materials to prevent rain and water from entering, such as goose, windbreaker, jacquard, tent, gloves, and waterproof boots for fishing. As such a waterproof cloth, for example, a coated cloth (Patent Document 1) or a fiber cloth having a microporous film obtained by coating a resin solution of a polyurethane polymer on one surface of a fiber cloth and wet coagulating it. A moisture-permeable waterproof fabric (Patent Document 2) obtained by bonding a non-porous film of urethane resin on one side is known.
Japanese Patent Laid-Open No. 55-80583 JP-A-7-9631

In recent years, outdoor activities such as fishing and camping have flourished, and insect repellents for repelling and repelling insects that are harmful to human bodies such as mosquitoes, gnats, fleas, and ticks are sometimes used. This insect repellent generally contains N, N′-diethyl-m-toluamide (DEET) or the like as a main component, and this DEET includes N, N′-dimethylformamide (DMF) and The chemical structure is similar. Dimethylformamide is generally used as a solvent for polyurethane resins and has the ability to dissolve the polyurethane resin film. DEET, which has a similar chemical structure, also has the ability to dissolve the polyurethane resin film. When it comes into contact with a conventional moisture-permeable waterproof sheet, the polyurethane resin surface layer dissolves and breaks down, making it waterproof. Will drop significantly. Furthermore, even when contacted and used with lower alcohols contained in cosmetics and the like, the surface layer of the polyurethane resin was often destroyed.

In recent years, lighter clothing and the like have been demanded, and waterproof clothing and the like not using a lining have been increasing. Therefore, the chance that DEET and cosmetics come into direct contact with the urethane resin film increases, and there is a greater concern about the deterioration of waterproofness due to destruction of the polyurethane resin. This invention is made | formed in view of the said situation, Comprising: It aims at providing the waterproof sheet which has durability with respect to chemicals, such as an organic solvent contained in an insect repellent or cosmetics, and its manufacturing method. . Furthermore, it is preferable to provide a waterproof sheet that also has moisture permeability, is excellent in both moisture permeability and waterproof property, and has durability against chemicals such as organic solvents contained in insect repellents and cosmetics, and a method for producing the same. It is an object.

As a result of intensive studies, the present inventors have found that the problem is solved, and have completed the present invention. In order to achieve the above object, the present invention employs the following configuration. (1) A waterproof sheet in which a microporous polyurethane resin film is located at or near the outermost layer, and the water resistance of JIS L1092 after treatment with an organic solvent is 19.6 KPa or more. (2) The waterproof sheet according to (1), wherein the organic solvent contains at least one selected from N, N′-diethyl-m-toluamide and amide solvents. (3) The waterproof sheet according to (1) or (2) above, wherein the urethane resin film is made of a polyurethane resin composition containing a two-component polyurethane resin (A).

(4) The waterproof sheet according to (3), wherein the polyurethane resin composition also contains an organic polyisocyanate (B) having a polyisocyanate (B0) having 3 or more functional groups. (5) The two-component polyurethane resin (A) is a polyurethane resin comprising an oxyethylene group-containing polymer diol (d), an organic diisocyanate (e), and a chain extender (f), and the hydrophilic property The waterproof sheet according to (3) or (4), wherein the oxyethylene group content is 10 to 80% by mass relative to the polyurethane resin (A). (6) The organic polyisocyanate (B) is at least one selected from the group consisting of an aliphatic polyisocyanate having an average functional group number of 2.3 to 5 and an alicyclic polyisocyanate (4) or ( The waterproof sheet according to 5).

(7) The waterproof sheet according to any one of (3) to (6), wherein the polyurethane resin composition also includes a polyurethane resin for wet coagulation. (8) The water pressure resistance is 19.6 to 196 KPa, the moisture permeability in the calcium chloride method is 6000 to 15000 g / m ² · 24 hrs, and the moisture permeability in the potassium acetate method is 8000 to 30000 g / m ² · 24 hrs. The waterproof sheet according to any one of (1) to (7), wherein (9) The waterproof sheet according to any one of (1) to (8), which also includes a fiber fabric.

(10) An organic solvent solution of a polyurethane resin composition containing a two-component polyurethane resin (A) and an organic polyisocyanate (B) having a polyisocyanate (B0) having 3 or more functional groups is applied to at least one surface of the fiber fabric. And wet coagulating to form a microporous polyurethane resin film.

INDUSTRIAL APPLICABILITY According to the present invention, there are provided a waterproof sheet excellent in waterproofness and having durability against chemicals such as organic solvents contained in insect repellents and cosmetics, and a method for producing the same. Accordingly, even when DEET or cosmetics adheres to general clothing, sports clothing, cold clothing, military clothing, tents, gloves, shoes, etc. obtained using the waterproof sheet of the present invention, a waterproof product having waterproofness is obtained. Can be provided. It can also be used for special work clothes such as chemical special protective clothes. Furthermore, in a preferred embodiment of the present invention, a waterproof product having moisture permeability and having waterproof properties excellent in durability while suppressing stuffiness can be provided.

<Structure of Waterproof Fabric> The waterproof sheet of the present invention has a water resistance of JIS L1092 of 19.6 KPa or more after the microporous urethane resin film is positioned at or near the outermost layer and treated with an organic solvent. It is what is. In addition, the waterproof sheet of the present invention may be a laminate of a microporous urethane resin film on at least one side of another sheet-like material, and other sheet-like materials may be nonporous and porous. A urethane resin sheet, a polytetrafluoroethylene sheet, a fiber fabric, or a combination thereof may be used. From the viewpoint of the strength, texture, and designability of the resulting waterproof sheet, it is preferable to include a fiber fabric. The fiber fabric may be a synthetic fiber such as polyester, nylon or acrylic, a regenerated fiber such as rayon, a semi-synthetic fiber such as acetate, a natural fiber such as cotton, silk or wool, or a composite of these. Moreover, these forms can use arbitrary things, such as a woven fabric, a knitted fabric, and a nonwoven fabric. Further, these fiber fabrics may be subjected to processing such as dyeing and printing, water repellent processing, antibacterial and deodorizing processing, antibacterial processing, antistatic processing, and raising.

<Microporous urethane resin film> The microporous urethane resin film of the present invention refers to one having a large number of pores inside the urethane resin film. In particular, from the viewpoint of moisture permeability, those having connected pores are preferable, and a microporous urethane resin film having connected pores obtained by wet coagulation is particularly preferable. The thickness of the microporous polyurethane resin film may be set to an arbitrary thickness depending on the use for which the waterproof sheet is used, but is preferably 10 to 500 μm. If the thickness is less than 10 μm, sufficient waterproofness may not be obtained, and if it exceeds 500 μm, the texture may be cured. Further, from the viewpoint of moisture permeability, the thickness is preferably 500 μm or less.

The microporous urethane resin film is located in the outermost layer of the waterproof sheet of the present invention or in the vicinity thereof. The outermost layer refers to the outermost layer of the waterproof sheet. When the waterproof sheet is sewn on clothes, it is not limited to the one used directly on the surface where rain hits, but the outermost sheet as a waterproof sheet including the case where a microporous urethane resin film is used on the body side The one located in. In addition, as the outermost layer, a resin film for imparting design properties, slipping and touching, increasing the film strength, providing functions such as antibacterial properties, etc. is partially applied on the microporous urethane resin film. Even if it is a thing, the thing in which at least one part of a microporous urethane resin film is located in the outermost layer is said to be located in the vicinity. Further, it is assumed that a state covered with a film made of a water repellent agent used for finishing or the like, a film made of a softening agent, an antistatic agent or the like on a microporous urethane resin film is also located in the vicinity.

Further, the treatment with an organic solvent means that an organic solvent containing at least one selected from DEET and an amide solvent (DMF, dimethylacetamide, etc.) is applied to absorbent cotton, and the resin film surface of the sheet is formed. Lightly rub once and repeat the process of drying for 2 minutes 20 times. More specifically, a commercially available insect repellent containing DEET (trade name: Cutter OUTDOORSMAN, composition: DEET 21.85%, DEET isomer 1.15%, other components 77.0%) Applying to absorbent cotton, rubbing the surface of the resulting waterproof sheet once and drying for 2 minutes 20 times, and using the 50% DMF / 50% ethanol solution instead of the insect repellent Refers to processing.

In addition, the water resistance of JIS L1092 after treatment with an organic solvent is 19.6 KPa or more means that the water resistance is measured according to JIS L1092-1998 (hydrostatic pressure method) B method (high water pressure method). 19.6 KPa or more. More preferably it is 48 KPa or more. When water resistance is measured, the test piece is stretched by applying water pressure. Nylon taffeta (the total density of warp and weft yarns per 2.54 cm is about 210) is superimposed on the test piece. Attach to the test machine and measure. Moreover, the waterproof sheet of this invention is a thing before processing using an organic solvent, and it is preferable in water resistance being 48 KPa or more. In addition, the waterproof sheet of the present invention preferably has moisture permeability, and is before being treated with an organic solvent. The moisture permeability is 6000 g / m ² · 24 hrs as measured by the calcium chloride method. The moisture permeability in the potassium acetate method is preferably 8000 g / m ² · 24 hrs.

More preferably, the water resistance is 19.6 to 196 KPa, the moisture permeability in the calcium chloride method is 6000 to 15000 g / m ² · 24 hrs, and the moisture permeability in the potassium acetate method is 8000 to 30000 g / m ² · It is preferably 24 hrs. The moisture permeability was measured according to JIS L1099-1993 calcium chloride method A-1 method and potassium acetate method B-1 method. Both the calcium chloride method and the potassium acetate method were converted to moisture permeability per 24 hours.

Those having moisture permeability and waterproof properties can provide an excellent waterproof sheet that suppresses stuffiness and prevents water leakage while maintaining a balance between moisture permeability and waterproof properties.

<Two-pack type polyurethane resin (A)> The microporous polyurethane resin film of the present invention may comprise a polyurethane resin composition containing the two-pack type polyurethane (A). The two-component polyurethane resin is a polyurethane resin that can form a film by reacting a urethane resin with an isocyanate group, and is generally used to form an adhesive or nonporous urethane resin film. It is what is done. The two-component polyurethane resin (A) of the present invention is preferably a hydrophilic two-component polyurethane resin from the viewpoint of moisture permeability.

<Polyurethane resin composition> Here, the polyurethane resin composition preferably contains a two-component polyurethane resin (A) and an organic polyisocyanate (B) having a polyisocyanate (B0) having 3 or more functional groups. The two-component polyurethane resin (A) in the present invention is a polyurethane resin comprising a polymer diol, an organic diisocyanate (e), and a chain extender (f). As the polymer diol, an oxyethylene group-containing polymer diol (d) is particularly preferable. Examples of the oxyethylene group-containing polymer diol (d) include polyoxyethylene glycol (hereinafter abbreviated as PEG), polyoxyethyleneoxypropylene block copolymer diol, polyoxyethyleneoxytetramethylene block copolymer diol, ethylene oxide and propylene oxide. Random copolymerization diol, ethylene oxide and tetrahydrofuran random copolymer diol; ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexamethylene glycol, bis (hydroxymethyl) cyclohexane, 4,4'- Ethylene oxide adduct of low molecular weight glycol such as bis (2-hydroxyethoxy) -diphenylpropane; PEG having a molecular weight of 1000 or less and dicarboxylic acid (for example, succinic acid, adipic acid Acid, sebacic acid, terephthalic acid, condensed polyetherester diols obtained by reacting the isophthalic acid) and mixtures of two or more thereof. Among these, PEG, polyoxyethyleneoxypropylene block copolymer diol, and polyoxyethyleneoxytetramethylene block copolymer diol are preferable, and PEG is particularly preferable.

The oxyethylene group content in the oxyethylene group-containing polymer diol (d) is preferably at least 40% by mass and more preferably at least 50% by mass from the viewpoint of moisture permeability. The molecular weight of (d) is preferably 700 to 20,000, more preferably 1,000 to 15,000. In addition, other polymer diol (d1) can be used in combination with the diol as long as the moisture permeability is not inhibited. (D1) is 0-60 mass% normally based on the mass of said (d), Preferably 10-50 mass% can be used together.

Examples of the other polymer diol (d1) include polyether diol (A), polyester diol (B), polycarbonate diol (C), and mixtures thereof. The molecular weight is usually 600 to 5,000. Polyether diol (I) does not contain an oxyethylene group, for example, polyoxypropylene glycol, polyoxytetramethylene glycol (hereinafter abbreviated as PTMG), polyoxypropyleneoxytetramethylene block copolymer diol, and two of these The above mixture etc. are mentioned. Examples of the polyester diol (b) include a low-molecular diol and / or a condensed polyester diol obtained by reacting a polyether diol having a molecular weight of 1000 or less and a dicarboxylic acid, and a polylactone diol obtained by ring-opening polymerization of a lactone. It is done.

Examples of the low molecular diol include the low molecular glycol described in the section of the oxyethylene group-containing polymer diol. Examples of the polyether diol having a molecular weight of 1000 or less include polypropylene glycol and PTMG. Examples of the dicarboxylic acid include aliphatic dicarboxylic acids (for example, succinic acid, adipic acid, and sebacic acid), aromatic dicarboxylic acids (terephthalic acid, isophthalic acid, and the like), and mixtures of two or more of these.

Examples of lactones include ε-caprolactone. Specific examples of the polyester diol (b) include polyethylene adipate, polybutylene adipate, poly 2,2-dimethyltrimethylene adipate, poly 3-methylpentamethylene adipate, polyhexamethylene adipate, polycaprolactone diol, and two or more thereof. And the like. Examples of the polycarbonate diol (c) include polyhexamethylene carbonate diol.

Examples of the organic diisocyanate (e) used in the two-component polyurethane resin of the present invention include (1) 6 to 12 carbon atoms [excluding carbon in the NCO group, hereinafter the same applies to (2) to (4)]. (2) alicyclic diisocyanate having 6 to 15 carbon atoms, (3) araliphatic diisocyanate having 8 to 12 carbon atoms, (4) aromatic diisocyanate having 6 to 30 carbon atoms, and two of these The above mixture etc. are mentioned. Specific examples of the aliphatic diisocyanate (1) include hexamethylene diisocyanate (HDI), dodecamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 1,3,6-trimethylhexamethylene diisocyanate and the like. It is done.

Specific examples of the alicyclic diisocyanate (2) include isophorone diisocyanate (IPDI), dicyclohexylmethane-4,4′-diisocyanate (hydrogenated MDI), 1,4-cyclohexane diisocyanate, methylcyclohexane-2,4-diisocyanate ( And hydrogenated TDI) and 1,4-bis (2-isocyanatoethyl) cyclohexane. Specific examples of the araliphatic diisocyanate (3) include p- or m-xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like. Specific examples of the aromatic diisocyanate (4) include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (TDI), 2,4′- or 4,4 ′. -Diphenylmethane diisocyanate (MDI), naphthalene-1,5-diisocyanate, 3,3'-dimethyldiphenylmethane-4,4'-diisocyanate and the like. Of these, preferred are aromatic diisocyanates, and particularly preferred is MDI.

Examples of the chain extender (f) include low molecular diols [ethylene glycol (hereinafter abbreviated as EG), propylene glycol, 1,4-butanediol (hereinafter abbreviated as BG)], aliphatic diamines (ethylene diamine, etc.), Alicyclic diamines (isophorone diamine, 4,4′-diaminodicyclohexylmethane, etc.), aromatic diamines (4,4′-diaminodiphenylmethane, etc.), alkanolamines (ethanolamine, etc.), hydrazine and mixtures of two or more thereof The low molecular diol is preferable.

The oxyethylene group content of the two-component polyurethane resin (A) is preferably 10% by mass or more, more preferably 20% by mass or more, more preferably 25% by mass or more from the viewpoint of moisture permeability with respect to (A). is there. Moreover, from a viewpoint of the intensity | strength of a film | membrane, Preferably it is 80 mass% or less, More preferably, it is 70 mass% or less, More preferably, it is 65 mass% or less.

In the two-component polyurethane resin (A), the ratio (NCO: OH + NH equivalent ratio) of the organic diisocyanate, the polymer diol and the chain extender is usually (0.95 to 1.05): 1, preferably substantially. 1: 1. When (NCO / OH + NH equivalent ratio) is in the above range, the polyurethane resin has a high molecular weight, and a polyurethane resin having practically useful physical properties can be produced. The molecular weight of the hydrophilic polyurethane resin (d) is a number average molecular weight, preferably 5,000 to 300,000, more preferably 8,000 to 200,000.

The two-component polyurethane resin (A) reacts with the organic polyisocyanate (B) to become a polyurethane resin having durability against chemicals such as an insect repellent such as DEET and an organic solvent contained in cosmetics. It is preferable to have OH as a terminal group. The terminal group concentration is preferably 0.5 to 25, more preferably 1 to 20, and more preferably 1.5 to 15 as the solid content of (A).

Suitable organic solvents for the production of the two-component polyurethane resin (A) in the presence of a solvent include, for example, amide solvents (DMF, dimethylacetamide, etc.), sulfoxide solvents (dimethyl sulfoxide, etc.), and ketones. Solvents (such as methyl ethyl ketone (MEK)), aromatic solvents (such as toluene and xylene), ether solvents (such as dioxane and tetrahydrofuran), ester solvents (such as ethyl acetate and butyl acetate), and mixtures of two or more of these Is mentioned. Of these, amide solvents, ketone solvents, aromatic solvents, and mixtures of two or more thereof are preferred. The amount of the organic solvent is such that the resin solid content concentration of the polyurethane resin is usually 5 to 50% by mass, preferably 10 to 40% by mass.

In the production of the two-component polyurethane resin (A), the reaction temperature may be the same as that usually employed in the polyurethane reaction, and is usually 20 to 100 ° C. when a solvent is used, and usually 20 to 20 when no solvent is used. 220 ° C. In order to accelerate the reaction, a catalyst usually used in a polyurethane reaction [for example, an amine-based catalyst (such as triethylamine or triethylenediamine) or a tin-based catalyst (such as dibutyltin dilaurate)) can be used as necessary. If necessary, a polymerization terminator [for example, monohydric alcohol (ethanol, butanol, etc.), monovalent amine (diethylamine, dibutylamine, etc.), low molecular diol (EG, BG, etc.), alkanolamine (monoethanolamine, diethanolamine, etc.) ) Etc.] can also be used.

The production of the two-component polyurethane resin (A) can be usually performed by a production apparatus employed in the industry. Moreover, when not using a solvent, manufacturing apparatuses, such as a kneader and an extruder, can be used. As the polyurethane resin thus produced, the solution viscosity measured as a 30% by mass (solid content) DMF solution is usually 1-1000 Pa · s / 20 ° C., and practically preferred is 5-200 Pa · s /. 20 ° C.

<Organic polyisocyanate (B)> The organic polyisocyanate (B) in the present invention contains a polyisocyanate (B0) having 3 or more functional groups. As other things, organic diisocyanate (e) may be contained. When (B) contains only the organic diisocyanate (e) having 2 functional groups, the durability against DEET or the like is insufficient. The average functional group number of the organic polyisocyanate (B) is preferably 2.3 to 5, more preferably 2.5 to 5, from the viewpoint of durability against DEET or the like.

Examples of the polyisocyanate (B0) having 3 or more functional groups include, for example, a urethane-modified product obtained by reacting the organic diisocyanate (e) (3 mol) with trimethylolpropane (TMP) (1 mol) (for example, HDI or IPDI or Modified products obtained by reacting TDI and TMP, etc.) (e) Burette modified products obtained by reacting (3 mol) and water (1 mol) (for example, modified products obtained by reacting HDI or IPDI with water) , (E) isocyanurate-modified products (for example, HDI, IPDI, or TDI trimer), dimers of the modified products (for example, the urethane-modified product, the burette-modified product, or the isocyanurate-modified product (2 Mole) and water or EG (1 mole), etc., etc.), trimers of the modified body (for example, the urethane modified body or Biuret modified products or isocyanurate modified product (3 moles) with water or EG (2 moles) and modified products obtained by reacting, etc.), and the like mixtures of two or more thereof. Among these, preferred are aliphatic polyisocyanate, which is the modified product using aliphatic diisocyanate, and alicyclic polyisocyanate, which is the modified product using alicyclic diisocyanate, and a mixture of two or more thereof. More preferably, an isocyanurate-modified aliphatic polyisocyanate, an isocyanurate-modified alicyclic polyisocyanurate and a mixture of two or more thereof, particularly preferably an HDI isocyanurate-modified product, IPDI Examples include isocyanurate-modified products and mixtures thereof. The mass ratio (B0) :( e) of the polyisocyanate (B0) having 3 or more functional groups and the organic diisocyanate (e) is preferably 50:50 to 100: 0, more preferably 60:40 to 100: 0. .

In the present invention, the use ratio of the two-component polyurethane resin (A) and the organic polyisocyanate (B) is preferably 3 to 100 with respect to 100 parts by mass of the two-component polyurethane resin (as a solid content). It is 10 mass parts, More preferably, it is 10-90 mass parts, More preferably, it is 15-85 mass parts. If it is less than 3 masses, durability, such as DEET, may be insufficient, and if it exceeds 100 mass parts, the texture may be cured.

<Polyurethane resin for wet coagulation> The polyurethane resin for wet coagulation is a solution in which an organic solvent solution of a urethane resin composition dissolved in a polar organic solvent such as DMF is immersed in water or water containing DMF. It refers to a polyurethane resin that can be extracted to form a microporous membrane, and is not particularly limited to an ether type, an ester type, an ether / ester type, or the like. In general, a one-component urethane resin is used. Moreover, it is preferable that the mixing ratio (mass ratio) of the polyurethane resin for wet coagulation in the polyurethane resin composition and the two-component polyurethane resin (A) is 1: 9 to 9: 1.

[Other Additives] As other additives, a water repellent may be added. By adding a water repellent, moisture permeability by the potassium acetate method can be remarkably improved. In general, when a water repellent is added to a microporous urethane resin film, the hydrophobicity of the urethane resin film is improved and the waterproof property is improved. The moisture permeability by the potassium acetate method is considered to decrease, but when the two-component polyurethane resin of the present invention and a water repellent are used in combination, the moisture permeability by the potassium acetate method is remarkably improved. As the water repellent, a known water repellent such as fluorine or silicon can be used.

In addition, in the polyurethane resin composition of the present invention, fine particles having a particle size of several nanometers to several micrometers such as silicon oxide, magnesium oxide, aluminum oxide and calcium carbonate are added or necessary for improving moisture permeability and waterproofness. To contain various stabilizers, colorants, inorganic fillers, organic modifiers, penetration improvers for the purpose of improving adhesive strength, and other additives for improving weather resistance, heat deterioration, etc. Can do. Even when these various fillers and crosslinking agents are added, the thickness of the polyurethane resin film can be freely controlled. Further, the mixing method of the polyurethane resin, polyisocyanate, and other additives of the present invention may be only ordinary stirring and mixing, or may be mixed using a mixing device (ball mill, kneader, sand blaster, roll mill, etc.). it can.

<Method for Producing Waterproof Sheet> Next, a preferred method for producing the waterproof sheet of the present invention will be described. The waterproof sheet of the present invention is an organic urethane resin composition comprising a two-component polyurethane resin (A) and an organic polyisocyanate (B) having a polyisocyanate (B0) having 3 or more functional groups on at least one surface of a fiber fabric. A solvent solution is applied and wet coagulated to form a microporous polyurethane resin film. Furthermore, when the polyurethane resin for wet coagulation is contained in the organic solvent solution of the urethane resin composition, it is preferable from the viewpoint of microporous formation, moisture permeability by the calcium chloride method, and water swelling resistance of the resulting urethane resin film. In addition, from the viewpoint of moisture permeability by the potassium acetate method, a water repellent may be included in the urethane resin composition. Organic solvents used at this time include amide solvents (DMF, dimethylacetamide, etc.), sulfoxide solvents (dimethyl sulfoxide, etc.), ketone solvents (methyl ethyl ketone (MEK), etc.), aromatic solvents (toluene, xylene, etc.) , Ether solvents (dioxane, tetrahydrofuranone, etc.), ester solvents (ethyl acetate, butyl acetate, etc.) and mixtures of two or more thereof. From the viewpoint of forming a microporous polyurethane resin film, DMF and dimethylacetamide are preferable.

The amount of the organic solvent is such that the solid content in the organic solvent solution of the urethane resin composition is 1 to 50% by mass, preferably 5 to 40% by mass. Moreover, about a fiber cloth, in order to prevent the impregnation of the excessive urethane resin composition to a fiber cloth, you may perform a calendar process and a water-repellent process. As a method for applying the organic solvent solution of the urethane resin composition to one side of the fiber fabric, a knife coater, a pipe coater, a comma coater or the like may be used. After the application, it is immersed in a coagulation bath of an aqueous solution containing DMF or the like used in an organic solvent solution of water or a urethane resin composition, and wet coagulated to form a microporous polyurethane resin film. The solidification temperature is preferably in the range of 10 to 50 ° C. from the viewpoint of appropriately adjusting the pores formed in the urethane resin film.

Next, the solvent is removed. Water is preferably used for the solvent removal, and the temperature of the solvent removal is preferably selected in the range of 10 ° C to 80 ° C. The desolvated tarpaulin is then dried. The drying temperature is preferably selected in the range of 90 to 150 ° C. In addition, it is good to heat-process at 90-150 degreeC further from a viewpoint of bridge | crosslinking of organic polyisocyanate (B). In addition, after drying, if necessary, a resin film for partially imparting designability, slipperiness, abrasion resistance, antibacterial properties, and heat retention properties using a gravure coater on a microporous polyurethane resin film Or may be subjected to water repellent treatment.

The waterproof sheet obtained by the above manufacturing method has excellent waterproofness, can provide a comfortable work (exercise) environment, and even when contacted and used with insect repellents, there is little decrease in performance. It can be suitably used for outdoor and military clothes, kappa, jackets, shoes and the like. In addition, since organic solvents such as DEET, DMF, and ethanol have durability against contact and use, a comfortable working environment and equipment can be provided if used for special work clothes.

Next, examples according to the present invention will be described. However, the present invention is not limited to these examples. (Evaluation items and evaluation method) Various performances of the obtained waterproof sheet were measured by the following methods. [Moisture permeability] The moisture permeability is measured according to JIS L1099-1993 calcium chloride method A-1 method and potassium acetate method B-1 method. Both the calcium chloride method and the potassium acetate method were converted to moisture permeability per 24 hours. [Water resistance] The water resistance was measured according to JIS L1092-1998 (hydrostatic pressure method) B method (high water pressure method). When water resistance is measured, the test piece is stretched by applying water pressure. Nylon taffeta (the total density of warp and weft yarns per 2.54 cm is about 210) is superimposed on the test piece. Attach to the test machine and measure.

[Treatment with an organic solvent: chemical resistance] The treatment with an organic solvent was carried out as a DEET treatment using a commercially available insect repellent containing DEET (trade name: Cutter OUTDOORSMAN, composition: DEET 21.85). %, DEET isomer 1.15%, other components 77.0%) were applied to absorbent cotton, and the surface of the resulting waterproof sheet was lightly rubbed once and dried for 2 minutes. The later water resistance was measured by the above method and evaluated. Further, as a DMF / ethanol treatment, the same measurement was performed using a 50% DMF / 50% ethanol solution instead of the insect repellent, and evaluation was performed.

<Preparation of two-component polyurethane resin solution> Unless otherwise specified, “parts” and “%” are solid contents excluding water, and indicate mass parts and mass%, respectively. Two-component polyurethane resin solutions having different oxyethylene group (abbreviated as OE group) contents were prepared, and various waterproof sheets shown in Examples were prepared. (Two-component polyurethane resin having an OE group content of 50%: A-1) In a four-necked flask equipped with a stirrer and a thermometer, 148.6 parts of PEG having a number average molecular weight of 2000 (calculated from the hydroxyl value), 26.4 parts of EG, 125 parts of MDI and 700 parts of DMF were charged and reacted at 70 ° C. for 7 hours in a dry nitrogen atmosphere. Next, 0.5 parts of EG was added to complete the reaction, and a two-component polyurethane resin (A-1) solution having a resin concentration of 30% and a viscosity of 10,000 mPa / 20 ° C. was obtained. The OE group content of A-1 is 50%.

(2-pack type polyurethane resin having an OE group content of 30%: A-2) 89.9 parts of PEG having a number average molecular weight of 2000, 59.9 parts of polyethylene adipate having a number average molecular weight of 2000, 34.8 parts of BG, MDI 115.4 parts and 700 parts of DMF were charged and reacted in the same manner as in A-1. Next, 0.5 parts of EG was added to complete the reaction, and a two-component polyurethane resin (A-2) solution having a resin concentration of 30% and a viscosity of 9,000 mPa / 20 ° C. was obtained. The OE group content of A-2 is 30%.

(Two-component polyurethane resin with 0% OE group content: A-3) 149.8 parts of polyethylene adipate having a number average molecular weight of 2000, 34.8 parts of BG, 115.4 parts of MDI and DMF
700 parts were charged and reacted in the same manner as in A-1. Next, 0.5 parts of EG was added to complete the reaction, and a two-component polyurethane resin (A-3) solution having a resin concentration of 30% and a viscosity of 9,000 mPa / 20 ° C. was obtained. The OE group content of A-3 is 0%.

In the following examples, “parts” and “%” represent parts by mass and mass%, respectively. (Example 1) Polyester twill fabric (both warp and weft 110 decitex 50 filaments, warp density: 171 / 2.54 cm, weft density: 84 / 2.54 cm) fluorine-based water repellent Asahi Guard AG710 ( Asahi Glass Co., Ltd.) 5% aqueous solution was padded, dried and cured, and crushed with a plast calender. Next, the organic solvent solution of the following urethane resin composition was apply | coated using the knife coater, and it solidified for 5 minutes in DMF15% aqueous solution. Thereafter, the solvent is removed in 25 ° C. water, washed, dried, further subjected to water repellency treatment using a fluorine-based water repellent, and subjected to a finishing set at 150 ° C., and a fine fabric having a thickness of 40 μm is formed on one side of the fiber fabric. A waterproof sheet having a porous polyurethane resin film was obtained. The performance of the obtained waterproof sheet is shown in Table 1.

Organic solvent solution of urethane resin composition A-1 (resin solid content 30%) 25 parts by mass, one-component wet coagulation polyurethane resin (solid content 30%) 75 parts by mass, DMF 30 parts by mass, calcium carbonate fine particles (average (Particle size 0.3 μm) 3 parts by mass, Duranate TPA-100 5 parts by mass (manufactured by Asahi Kasei Kogyo Co., Ltd., HDI isocyanurate modified substance, functional group number 3.0, solid content 100%), HI-215 (Daiichi Seikagaku ( Co., Ltd., Catalyst) 0.5 parts by mass, L-1500 (Dainippon Ink & Chemicals, Inc., white pigment) 5 parts by mass, fluorinated water repellent (solvent, solid content 10%) 5 parts by mass

(Comparative Example 1) A waterproof sheet was obtained in the same manner as in Example 1 except that the following organic solvent solution of the urethane resin composition was used. The performance of the obtained waterproof sheet is shown in Table 1.

Organic solvent solution of urethane resin composition A-1 (resin solid content 30%) 25 parts by mass, one-component wet coagulation polyurethane resin (solid content 30%) 75 parts by mass, DMF 30 parts by mass, calcium carbonate fine particles (average Particle size 0.3 μm) 3 parts by mass, L-1500 (manufactured by Dainippon Ink & Chemicals, Inc., white pigment) 5 parts by mass, fluorine-based water repellent (solvent type, solid content 10%) 5 parts by mass

(Comparative Example 2) A waterproof sheet was obtained in the same manner as in Example 1 except that the following organic solvent solution of the urethane resin composition was used. The performance of the obtained waterproof sheet is shown in Table 1.

Organic solvent solution of urethane resin composition A-1 (resin solid content 30%) 25 parts by mass, one-component wet coagulation polyurethane resin (solid content 30%) 75 parts by mass, DMF 30 parts by mass, calcium carbonate fine particles (average Particle size 0.3 μm) 3 parts by mass, Duranate TPA-100 0.2 parts by mass (manufactured by Asahi Kasei Kogyo Co., Ltd., HDI isocyanurate modified product, functional group number 3.0, solid content 100%), HI-215 (Daisen Seika) Industrial Co., Ltd., Catalyst) 0.5 parts by mass, L-1500 (Dainippon Ink & Chemicals, Inc., white pigment) 5 parts by mass, fluorinated water repellent (solvent type, solid content 10%) 5 Parts by mass

(Comparative Example 3) A waterproof sheet was obtained in the same manner as in Example 1 except that the following organic solvent solution of the urethane resin composition was used. The performance of the obtained waterproof sheet is shown in Table 1.

Organic solvent solution of urethane resin composition One-part polyurethane resin for wet coagulation (solid content 30%) 100 parts by mass, DMF 30 parts by mass, calcium carbonate fine particles (average particle size 0.3 μm) 3 parts by mass, Duranate TPA-100 5 parts by mass (manufactured by Asahi Kasei Kogyo Co., Ltd., modified HDI isocyanurate, functional group number 3.0, solid content 100%), HI-215 (manufactured by Dainichi Seika Kogyo Co., Ltd., catalyst) 0.5 parts by mass, L- 1500 (Dainippon Ink & Chemicals, white pigment) 5 parts by mass, fluorinated water repellent (solvent, solid content 10%) 5 parts by mass

(Example 2) A waterproof sheet was obtained in the same manner as in Example 1 except that a fluorine-based water repellent was not used in the organic solvent solution of the urethane resin composition. The performance of the obtained waterproof sheet is shown in Table 2.

Example 3 A waterproof sheet was obtained in the same manner as in Example 1 except that the following organic solvent solution of the urethane resin composition was used. The performance of the obtained waterproof sheet is shown in Table 2.

Organic solvent solution of urethane resin composition A-1 (resin solid content 30%) 40 parts by mass, one-component wet coagulation polyurethane resin (solid content 30%) 60 parts by mass, DMF 30 parts by mass, silicon dioxide fine particles (average Particle size 0.7 μm) 3 parts by mass, Duranate TPA-100 5 parts by mass (manufactured by Asahi Kasei Kogyo Co., Ltd., modified HDI isocyanurate functional group 3.0 solid content 100%), HI-215 (Daiichi Seika Kogyo ( Co., Ltd., Catalyst) 0.5 parts by mass, L-1500 (Dainippon Ink & Chemicals, Inc., white pigment) 5 parts by mass, fluorinated water repellent (solvent, solid content 10%) 5 parts by mass

(Example 4) A waterproof sheet was obtained in the same manner as in Example 1 except that A-2 was used in place of the two-component polyurethane resin A-1 as the organic solvent solution of the urethane resin composition. The performance of the obtained waterproof sheet is shown in Table 2.

(Example 5) A waterproof sheet was obtained in the same manner as in Example 1 except that A-3 was used in place of the two-component polyurethane resin A-1 as the organic solvent solution of the urethane resin composition. The performance of the obtained waterproof sheet is shown in Table 2.

Claims (7)

Polyurethane resin film of microporous obtained by wet coagulation is positioned at the outermost layer or near the water resistance of JIS L1092 after treatment with an organic solvent is not less than 19.6 kPa, the poly urethane resin The film is made of a polyurethane resin composition containing a two-component polyurethane resin (A) and a polyurethane resin for wet coagulation, and the wet coagulation polyurethane resin and the two-component polyurethane resin (A) in the polyurethane resin composition A waterproof ratio, wherein the weight ratio is 1: 9 to 9: 1 and the organic solvent contains at least one selected from N, N′-diethyl-m-toluamide and N, N′-dimethylformamide. Sheet.   The waterproof sheet according to claim 1, wherein the polyurethane resin composition also contains an organic polyisocyanate (B) having a polyisocyanate (B0) having 3 or more functional groups.   The two-part polyurethane resin (A) is a polyurethane resin comprising an oxyethylene group-containing polymer diol (d), an organic diisocyanate (e), and a chain extender (f), and the two-part polyurethane resin The waterproof sheet according to claim 1 or 2, wherein the oxyethylene group content is 10 to 80% by mass relative to (A).   The waterproof sheet according to claim 2 or 3, wherein the organic polyisocyanate (B) is at least one selected from the group consisting of an aliphatic polyisocyanate having an average functional group number of 2.3 to 5 and an alicyclic polyisocyanate. . The water pressure resistance is 19.6 to 196 KPa, the moisture permeability by the calcium chloride method is 6000 to 15000 g / m ² · 24 hrs, and the moisture permeability by the potassium acetate method is 8000 to 30000 g / m ² · 24 hrs. The waterproof sheet according to any one of claims 1 to 4 , wherein: The waterproof sheet according to any one of claims 1 to 5 , further comprising a fiber fabric. Polyurethane resin film of microporous obtained by wet coagulation is positioned at the outermost layer or near the water resistance of JIS L1092 after treatment with an organic solvent is not less than 19.6 kPa, the poly urethane resin The film comprises a polyurethane resin composition containing a two-component polyurethane resin (A) and a polyurethane resin for wet coagulation, and the organic solvent is selected from N, N′-diethyl-m-toluamide and N, N′-dimethylformamide in that it contains at least one method for manufacturing a waterproof sheet, characterized that, on at least one surface of the fiber fabric, poly urethane resin composition comprising a 2-component polyurethane resin (a) and polyurethane resin for wet coagulation an organic solvent solution, wherein for wet coagulation polyurethane resin and two-component polyurethane resin (a) and of the The amount ratio of 1: 9 to 9: 1 organic solvent solution was applied a, is wet coagulation method of a waterproof sheet and forming a polyurethane resin film of microporous.