JP2017101115A - Adhesive for moisture-permeable waterproof material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin for a moisture-permeable waterproof material exhibiting sufficient adhesive strength in aging for a short time and a sufficiently long usable life after mixing with a cured agent.SOLUTION: There is provided a polyurethane resin formable composition for a moisture permeable waterproof material constituted by a main agent (D), which contains a polyurethane resin (u) containing a polyoxyethylene diol (a1), a polymer diol (a2) other than (a1) and an organic diisocyanate (B) as essential constitutional monomers and which satisfies all of the following (1) to (3), and a curing agent (E) containing an organic polyisocyanate (C) having 3 or more isocyanate groups. Conditions: (1) the polyurethane resin has hydroxyl groups and a hydroxyl value thereof is 1.4 to 11.2 mgKOH/g; (2) a total of the urethane group concentration and the urea group concentration is 7.0 to 13.0 wt.%; and (3) a weight percentage of a polyoxyethylene chain to which 2 or more oxyethylene groups are bound is 20 to 50 wt.% based on the weight of (u).SELECTED DRAWING: None

Description

The present invention relates to an adhesive. More specifically, the present invention relates to an adhesive suitable for a moisture permeable waterproof material.

Conventionally, various adhesives have been studied as adhesives used for moisture-permeable and waterproof materials in consideration of performance of moisture-permeable and waterproof materials such as texture, water pressure resistance, moisture permeability, and washing resistance. For example, Patent Document 1 discloses a nonporous membrane-type moisture permeable waterproofing process obtained by blending an aqueous dispersion of a urethane prepolymer having a polyoxyethylene group and a terminal hydroxyl group with a water-dispersed polyisocyanate-based crosslinking agent. An adhesive composition is disclosed. However, although the adhesive described in Patent Document 1 is excellent in terms of the texture, moisture resistance, moisture permeability, washing resistance, etc. of the moisture permeable waterproof material using the adhesive, it has an adhesive strength (particularly initial adhesive strength). There was a problem that the speed of expression was slow, and it took a long time to obtain sufficient adhesive strength and sufficient water resistance of the moisture-permeable waterproof material. On the other hand, the adhesive described in Patent Document 2 has a problem that the usable time of the two-part curable liquid with the curing agent is shortened when the adhesive strength is accelerated.

JP 2007-77191 A Japanese Patent Application Laid-Open No. 2015-078353

  The present invention has been made in view of the above problems, and an object of the present invention is to provide a moisture-permeable waterproof material that exhibits sufficient adhesive strength in a short time of aging and has a sufficiently long pot life after mixing with a curing agent. It is to provide a polyurethane resin.

The inventors of the present invention have arrived at the present invention as a result of intensive studies to solve the above problems. That is, the present invention uses polyoxyethylene diol (a1), high molecular diol (a2) other than (a1) and organic diisocyanate (B) as essential constituent monomers, and the following (1) to (3): Adhesion for moisture-permeable and water-proof material composed of a main agent (D) containing a polyurethane resin (u) satisfying all and a curing agent (E) containing an organic polyisocyanate (C) having three or more isocyanate groups Polyurethane resin (U) -forming composition for adhesive; adhesive for moisture-permeable and waterproof material formed by reacting main agent (D) and curing agent (E) in the composition; moisture-permeable and waterproof formed using the adhesive It is a material.
(1) It has a hydroxyl group, and the hydroxyl value is 1.4 to 11.2 mgKOH / g.
(2) The total value of the urethane group concentration and the urea group concentration is 7.0 to 13.0% by weight.
(3) The weight ratio of the polyoxyethylene chain is 20 to 50% by weight.

  The adhesive for moisture permeable and waterproof material of the present invention exhibits sufficient adhesive strength in a short time aging and has a sufficiently long pot life after mixing with a curing agent.

The adhesive for moisture permeable waterproof material of the present invention is a two-part liquid obtained by reacting the main agent (D) and the curing agent (E) constituting the polyurethane resin (U) -forming composition for moisture permeable waterproof material. Adhesive.

The main agent (D) contains a polyurethane resin (u) obtained by reacting a polyoxyethylene diol (a1), a polymer diol (a2) other than (a1), and an organic diisocyanate (B). The curing agent (E) contains an organic polyisocyanate (C) having 3 or more isocyanate groups.

The polyurethane resin (u) has a hydroxyl group, and the hydroxyl value is 1.4 to 11.2 mg KOH / g, preferably 1.9 to 7.5 mg KOH / g, and more preferably 2.8 to 5. 6 mg KOH / g. When the hydroxyl value is less than 1.4 mg KOH / g, the speed of expression of the adhesive strength is slow, and when it exceeds 11.2 mg KOH / g, the pot life of the two-part curable liquid with the curing agent is shortened.
In the present invention, the hydroxyl value is measured according to JIS K 1557-1.

The total value of the urethane group concentration and the urea group concentration of the polyurethane resin (u) is 7.0 to 13.0% by weight, preferably 8.0 to 12.0% by weight, more preferably 9.0 to 11.0% by weight. If the total value of the urethane group concentration and the urea group concentration is less than 7.0% by weight, the tensile physical properties are insufficient and the water pressure is poor, and if it exceeds 13.0% by weight, the texture is hard and the moisture permeability is impaired.
In the present invention, the urethane group concentration and urea group concentration of the polyurethane resin (U) are determined based on the nitrogen content in the urethane resin using a nitrogen analyzer, and the molar ratio identification of the urethane group and urea group using 1H-NMR. It can be measured.

Nitrogen analysis can be measured by chemiluminescence.
Measurement conditions-Combustion temperature: 900 ° C
Measuring device: “Antek7000” manufactured by Antek

1H-NMR can be measured under the following conditions.
・ Equipment: “AVANCEIII400” manufactured by Bruker BioSpin
-Sample solution: 1% DMSO-d6 solution-Integration count: 16 times

The weight ratio of the polyoxyethylene chain in which two or more oxyethylene groups of the polyurethane resin (u) are bonded is 20 to 50% by weight, preferably 25 to 45% by weight from the balance of moisture permeability and water pressure resistance, more preferably 30 to 40% by weight. If it is less than 20% by weight, the moisture permeability is insufficient, and if it exceeds 50% by weight, the water pressure resistance is insufficient. Here, the polyoxyethylene chain means a chain in which two or more oxyethylene groups are bonded.

The weight ratio of the polyoxyethylene chain in the polyurethane resin (u) is 1H-NMR and 13C-NMR. The weight ratio of the polyoxyethylene diol (a1), the polymer diol (a2) other than (a1), and the organic diisocyanate (B) Can be calculated by obtaining.

1H-NMR can be measured under the following conditions.
・ Equipment: “AVANCEIII400” manufactured by Bruker BioSpin
-Sample solution: 1% DMSO-d6 solution-Integration count: 16 times

1H-NMR can be measured under the following conditions.
・ Equipment: “AVANCEIII400” manufactured by Bruker BioSpin
・ Sample solution: 1% DMSO-d6 solution ・ Number of integration: 1024 times

The ratio of (a1) to the total weight of the polymer diol (a2) other than the polyoxyethylenediol (a1) and (a1) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight. preferable.
The number average molecular weight of the polyoxyethylene diol (a1) is 500 to 20000.
Polyoxyethylene diol (a1) is an essential component for expressing moisture permeability.
The content of (a1) is preferably 20 to 80% by weight, more preferably 30 to 70% by weight, based on the total weight of the polymer diol (a2) other than (a1) and (a1).
The number average molecular weight (hereinafter also referred to as Mn) of the polyoxyethylene diol (a1) is 500 to 20000, preferably 1000 to 10,000. The number average molecular weight of the polymer diol (a2) other than (a1) is 500 to 20000, preferably 1000 to 10,000.

The polymer diol (a2) other than the polyoxyethylene diol (a1) contains a polyether diol (a21), a polycarbonate diol (a22), a polyester diol (a23), and the like.
Examples of the polyether diol (a21) include polyoxypropylene glycol, polyoxytetramethylene glycol, polyoxypropylene / polyoxytetramethylene block copolymer diol, and the like.

Examples of the polycarbonate diol (a22) include polyhexamethylene carbonate diol, polypentamethylene carbonate diol, polytetramethylene carbonate diol, poly (tetramethylene / hexamethylene) carbonate diol, and the like.

Examples of the polyester diol (a23) include polyethylene adipate diol, polybutylene adipate diol, polyhexamethylene adipate diol, polyhexamethylene isophthalate diol, polyneopentyl adipate diol, polyethylene propylene adipate diol, polyethylene butylene adipate diol, polybutylene hexa Methylene adipate diol, polydiethylene adipate diol, poly (polytetramethylene ether) adipate diol, poly (3-methylpentylene adipate) diol, polyethylene azelate diol, polyethylene sebacate diol, polybutylene azelate diol, polybutylene sebacate Diol, polyneopentyl terephthalate diol, polycap Lactone diol, polyvalerolactone diol.

The Mn of the polymer diol (a2) other than the polyoxyethylene diols (a1) and (a1) in the present invention can be measured using gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions. .
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 each connected one” [all manufactured by Tosoh Corporation]
・ Sample solution: 0.25 wt% THF solution ・ Solution injection amount: 10 μl
・ Flow rate: 0.6 ml / min ・ Measurement temperature: 40 ° C.
・ Detection device: Refractive index detector ・ Reference material: Standard polyethylene glycol

As the organic diisocyanate component (B) in the present invention, those conventionally used for the production of polyurethane can be used, an aromatic diisocyanate having 8 to 26 carbon atoms having two isocyanate groups (B1), and 4 to 4 carbon atoms. 22 chain aliphatic diisocyanate (B2), C8-18 alicyclic diisocyanate (B3), C10-18 araliphatic diisocyanate (B4), and the like. An organic diisocyanate component (B) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the aromatic diisocyanate (B1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter, tolylene diisocyanate is abbreviated as TDI). ), 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter diphenylmethane diisocyanate is abbreviated as MDI), 4,4′-diisocyanatobiphenyl, 3,3′-dimethyl-4,4′-diisocyanate Natobiphenyl, 3,3′-dimethyl-4,4′-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate and m- or p-isocyanatophenylsulfonyl isocyanate.

  Examples of the aliphatic polyisocyanate (B2) having 4 to 22 carbon atoms include ethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate (hereinafter abbreviated as HDI), dodecamethylene diisocyanate, 1,6,11-undecane triisocyanate, 2 2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, 2,6-diisocyanatomethylcaproate, bis (2-isocyanatoethyl) fumarate and bis (2-isocyanatoethyl) carbonate.

  Examples of the alicyclic polyisocyanate (B3) having 8 to 18 carbon atoms include isophorone diisocyanate (hereinafter abbreviated as IPDI), 4,4-dicyclohexylmethane diisocyanate (hereinafter abbreviated as hydrogenated MDI), cyclohexylene diisocyanate, and methyl. Examples include cyclohexylene diisocyanate, bis (2-isocyanatoethyl) -4-cyclohexene-1,2-dicarboxylate and 2,5- or 2,6-norbornane diisocyanate.

  Examples of the araliphatic polyisocyanate (B4) having 10 to 18 carbon atoms include m- or p-xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.

The method for producing the polyurethane resin (u) of the present invention is not particularly limited, and can be produced by a known method or the like. For example, the polyoxyethylene diol (a1) in which the weight ratio of the polyoxyethylene chain in the resin (u) is 20 to 50% by weight, the polymer diol (a2) other than (a1), and the urethane group concentration An organic diisocyanate component (B) in an amount such that the total urea group concentration is 7.0 to 13.0% by weight, and if necessary, an organic solvent and an additive are charged together and reacted to give a hydroxyl value of 1. When reaching the range of 4 to 11.2 mg KOH / g, a termination reaction with a reaction terminator may be performed as necessary, and the weight ratio of the polyoxyethylene chain in the resin is 20 to 50% by weight ( a1), (a2) and an organic diisocyanate component (B) in an amount such that the total value of the urethane group concentration and the urea group concentration is 7.0 to 13.0% by weight to react with the isocyanate group. After obtaining the terminal prepolymer, it may be reacted with a chain extender. By using a kneader or the like as the reaction apparatus, the above reaction can be carried out in the absence of a solvent.

  In order to promote the reaction in the urethanization reaction, a catalyst used in a normal urethanization reaction may be used as necessary. Examples of the catalyst include amine catalysts [triethylamine, N-ethylmorpholine, triethylenediamine, and cycloamidines described in US Pat. No. 4,524,104 [1,8-diaza-bicyclo [5.4.0] -7-undecene { "DBU"} manufactured by San Apro Co., Ltd.]]; tin-based catalyst (dibutyltin dilaurate, dioctyltin dilaurate and tin octylate); titanium-based catalyst (tetrabutyl titanate, etc.); bismuth-based catalyst (bismuth trioctylate, etc.); Etc.

The main agent (D) of the present invention can contain an organic solvent and a stabilizer as necessary. The content of the organic solvent is preferably 0 to 60% by weight. Further, the content of the stabilizer is preferably 0 to 4% by weight based on the resin solid content.

  Examples of the organic solvent for the main agent (D) include a solvent containing no active hydrogen group. Specific examples include amide solvents (DMF, N, N-dimethylacetamide, N-methylpyrrolidone, etc.), sulfoxide solvents (dimethyl sulfoxide, etc.), ketone solvents (methyl ethyl ketone, methyl isobutyl ketone, etc.), ether solvents ( Dioxane, THF, etc.), ester solvents (methyl acetate, ethyl acetate, butyl acetate, etc.), aromatic solvents (toluene, xylene, etc.) and the like. An organic solvent may be used individually by 1 type, and may use 2 or more types together.

The stabilizer is not particularly limited, and a known antioxidant and / or ultraviolet absorber can be used, and is usually 0 to 5% by weight, preferably 0.1%, based on the weight of the polyurethane resin (U). ~ 3% by weight is used.

Antioxidants include phenolic [2,6-di-t-butyl-p-cresol and butylated hydroxyanisole, etc.]; bisphenol [2,2′-methylenebis (4-methyl-6-t-butylphenol) Etc.]; phosphorus-based [triphenyl phosphite and diphenylisodecyl phosphite etc.] and the like.

Examples of the ultraviolet absorber include benzophenone [2,4-dihydroxybenzophenone and 2-hydroxy-4-methoxybenzophenone and the like]; benzotriazole [2- (2′-hydroxy-5′-methylphenyl) benzotriazole and the like]; Salicylic acid type [phenyl salicylate and the like]; hindered amine type [bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate and the like] and the like.
Other additives include anti-fusing agents and flame retardants.

The curing agent (E) contains an organic polyisocyanate (C) having 3 or more isocyanate groups.
The content of (C) is preferably 50 to 100% by weight with respect to the weight of the curing agent (E).
Examples of (C) include crude TDI having 3 or more isocyanate groups, crude MDI having 3 or more isocyanate groups, 4,4 ′, 4 ″ -triphenylmethane triisocyanate, 2-isocyanatoethyl-2, 6-diisocyanatohexanoate or aromatic diisocyanate having 8 to 26 carbon atoms (B1) having two isocyanate groups exemplified as the organic diisocyanate component (B), chain aliphatic diisocyanate having 4 to 22 carbon atoms Of (B2), C8-18 alicyclic diisocyanate (B3), C10-18 araliphatic diisocyanate (B4), a modified product having three or more isocyanate groups, A trimer etc. are mentioned.
The curing agent (E) can contain an organic solvent, a catalyst, a pigment, a stabilizer and the like as required in addition to (C).

As an organic solvent, the solvent which does not contain the active hydrogen group illustrated as an organic solvent of a main ingredient (D) is mentioned. The content of the organic solvent is preferably 0 to 50% by weight.

  As a catalyst, the thing similar to what was illustrated as a catalyst used as needed at the time of manufacture of a polyurethane resin (u) is mentioned.

  It does not specifically limit as a pigment, A well-known organic pigment and / or an inorganic pigment can be used, Usually 0-5 weight% on the basis of the weight of a polyurethane resin (U), Preferably it is 0.1-3 weight %used.

Examples of organic pigments include insoluble azo pigments, soluble azo pigments, copper phthalocyanine pigments, and quinacridone pigments. Examples of inorganic pigments include chromates, ferrocyan compounds, metal oxides, selenium sulfide compounds, metal salts. (Sulfates, silicates, carbonates, phosphates, etc.), metal powders, carbon black and the like.

As a stabilizer, the thing similar to what was illustrated as a stabilizer contained in a main ingredient (D) as needed is mentioned. Usually, 0 to 5% by weight, preferably 0.1 to 3% by weight, is used based on the weight of the polyurethane resin (u).

The polyurethane resin (U) -forming composition for an adhesive for moisture-permeable and waterproof material of the present invention is composed of a main agent (D) and a curing agent (E). The weight ratio of the curing agent (E) to the main agent (D) is 1 to 100% by weight, preferably 5 to 50% by weight, and more preferably 10 to 50% by weight in terms of both adhesive strength and pot life. It is.
The equivalent ratio of the isocyanate group of the organic polyisocyanate (C) to the hydroxyl group of the polyurethane resin (u) (equivalent of isocyanate group / equivalent of hydroxyl group) is 0.5 / 1 to 20/1.

The main agent (D) and the curing agent (E) are preferably blended and used within 12 hours for bonding at room temperature.
The adhesive for moisture permeable waterproof material of the present invention is obtained by mixing and reacting the main agent (D) and the curing agent (E).
Propeller stirring is preferably performed in the mixing tank, and the mixing temperature is preferably room temperature.

The polyurethane resin-forming composition for adhesives for moisture-permeable and waterproof materials of the present invention is used when producing a moisture-permeable and waterproof material that is a composite material in which a polyurethane resin layer is provided on at least one surface of a fibrous base material. .

The base material of the fibrous base material may be any of cellulose fibers such as cotton, hemp and rayon, and synthetic fibers such as polyester, polyamide and polyolefin. Moreover, as a form of the fibrous base material, those having any structure such as a woven fabric, a knitted fabric, and a non-woven fabric can be used, but a woven fabric and a knitted fabric are preferable.

Examples of the method for producing a moisture permeable waterproof material include the following methods (1) to (3).
(1) A method for producing a moisture-permeable and waterproof material in which at least a part of one side of a fibrous base material is bonded to a skin layer made of polyurethane resin:
At least a part of one side of the fibrous base material is formed on the adhesive layer side surface of the laminate obtained by laminating the release paper, the skin layer made of polyurethane resin, and the adhesive layer formed of the adhesive of the present invention in this order. It is a method of manufacturing a moisture permeable waterproof material by peeling the release paper after bonding, specifically, a moisture permeable waterproof layer by applying a resin solution for a moisture permeable waterproof cloth for the skin layer on the release paper Forming the adhesive layer by applying the adhesive of the present invention on the moisture permeable waterproof layer, attaching at least a part of one side of the fibrous base material to the adhesive layer, main agent (D) And a step of reacting the curing agent (E) and a step of peeling the release paper.

(2) A method for producing a moisture permeable waterproof fabric in which at least a part of both surfaces of a fibrous base material and a plurality of skin layers made of polyurethane resin are bonded to each other:
A step of applying a resin solution for a moisture permeable waterproof cloth for a skin layer onto a release paper to form a skin layer, a step of applying an adhesive of the present invention on the skin layer to form an adhesive layer, the adhesive layer The step of attaching at least a part of the moisture permeable waterproof material obtained in (1) above to the fibrous base material, the step of reacting the main agent (D) and the curing agent (E), and the release paper are peeled off. A manufacturing method including a process.

(3) A method for producing a moisture permeable waterproof material in which at least a part of both surfaces of a moisture permeable waterproof layer made of polyurethane resin and a plurality of fibrous base materials are bonded to each other:
The manufacturing method including the process of apply | coating the adhesive agent of this invention on the skin layer of the moisture-permeable waterproof material obtained by said (1), and forming the adhesive layer, and the process of affixing a fibrous base material on this adhesive layer .

  In addition, as a polyurethane resin forming composition for the said skin layer, a well-known thing (For example, thing of Unexamined-Japanese-Patent No. 2007-211239) etc. can be used.

  Below, one manufacturing method of the dry lamination method applicable to the method of said (1) is demonstrated in detail. First, a coating liquid composed of the polyurethane resin-forming composition for the skin layer is prepared, and this is coated on a release paper using a knife coater, a pipe coater, a bar coater or the like. Then, it is dried with a dryer such as an air oven at about 100 to 160 ° C. for about 30 seconds to 5 minutes to form a skin layer made of polyurethane resin. The thickness of the skin layer can be adjusted by repeatedly adjusting the slit of the coater, applying, and drying when applying the coating liquid.

  Next, the adhesive of the present invention is applied on the obtained skin layer to form an adhesive layer. The adhesive is applied on the entire surface of the skin layer using a gravure coater, knife coater, pipe coater, bar coater or the like, and is dried as necessary.

  Next, the fibrous base material surface is affixed to the formed adhesive layer. The laminated body after pasting has a structure in which a fibrous base material, an adhesive layer, and a skin layer are sequentially laminated. The obtained laminate is subjected to thermocompression bonding at a temperature of 80 to 160 ° C. and aged at 30 to 110 ° C. for 20 to 100 hours as necessary. Next, by peeling the skin layer and the release paper, a moisture permeable waterproof material in which a skin layer made of polyurethane resin is formed in this order on one side of the fibrous base material via an adhesive layer is obtained.

  Moreover, you may perform a water-repellent process to the obtained moisture-permeable waterproof material using water-repellent agents, such as a fluorine type and a silicon type, as needed. Furthermore, the adhesive layer is again applied on the skin layer after peeling the release paper (the surface on the opposite side of the previously bonded fibrous base material), and another fibrous base prepared in addition to the surface. The material may be thermocompression bonded in the same manner as described above to have a skin layer between the fibrous base material and the fibrous base material.

  The moisture permeable waterproof material using the adhesive for moisture permeable waterproof material of the present invention is used for outdoor wear, ski related wear, windbreaker, athletic wear, golf wear, rain wear, casual coat, outdoor work for fishing and climbing. It can be suitably used for hygiene materials such as clothes, gloves, shoes, mountain climbing tools such as shoes and tents, paper diapers, sanitary products and the like that require moisture permeability.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited to these. In the following, parts represent parts by weight.

The hexamethylene diisocyanate trimer in Tables 1 and 2 is “Coronate HL” (trimethylolpropane / hexamethylene diisocyanate trimer) manufactured by Nippon Polyurethane Co., Ltd.

Examples 1 to 12 and Comparative Examples 1 to 6 [Production of polyurethane resin]
In accordance with the formulation shown in Table 1 and Table 2, a polymer diol (a2) other than polyoxyethylene diol (a1) and (a1), an organic diisocyanate (B), and a chain extender and a solvent as necessary are charged into a reaction vessel. The reaction is carried out at 65 ° C. for 12 hours under a dry nitrogen atmosphere, and then a reaction terminator is added as necessary to conduct a terminal termination reaction for 1 hour, and the polyurethane resins (u-1) to (u-12) A main agent consisting of a solution and a main agent consisting of solutions of polyurethane resins (u′-1) to (u′-6) for comparison were obtained.
The obtained main agent, the main agent for comparison, a curing agent composed of an organic polyisocyanate (C) and an organic solvent, and a curing agent for comparison were charged into a container according to the formulations shown in Tables 1 and 2, and in a dry nitrogen atmosphere, By mixing at 25 ° C. for 10 minutes, the adhesive of the present invention was obtained.
Table 1 and Table 2 show the hydroxyl value of the polyurethane resin (u), the total value of the urethane group concentration and the urea group concentration, and the weight ratio of the polyoxyethylene chain of the polyurethane resin (u) measured by the methods described above. did.
Moreover, the performance of the adhesive was evaluated by the following method, and the results are shown in Tables 1 and 2.

[1] Viscosity increase rate (%) after mixing for 12 hours at 40 ° C after mixing of main agent (D) and curing agent (E)
After mixing the main agent (D) and curing agent (E) according to the formulations shown in Tables 1 and 2, the temperature was adjusted to 20 ° C and a BM viscometer (TV-10, No. 4 rotor manufactured by Toki Sangyo Co., Ltd.) was used. The initial viscosity (V1) was measured at 20 rpm). The container was sealed, temperature-controlled at 40 ° C. for 12 hours, and the viscosity (V2) was measured again under the same conditions.
The viscosity increase rate (%) was calculated from the following formula.
Viscosity increase rate (%) = {V2 / V1} × 100

[2] Method of measuring adhesive strength at each aging time Polyester taffeta (for both warp and weft, 83 dtex / 72 filaments, warp density 160 / 2.54 cm, weft density 70 / 2.54 cm, polyester taffeta thickness 0 0.1 mm) is scoured and dyed by a conventional method, and then a fluorine-based water repellent [a water repellent used before adhering the fiber fabric and the polyurethane resin skin layer, trade name “Asahi Guard AG710”, Asahi Glass Co., Ltd. , Manufactured hereinafter, the same was used as a fiber fabric. Sanyo Chemical's skin layer polyurethane resin solution “Samprene H-600” was applied onto the entire surface of the release paper using a knife coater and dried at 100 ° C. in an air oven to obtain a skin layer having a thickness of 10 μm. Next, the adhesive of the present invention or comparative adhesive prepared according to the formulation shown in Table 1 and Table 2 was applied onto the entire surface of the obtained skin layer using a knife coater and dried at 100 ° C. in an air oven. An adhesive layer having a thickness of 10 μm was obtained. Furthermore, the fiber fabric and the adhesive layer on the skin layer were superposed and bonded using a nip roll heated to 100 ° C. to obtain a moisture-permeable and waterproof material.
About the obtained moisture-permeable waterproof material, after leaving it to stand at a temperature of 60 ° C. and a humidity of 65% RH for 24 hours, 48 hours and 72 hours, the release paper is peeled off and the adhesive strength is measured according to JIS K 6256-1. did.

  The adhesive for moisture permeable waterproof material of the present invention exhibits sufficient adhesive strength in short-time aging, is excellent in both the texture and water pressure resistance of the obtained moisture permeable waterproof material, and after mixing with a curing agent Because the pot life is guaranteed, outdoor wear, ski-related wear, windbreakers, athletic wear, golf wear, rainwear, casual coats, outdoor work wear, gloves, shoes and tents when fishing or climbing. In addition to moisture-permeable and waterproof materials used for mountain climbing tools such as paper diapers, sanitary materials and other hygroscopic waterproof materials such as sanitary material back sheets that require moisture permeability are particularly useful. .

Claims (8)

Polyurethane resin having polyoxyethylene diol (a1) and polymer diol (a2) other than (a1) and organic diisocyanate (B) as essential constituent monomers and satisfying all of the following (1) to (3) ( Polyurethane resin for adhesives for moisture-permeable and waterproof materials (U) comprising a main agent (D) containing u) and a curing agent (E) containing an organic polyisocyanate (C) having three or more isocyanate groups ) Formable composition.
(1) It has a hydroxyl group, and the hydroxyl value is 1.4 to 11.2 mgKOH / g.
(2) The total value of the urethane group concentration and the urea group concentration is 7.0 to 13.0% by weight.
(3) The weight ratio of the polyoxyethylene chain in which two or more oxyethylene groups are bonded is 20 to 50% by weight with respect to the weight of the polyurethane resin (u). Furthermore, the composition of Claim 1 containing the organic solvent (M) which does not have active hydrogen. The equivalent ratio of the isocyanate group of the organic polyisocyanate (C) and the hydroxyl group of the polyurethane resin (u) (equivalent of isocyanate group / equivalent of hydroxyl group) is 0.5 / 1 to 20/1. Composition. The ratio of (a1) is 20 to 80% by weight with respect to the total weight of the polymer diol (a2) other than the polyoxyethylene diol (a1) and (a1). The composition as described. The number average molecular weight of polyoxyethylene diol (a1) is 500-20000, The composition of any one of Claims 1-4. Moisture permeable waterproofing formed by reacting the main agent (D) and the curing agent (E) in the polyurethane resin (U) -forming composition for adhesives for moisture permeable waterproof materials according to any one of claims 1 to 5. Adhesive for materials. A moisture-permeable waterproof material using the adhesive according to claim 6. A back sheet for paper diapers using the adhesive according to claim 6.