JP2015193810A - Polyurethane resin for moisture-permeable water-proof material - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyurethane resin composition for a moisture-permeable waterproof material which has excellent moisture permeability and is more suppressed in water-swelling than a conventional resin.SOLUTION: There is provided a polyurethane resin composition for a moisture-permeable waterproof material which is obtained by reacting an active hydrogen component (A) containing a polyamine (a1) represented by the formula (1) and a polymer polyol (a2) with an organic polyisocyanate component (B). [Rand Reach independently represents an alkylene group having 2 to 10 carbon atoms; a represents an integer of 1 to 5; (x1) represents an ethyleneoxy group; (x2) represents an alkyleneoxy group having 3 to 12 carbon atoms; b represents an integer of 5 to 200; a represents an integer of 0 to 195; 5≤b+c≤200; when c is 1 or more; the binding forms of b (x1)s and c (x2)s are optional.)

Description

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

Conventionally, as a moisture permeable material used for a moisture permeable waterproof material, a material using a microporous sheet such as a polytetrafluoroethylene resin stretched porous film or a polyurethane resin wet film-forming film (for example, Patent Document 1) is known. However, the conventional porous sheet has a problem that it becomes clogged with sweat, dirt, and the like, resulting in a decrease in moisture permeability and a problem that sufficient waterproofness cannot be obtained. As a solution to such a problem, a nonporous sheet coated with a hydrophilic moisture-permeable polyurethane resin has been proposed (see, for example, Patent Document 2). In these moisture-permeable polyurethane resins, a polyol component such as polyoxyethylene glycol, which is a hydrophilic segment, or a block copolymer of polyoxyethylene and polyoxypropylene is introduced.
These non-porous sheets are remarkably improved in moisture permeability by reducing the thickness of the polyurethane resin film. However, since the resin strength is lowered by reducing the thickness, the sheet strength is lowered and sufficient waterproofness cannot be obtained. Here, if the thickness of the resin film is increased in order to increase the sheet strength, the moisture permeability decreases.
In addition, the presence of the hydrophilic segment causes water swelling when wet, resulting in a decrease in water pressure resistance. In addition, the appearance becomes poor due to generation of wrinkles. Here, if the hydrophilic segment is reduced in order to suppress water swelling, the moisture permeability decreases.

JP 56-26076 A Japanese Unexamined Patent Publication No. 64-62320

The present invention has been made in view of the above problems, and an object of the present invention is to provide a polyurethane resin for a moisture-permeable and waterproof material that has good moisture permeability and further suppresses water swelling compared to conventional resins. .

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 provides a transparent substance obtained by reacting an active hydrogen component (A) containing the diamine (a1) represented by the general formula (1) and the polymer polyol (a2) with the organic polyisocyanate component (B). Polyurethane resin for moisture-proof material (U); a moisture-permeable and waterproof material containing the polyurethane resin for moisture-permeable and waterproof material.

［式中、Ｒ¹及びＲ²はそれぞれ独立に炭素数２〜１０のアルキレン基を表し、ａは１〜５の整数を表す。（ｘ１）はエチレンオキシ基を表し、（ｘ２）は炭素数３〜１２のアルキレンオキシ基を表し、複数個ある（ｘ２）は同一でも異なっていてもよい。ｂが５〜２００の整数であり、ｃが０〜１９５の整数であり、かつ５≦ｂ＋ｃ≦２００を満たし、ｃが１以上の場合ｂ個の（ｘ１）とｃ個の（ｘ２）の結合形式はランダムでもブロックでもこれらの併用でもよい。］

[In formula, R < ¹ > and R < ² > represents a C2-C10 alkylene group each independently, and a represents the integer of 1-5. (X1) represents an ethyleneoxy group, (x2) represents an alkyleneoxy group having 3 to 12 carbon atoms, and a plurality of (x2) may be the same or different. When b is an integer of 5 to 200, c is an integer of 0 to 195, 5 ≦ b + c ≦ 200 is satisfied, and c is 1 or more, b (x1) and c (x2) bonds The format may be random, block, or a combination of these. ]

By using the polyurethane resin of the present invention, a moisture-permeable waterproof material excellent in moisture permeability and suppressed in water swelling can be obtained.

Water swell ratio (%) with respect to moisture permeability (A-1 method) of polyurethane resin (C)

The polyurethane resin (U) for moisture-permeable and waterproof material of the present invention comprises an active hydrogen component (A) and an organic polyisocyanate component (A) containing a polyamine (a1) represented by the general formula (1) and a polymer polyol (a2). It is characterized by reacting with B).
Since the polyurethane resin (U) has a hydrophilic group in the side chain, the degree of freedom of molecular movement of the hydrophilic group is higher than that of a conventional resin for moisture permeable waterproof cloth. Therefore, the permeability of water molecules in the hydrophilic group is improved, and a higher level of moisture permeability is exhibited even when the amount of hydrophilic group is the same as before. In other words, it is possible to reduce the amount of hydrophilic groups necessary for expressing the moisture permeability equivalent to that of conventional resins, and to suppress the decrease in water pressure resistance. Moreover, the swelling of the main chain at the time of water contact can be suppressed by using the hydrophilic group as a side chain, and the water swelling of the resin can be suppressed by preventing the main chain having a great influence of water swelling from swelling.

In General Formula (1), R ¹ and R ² are each independently an alkylene group having 2 to 10 carbon atoms (such as an ethylene group, a propylene group, a butylene group, a pentylene group, a hexylene group, an octylene group, and a decylene group). When there are a plurality of R ^{1 s,} they may be the same or different.
The

From the viewpoint of moisture permeability, R ¹ and R ² are preferably an alkylene group having 1 to 5 carbon atoms, more preferably an ethylene group, a 1,3-propylene group, a 1,4-butylene group, and 1, 5-pentylene group.

R ³ represents an organic group having 8 or less carbon atoms having no active hydrogen, or a hydrogen atom.

As an organic group having 8 or less carbon atoms and having no active hydrogen, when the polyamine (a1) represented by the general formula (1) having a terminal hydroxyl group is represented by R—OH, it reacts with the hydroxyl group of the polyamine (a1). The residue obtained by removing the R—O— group from the reaction product of the compound (Q0) and the polyamine (a1).
Specific examples of R ³ include the following groups.

(1) When compound (Q0) is monoisocyanate.
Examples of (Q0) include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, cyclohexyl isocyanate, butyl isocyanate, naphthyl isocyanate, and octadecyl isocyanate.

(2) Acyl group: As acetyl group, benzoyl group and the like (Q0), carboxylic anhydride, specifically, acetic anhydride, propionic anhydride, butyric anhydride, benzoic anhydride and the like can be mentioned.
(3) Benzyl group (Q0) includes benzyl bromide, 4-methoxybenzyl 2,2,2-trichloroacetimidate and the like.
(4) Examples of the alkyl group (Q0) include methyl bromide, methyl iodide, ethyl iodide and the like.
(5) Trialkylsilyl group (Q0) includes trimethylsilyl chloride, triethylsilyl chloride, t-butyldimethylsilyl chloride and the like.

a represents an integer of 1 to 5, and preferably 1 to 3 and more preferably 1 from the viewpoint of improving moisture permeability by improving the degree of freedom of the hydrophilic group. When a is 6 or more, the degree of freedom of the hydrophilic group in the side chain is insufficient, and the superiority of the conventional moisture-permeable waterproof cloth resin is lost.

b is an integer of 5 to 200, and 40 to 200 is preferable from the viewpoint of both moisture permeability and waterproofness. When b is smaller than 5, moisture permeability is not sufficiently exhibited. Moreover, when larger than 200, waterproofness falls and the solubility of resin falls when using as a solution.

c is an integer of 0 to 195, preferably 0 to 50, more preferably 0 from the viewpoint of moisture permeability. When it is larger than 195, moisture permeability is not sufficiently developed.

b and c satisfy 5 ≦ b + c ≦ 200, and preferably satisfy 50 ≦ b + c ≦ 150. The bonding mode of b ethyleneoxy groups (x1) and c alkyleneoxy groups (x2) having 3 to 12 carbon atoms may be random, block, or a combination thereof. When b + c is less than 5, the hydrophilic group of the side chain is too short, and the degree of freedom is insufficient, so that the superiority of the conventional resin for moisture-permeable waterproof fabric is lost. If it exceeds 200, the hydrophilic group of the side chain is too long and the difference in freedom of molecular motion from the linear hydrophilic group contained in the conventional linear urethane resin is lost. There is no advantage over it.

When there are a plurality of (x2), they may be the same or different, and an alkyleneoxy group having 3 to 5 carbon atoms is preferred from the viewpoint of moisture permeability. When (x2) is an alkyleneoxy group having 13 or more carbon atoms, the hydrophilicity of the side chain is insufficient.

Examples of the polyamine (a1) include those shown in the table below shown for each structural element of the general formula (1).

  The polyamine (a1) of the present invention may be used alone or in combination of two or more.

  The weight of the ethyleneoxy group in the polyamine (a1) is preferably 20 to 45% by weight based on the total weight of the active hydrogen component (A) and the organic polyisocyanate component (B) from the viewpoint of moisture permeability. 30 to 45% by weight is more preferable.

  The active hydrogen component (A) can contain a chain extender (a3) and, if necessary, a reaction terminator (a4) as long as the moisture permeability of the polyurethane resin (U) is not inhibited. (A3) and (a4) may be used individually by 1 type, and may be used in combination of 2 or more types.

The Mn of the polyamine (a1) is preferably from 500 to 20000, more preferably from 2000 to 6000, from the viewpoint of texture.

  Polyamine (a1) is, for example, poly (n = 2 to 6) alkylene (2 to 10 carbon atoms) poly (n = 3 to 7) amine (diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepenta Ethylene oxide (hereinafter referred to as EO) as an essential component of the imino group in which the amino group of amine, pentaethylenehexamine and hexaethyleneheptamine is ketiminated with ketones [methyl ethyl ketone (hereinafter abbreviated as MEK) and methyl isobutyl ketone, etc.] And a C3-12 alkylene oxide as an optional component by ring-opening addition, and hydrolyzing the ketiminated moiety to regenerate the amino group.

  Examples of the alkylene oxide having 3 to 12 carbon atoms include 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, 1,2-, 1,3- or 2,3-butylene oxide, tetrahydrofuran (Hereinafter abbreviated as THF), 3-methyltetrahydrofuran, α-olefin oxide, styrene oxide, epihalohydrin (eg, epichlorohydrin) and the like, and alkylene oxides having 1 to 5 carbon atoms are preferable from the viewpoint of moisture permeability. A C3-C12 alkylene oxide may be used individually by 1 type, or may use 2 or more types together.

  The addition form of EO and the alkylene oxide having 3 to 12 carbon atoms may be random addition, block addition or a combination thereof, but from the viewpoint of ensuring moisture permeability without impairing waterproofness, block addition is more preferable. Is the terminal block, that is, the block farthest from the nitrogen atom in the general formula (1) is the general formula (2) by adding an EO block.

Mn of polyamine (a1) in the present invention is obtained by dissolving 0.1 g of polyamine (a1) in about 20 mL of THF, adding 1 g of acetic anhydride and stirring at room temperature for 30 minutes to amidate a primary or secondary amine, and methanol. Excess acetic anhydride was decomposed by adding 1 g, and a sample from which volatile components were removed by drying under reduced pressure at 70 ° C. for 30 minutes was measured using gel permeation chromatography (hereinafter abbreviated as GPC) under the following conditions, for example. can do.
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel”
Super H2000, TSKgel SuperH3000, and TSKgel SuperH4000 connected to each 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

Mn of the polymer polyol (a2) in the present invention can be measured, for example, under the following conditions using gel permeation chromatography (hereinafter abbreviated as GPC).
Apparatus: “Waters Alliance 2695” [manufactured by Waters]
Column: “Guardcolumn Super HL” (1), “TSKgel”
Super H2000, TSKgel SuperH3000, and TSKgel SuperH4000 connected to each 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

  Examples of the polymer polyol (a2) having Mn of 500 or more include polyether diol and polyester diol.

  Examples of the polyether diol include polyethylene glycol, polyoxypropylene glycol, polyoxytetramethylene glycol, and polyoxypropylene / polyoxytetramethylene block copolymer diol.

  Examples of the polyester diol 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 hexamethylene 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, poly Neopentyl terephthalate diol, polycaprolactone Ol, poly-valerolactone diol, polycaprolactone triol, polyhexamethylene carbonate diol, poly pentamethylene carbonate diol, polytetramethylene carbonate diol and poly (tetramethylene / hexamethylene) carbonate diol.

  Mn of the polymer diol (a2) is usually 500 or more, preferably 500 to 4,000, from the viewpoint of texture.

  As the chain extender (a3), the divalent alcohol having 2 to 20 carbon atoms, water, diamine having 2 to 10 carbon atoms (for example, ethylenediamine, propylenediamine, hexamethylenediamine, isophoronediamine, toluenediamine and piperazine), poly (N = 2-6) alkylene (2-6 carbon atoms) poly (n = 3-7) amine (diethylenetriamine, dipropylenetriamine, dihexylenetriamine, triethylenetetramine, tetraethylenepentamine, pentaethylenehexamine and hexa Ethylene heptamine etc.), hydrazine or derivatives thereof (dibasic acid dihydrazide such as adipic acid dihydrazide etc.) and amino alcohols having 2 to 10 carbon atoms (eg ethanolamine, diethanolamine, 2-amino-2-methylpropanol and Ethanolamine) and the like.

  The chain extender (a3) other than (a1) is preferably a dihydric alcohol having 2 to 20 carbon atoms, water, or a diamine having 2 to 10 carbon atoms from the viewpoint of handling of the resin solution and synthesis.

  As the reaction terminator (a4), monoalcohols having 1 to 8 carbon atoms (methanol, ethanol, isopropanol, cellosolves, carbitols, etc.), monoamines having 1 to 10 carbon atoms (monomethylamine, monoethylamine, mono Mono- or dialkylamines such as butylamine, dibutylamine and monooctylamine, and mono- or dialkanolamines such as monoethanolamine, diethanolamine and diisopropanolamine).

The weight of the polyamine (a1) is preferably 15 to 90% by weight with respect to the total weight of the polyamine (a1) and the polymer polyol (a2), preferably 30 to 90% by weight, more preferably 50 to 50% from the viewpoint of moisture permeability. 90% by weight.

  As the organic isocyanate component (B) in the present invention, those conventionally used for the production of polyurethane can be used, and an aromatic polyisocyanate having 8 to 26 carbon atoms having 2 to 3 or more isocyanate groups (b1). ), C4-C22 chain aliphatic polyisocyanate (b2), C8-C18 alicyclic polyisocyanate (B3), C10-C18 araliphatic polyisocyanate (b4), and these Examples include a modified polyisocyanate (b5). An organic isocyanate component (B) may be used individually by 1 type, and may use 2 or more types together.

  Examples of the aromatic polyisocyanate (b1) having 8 to 26 carbon atoms include 1,3- or 1,4-phenylene diisocyanate, 2,4- or 2,6-tolylene diisocyanate (hereinafter referred to as tolylene diisocyanate as TDI). Abbreviation), crude TDI, 4,4′- or 2,4′-diphenylmethane diisocyanate (hereinafter, diphenylmethane diisocyanate is abbreviated as MDI), crude MDI, polyarylpolyisocyanate, 4,4′-diisocyanatobiphenyl, 3, 3'-dimethyl-4,4'-diisocyanatobiphenyl, 3,3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 1,5-naphthylene diisocyanate, 4,4 ', 4 "-triphenyl Methane triisocyanate and m- or p-isocyanatophenylsulfonyl Cyanate and the like.

  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, bis (2-isocyanatoethyl) carbonate and 2-isocyanatoethyl- 2,6-diisocyanatohexanoate is mentioned.

  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.

  As the modified polyisocyanate (b5) of (b1) to (b4), the modified polyisocyanate (urethane group, carbodiimide group, allophanate group, urea group, biuret group, uretdione group, uretoimine group, isocyanurate group) Or modified product containing oxazolidone group, etc .; free isocyanate group content is usually 8 to 33% by weight, preferably 10 to 30% by weight, especially 12 to 29% by weight), such as modified MDI (urethane modified MDI, carbodiimide modified MDI) And modified products of polyisocyanates such as urethane-modified TDI, biuret-modified HDI, isocyanurate-modified HDI, and isocyanurate-modified IPDI.

Of the organic polyisocyanate component (B), aromatic polyisocyanates having 8 to 26 carbon atoms are preferred from the viewpoint of tensile strength, and more preferred are TDI, crude TDI, MDI, crude MDI, and these isocyanates. Particularly preferred are MDI, crude MDI and a total content of these modified products of 10% by weight or more (particularly 15 to 80% by weight). The isocyanate group content (NCO%) of the organic polyisocyanate component (B) as a whole is preferably 25 to 45% by weight.
The ratio of the active hydrogen component (A) to the total weight of the active hydrogen component (A) and the organic polyisocyanate component (B) is preferably 17 to 57% by weight, more preferably 27 to 47% by weight.

  The weight average molecular weight (hereinafter abbreviated as Mw) of the polyurethane resin (U) for moisture permeable and waterproof material of the present invention is preferably 50,000 to 1,000,000, more preferably 100, from the viewpoint of improving tensile strength. 000-500,000.

  The Mw of the polyurethane resin in the present invention is measured by gel permeation chromatography using dimethylformamide (hereinafter abbreviated as DMF) as a solvent and polystyrene as a standard substance. The sample concentration may be 0.25 wt%, the column stationary phase may be TSKgel SuperH2000, TSKgel SuperH3000, TSKgel SuperH4000 (both manufactured by Tosoh Corporation), and the column temperature may be 40 ° C.

  The manufacturing method of the polyurethane resin (U) for moisture-permeable waterproof materials of this invention is not specifically limited, It can manufacture by a well-known method etc. For example, the active hydrogen component (A) and the organic polyisocyanate component (B) and, if necessary, an organic solvent and an additive may be charged and reacted, or the polyol (a2), the chain extender (a3), and the poly After the isocyanate component (B) is reacted to obtain an isocyanate group-terminated prepolymer, the elongation reaction may be carried out using the polyamine (a1) as a chain extender, or the polyamine (a1), the polyol (a2) and the polyamine You may make it react with a chain extender (a3), after making it react with an isocyanate component (B) and obtaining the prepolymer of an isocyanate group terminal. In these reactions, a reaction terminator (a4) may be added as necessary after completion of the reaction, or the above reaction can be carried out in the absence of a solvent by using a kneader or the like as a reaction apparatus.

  The polyurethane resin (U) for moisture permeable and waterproof material of the present invention can be used as an organic solvent solution by mixing with an organic solvent if necessary. Moreover, the polyurethane resin composition (W) of this invention can contain an organic solvent if needed.

  Examples of the organic solvent include solvents that do not contain an 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 polyurethane resin (U) of the present invention can be used by adding pigments, stabilizers and other additives (such as anti-fusing agents and flame retardants) as necessary.

  It does not specifically limit as a pigment, A well-known organic pigment and / or an inorganic pigment can be used, and it is 0-5 weight% normally with respect to a polyurethane resin, Preferably it mix | blends 0.1-3 weight%. 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.

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 to 3% by weight based on the polyurethane resin. The
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.

  The pigment, stabilizer and other additives can be added at any stage during the production of the polyurethane resin, and may be added after the production.

  The polyurethane resin (U) of the present invention is used for a polyurethane resin layer of a moisture permeable waterproof material, which 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. In addition, as the 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.

  The moisture permeable and waterproof material using the polyurethane resin (U) of the present invention includes outdoor wear, ski related wear, windbreaker, athletic wear, golf wear, rain wear, casual coat, outdoor work clothes, etc. It can be suitably used for climbing tools such as gloves, shoes and tents.

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

Production Example 1 [Production of polyamine (a1-1)]
A stainless steel reaction kettle equipped with a stirrer and temperature controller was charged with 37 parts of diethylenetriamine and 108 parts of methyl isobutyl ketone, and reacted at 120 ± 5 ° C. for 10 hours while distilling off the generated water from the reaction system. A ketimine compound obtained by ketiminating the terminal amino group with methyl isobutyl ketone was obtained. After excess methyl isobutyl ketone was distilled off, 2 parts of the ketimine compound and potassium hydroxide were charged into a stainless steel autoclave equipped with a stirrer and a temperature controller, and the pressure in the reaction vessel was reduced to 0.01 MPa. Next, 812 parts of EO was blown in at 21 ± 10 ° C. over 21 hours to obtain a compound in which EO was added to the imino group of the ketimine compound. Subsequently, 43 parts of phenyl isocyanate was charged and reacted with a hydroxyl group at the terminal end of the alkylene oxide group. Subsequently, the mixture was transferred to a stainless steel reaction kettle equipped with a stirrer and temperature controller, charged with 20 parts of ion exchange water and stirred at 90 ° C. for 1 hour, and then transferred to a stainless steel kettle equipped with a stirrer and temperature controller, followed by ion exchange. 150 parts of water was charged and methyl isobutyl ketone produced at 90 ± 5 ° C. was reacted for 10 hours while distilling out of the reaction system, followed by dehydration under reduced pressure to obtain polyamine (a1-1).

Production Examples 2 to 6 [Production of Polyamines (a1-2) to (a1-9)] Polyamines (a1-2) to (a) were produced in the same manner as in Production Example 1 except that the raw materials used were changed to those shown in Table 2. a1-6) was obtained. In addition, about polyamine (a1-3, a1-6), after blowing all the propylene oxide, all the ethylene oxide was blown.

Example 1 [Production of polyurethane resin (U-1) solution]
In a reaction vessel equipped with a stirrer and a temperature controller, 17 parts of polytetramethylene ether glycol (“PTMG2000” manufactured by Mitsubishi Chemical Corporation; Mn 2,000, hydroxyl value 56.1) as a polymer diol (a2), chain extension The mixture was charged with 22 parts of ethylene glycol as the agent (a3), 347 parts of DMF as the organic solvent and 110 parts of diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) as the organic polyisocyanate component (B). The reaction was performed at ± 3 ° C. for 3 hours. Subsequently, 504 parts of a 30% DMF solution of diamine (a1-1) as polyamine (a1) was added dropwise at 30 ° C. with stirring, and further subjected to an extension reaction at 30 ° C. for 1 hour, to obtain a polyurethane resin (U-1). A 30% DMF solution was obtained.

Examples 2 to 19 [Production of polyurethane resin (U-2) to (U-19) solutions]
Polyurethane resin (U-2) to (U-19) solutions were obtained in the same manner as in Example 1 except that the raw materials used were changed to those shown in Tables 3 and 4.

Comparative Example 1 [Production of polyurethane resin (U′-1) solution]
In a reaction vessel equipped with a stirrer and a temperature control device, 135 parts of polyethylene glycol (“PEG2000” manufactured by Sanyo Chemical Industries, Ltd .; Mn 2,000, hydroxyl value 56.1) as a polymer diol (a2) and polytetramethylene ether 34 parts of glycol ("PTMG2000" manufactured by Mitsubishi Chemical Corporation; Mn 2,000, hydroxyl value 56.1), 17 parts of ethylene glycol as chain extender (a3), 690 parts of DMF as organic solvent, and organic polyisocyanate component (B ) 110 parts of diphenylmethane diisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd.) was prepared, and the reaction was carried out in a nitrogen atmosphere at normal pressure and 60 ± 3 ° C for 3 hours. Subsequently, 14 parts of a 30% DMF solution of ethylenediamine as a polyamine (a1 ′) for comparison was added dropwise at 30 ° C. with stirring, and further an extension reaction was performed at 30 ° C. for 1 hour to obtain a polyurethane resin (U′-1). A 30% DMF solution was obtained.

Comparative Example 2 [Production of polyurethane resin (U′-2) to (U′-4) solution]
A polyurethane resin (U′-2) to (U′-4) solution was obtained in the same manner as in Comparative Example 1 except that the raw materials used were changed to those shown in Table 4.

In addition, the composition of the raw material represented by the trade name in Tables 3 to 5 is as follows.
PTMG2000: Poly (oxytetramethylene) glycol (hydroxyl value 56.1) with Mn = 2,000 [manufactured by Mitsubishi Chemical Corporation]
Sanester 4620: Polyester (hydroxyl value 56.1) of Mn = 2,000 obtained from adipic acid and 1,4-butanediol [manufactured by Sanyo Chemical Industries, Ltd.]
PEG2000: polyethylene glycol with Mn = 2,000 (hydroxyl value 56.1) [manufactured by Sanyo Chemical Industries, Ltd.]

  The results of moisture permeability and water pressure resistance measured using the polyurethane resin solutions obtained in Examples 1 to 19 and Comparative Examples 1 to 4 are shown in Table 3, Table 4, Table 5, and FIG. Each measurement was performed by the following method.

[1] Method for measuring moisture permeability A polyurethane resin solution or polyurethane resin composition is applied to a release-treated glass plate to a thickness of 33 μm and dried in a circulating dryer at 70 ° C. for 3 hours. By peeling off, a film for measuring moisture permeability having a thickness of 10 μm was produced. The moisture permeability of the obtained film for measuring moisture permeability was measured based on the JIS L-1099-1998 calcium chloride method (A-1).

[2] Measuring method of water pressure resistance About the test piece produced like the film for the above-mentioned moisture permeability measurement, water pressure resistance was measured according to JIS L1092-1998 high water pressure resistance method. When the test piece was stretched by applying water pressure, a nylon taffeta (density: warp yarn + weft yarn = 210 yarns / 2.54 cm equivalent) was overlaid on the test piece, and then attached to a tester for measurement.

[3] Water swelling ratio A polyurethane resin solution or a polyurethane resin composition is applied to a release-treated glass plate to a thickness of 660 μm, dried in a circulating dryer at 60 ° C. for 3 hours, and then peeled off from the glass plate. Thus, a film having a thickness of 200 μm was prepared.
Cut out a test piece with a width of 1 cm and a length of 10 cm from the film, draw two marked lines with an interval of 8 cm between them, and measure the distance L (cm) between the marked lines after being immersed in ion-exchanged water for 2 hours to swell. It was.
The water swelling rate (%) was calculated from the following formula.
Water swelling rate (%) = {(L-8) / 8} × 100

As shown to the said Tables 3-5, the moisture permeability / water swelling rate of the polyurethane resin (U) for moisture-permeable waterproofing materials of this invention and Examples 1-19 is large compared with Comparative Examples 1-4. That is, it was found that the resin had excellent moisture permeability and water swelling was suppressed.
This is clear from FIG.

  The polyurethane resin for moisture permeable and waterproof material (U) of the present invention is used for outdoor wear, ski-related wear, windbreaker, athletic wear, golf wear, rain wear, casual coat, outdoor work clothes, gloves, etc. It is particularly useful for the manufacture of moisture permeable and waterproof materials used for climbing tools such as shoes and tents.

Claims (6)

For moisture permeable and waterproof material obtained by reacting active hydrogen component (A) containing polyamine (a1) represented by general formula (1) and polymer polyol (a2) with organic polyisocyanate component (B) Polyurethane resin (U).

[In formula, R < ¹ > and R < ² > represents a C2-C10 alkylene group each independently, and a represents the integer of 1-5. (X1) represents an ethyleneoxy group, (x2) represents an alkyleneoxy group having 3 to 12 carbon atoms, and a plurality of (x2) may be the same or different. When b is an integer of 5 to 200, c is an integer of 0 to 195, 5 ≦ b + c ≦ 200 is satisfied, and c is 1 or more, b (x1) and c (x2) bonds The format may be random, block, or a combination of these. ]   The polyurethane resin for moisture-permeable and waterproof material according to claim 1, wherein b is 40 to 200 and c is 0 in the general formula (1).   The polyurethane resin for moisture permeable and waterproof material according to claim 1 or 2, wherein a in the general formula (1) is 1.   The weight ratio of the ethyleneoxy group (x1) in the polyamine (a1) represented by the general formula (1) based on the total weight of the active hydrogen component (A) and the organic polyisocyanate component (B) is 20 to 45. The polyurethane resin for moisture-permeable and waterproof material according to any one of claims 1 to 3, wherein the polyurethane resin is weight%.   The weight ratio of the ethyleneoxy group in the polyamine (a1) represented by the general formula (1) to the weight of the ethyleneoxy group in the active hydrogen component (A) is 70 to 100% by weight. The polyurethane resin for moisture-permeable and waterproof material according to any one of the above. The moisture-permeable waterproof material containing the polyurethane resin for moisture-permeable waterproof materials of any one of Claims 1-5.

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