TWI292407B - Polyurethane with hydrophilic side chain - Google Patents

Description

1292407 IX. Description of the Invention: TECHNICAL FIELD OF THE INVENTION The present invention relates to a waterproof and breathable material, and more particularly to a waterproof and breathable material having a polyurethane having a hydrophilic side chain. [Prior Art] In the development of waterproof and breathable materials, the first materials proposed were polyvinyl chloride (PVC), polyethylene, polychloroprene rubber and various other synthetic rubbers. The materials of the above materials have good waterproof performance. However, due to its poor moisture permeability, when the human body wears the garment made of the above materials, a large amount of sweat cannot be discharged in the form of water vapor, and condensed water is formed inside the garment, resulting in discomfort such as wet adhesion and sultry heat. Later developed Gore-Tex material, stretched PTFE film (expanded)

Polytetrafluoroethylene, ePTFE), excellent waterproof and breathable work

Yes, but the price is very expensive. In addition, thermoplastic polyurethane (TPU) coatings and laminated fabrics have good waterproof and breathable properties, and the development is also very fast, especially thermoplastic polyurethane materials have good wear resistance, chemical and hydrolysis resistance, insect proof and mold, Low temperature resistance, easy coloring, and a wide range of processing operations. In view of this, it is still necessary to study new polyurethane materials to increase their waterproof and breathable properties and mechanical strength, and to meet the industrial needs. SUMMARY OF THE INVENTION In view of the above-described background of the invention, in order to meet the industrial needs, the present invention provides a novel waterproof and breathable material having a polyurethane having a hydrophilic side chain. Page 6 of 22 Page 1292407 The purpose of this book is to introduce a hydrophilic side bond into the polyurethane material. When the film is formed, the hydrophilic side chains will attract each other and gather, thereby forming a Xuxiang on the film. The local hydrophilic region, through the hydrophilicity, functions as a moisture permeable gas by the adsorption-diffusion (diffusi〇n)-desorption (des〇_〇n) action of the water molecules. Another object of the present invention is to design the degree of polymerization and content of hydrophilic side chains so that

The glass transition temperature (Tg) of the hydrophilic side chain is in a temperature range in which the human body feels comfortable, so that when the ambient temperature is higher than that of the hydrophilic side chain, the hydrophilic side chain produces a phase change endotherm while the hydrophilic side chain thermal motion Intensified, the amount of moisture vapor transmission is increased, the heat exhaustion is accelerated, and the person feels cool; when the ambient temperature is lower than the Tg of the hydrophilic side chain, the hydrophilic side chain produces a phase change exotherm, and at the same time, the hydrophilic side chain thermal motion is reduced. Small, low ventilation performance' has a windshield insulation effect. Therefore, the material provided by the present invention can provide moisture permeability or wind-proof heat preservation function according to changes in ambient temperature, so that the human body feels comfortable under various types of earthen brothers. A further object of the present invention is to introduce a high strength, hydrophobic polyol onto the polyurethane backbone to enhance the mechanical properties (e.g., hardness, elasticity, tensile strength) of the material. Accordingly, the present invention can meet economic benefits and industrial applicability. In accordance with the above objects, the present invention discloses a polyurethane permeable gas permeable material having a hydrophilic side chain comprising a polyurethane backbone and a hydrophilic side chain. The polyaminophthalate backbone further comprises a hard segment and a soft segment, wherein the hard segment is formed by the reaction of a diisocyanate and a chain extender, and the soft page 7/22 1292407 The segment is formed by polyalcohols. Next, one end of the above hydrophilic side chain is covalently bonded to the polyurethane backbone, and the other end of the hydrophilic side chain is in a freely active state. . [Embodiment]

The direction of the invention discussed herein is a waterproof, breathable material having a hydrophilic side chain polyurethane. In order to thoroughly understand the present invention, detailed process steps or constituent structures will be set forth in the following description. Obviously, the invention is not limited to the specific details familiar to those skilled in the art. On the other hand, well-known components or process steps are not described in detail to avoid unnecessarily limiting the invention. The preferred system of the present invention will be described in detail below, but the present invention may be widely practiced in other systems in addition to the detailed description, and the scope of the present invention is not limited by the scope of the following patents. One embodiment of the present invention discloses a waterproof gas permeable material having a polyurethane having a hydrophilic side chain comprising a polyurethane backbone and a hydrophilic side chain. The polyurethane backbone further comprises a hard segment and a soft segment, wherein the hard segment is formed by reacting a bisisocyanate and a chain extender. The soft segments are formed from polyalcohols. Next, one of the above-mentioned hydrophilic side chains is covalently bonded to the polyurethane backbone, and the other end of the hydrophilic side chain is free-acting. The above hydrophilic side chains have a molecular weight of between about 200 and 3,000. Further, the above-mentioned bis-isocyanate further comprises one of the following groups or any combination thereof: Page 8 of 22 1292407 (1) aromatic polyisocyanates: tolylene diisocyanate (TDI) (2,4- or 2,6 -TDI), diphenylmethane diisocyanate (MDI) (4?4'- or 2,4 丨-MDI), polymeric MDI, xylylene diisocyanate (XDI), naphthylene diisocyanate (NDI) (usually 1,5-NDI), paraphenylene diisocyanate ( PPDI), tetramethylxylylene diisocyanate (TMXDI), tolidine diisocyanate (TODI), 3,3丨-dimethoxy-4,4'-biphenylene diisocyanate 〇dicyclohexylmethane 2,4'-HMDI),isophorone (IPDI),

(2) alicyclic polyisocyanates: diisocyanate (HMDI)(4,4'- or diisocyanate isopropylidene_bis-(4-cyclohexylisocyanate)(IPC), hydrogenated xylylene diisocyanate (hydrogenated XDI)? cyclohexylene diisocyanate (CHPI) (usually 1,4-CHPI) , l,5-tetrahydonaphthalene diisocyanate 〇(3) aliphatic polyisocyanates: hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), tetramethylene diisocyanate 〇 On the other hand, the above polyalcohols further comprise polyester polyols and copolymers thereof, E.g:

Polycaprolactone (PCL), Polybutylene-adipate glycol (PBA)? Polyhexylene-adipate glycol (PHA) 〇 More preferably, the polyurethane backbone described above may also comprise a hydrophilic segment, which is comprised of the following populations; One of them is formed: (1) a polyether polyglycol compound and a copolymer thereof, for example, poly(ethylene oxide) Glycol; PEG, poly(propylene oxide) (Poly(propylene oxide) ) Glycol; PPG), polyoxytetramethyl glycol, page 9 / total 22 pages 1292407

Poly(tetramethylene oxide) Glycol (PTMEG (2) polycarbonate type polyglycol compound and its copolymer, such as Polycarbonate Glycol. In a preferred embodiment of this embodiment, the formation of the above hydrophilic side chain To include an intermediate formation step, the formation step of the intermediate is a reaction

a compound of an isocyanato group and a hydrophilic polymer having at least three reactive functional groups, wherein the compound having a single isocyanate group and a hydrophilic polycondensation having at least three reactive functional groups The molar ratio of the object is 1:1, such that the intermediate formed has at least two reactive functional groups, and at least two reactive functional groups of the intermediate can be used to form a polyurethane backbone The hard segment of the double isocyanate reacts thereby forming a hydrophilic side chain. The above compound having a single isocyanate group further contains an alkyl isocyanate, an ary isocyanate and an arylaikyl isocyarLate. Further, the above reactive functional group further comprises one of the following groups: a hydroxyl group, a carboxyl group and an amine group. On the other hand, the above hydrophilic oligomer having at least three reactive functional groups further comprises one of the following groups: poly(oxyethylene) glycol, poly(propylene glycol) poly(B) a copolymer of poly(oxypropylene) poly(OXyethylene) triol, styrene sulfonic acid, and 4-amino styrene. In another preferred embodiment of the present embodiment, the formation of the hydrophilic side chain described above is 10th/total 22 pages 1292407

The method comprises the steps of: firstly providing and reacting a compound having a single isocyanate group and a hydrophilic oligomer having two first reactive functional groups to form a first intermediate, wherein the above has a single The isocyanate group-containing compound further includes an alkyl isocyanate, an aryl isocyanate, and an arylalkyl isocyanate. The molar ratio of the above compound having a single isocyanate group to the hydrophilic polymer having two first reactive functional groups is 1:1, so that the first intermediate formed has a first reaction Sex functional group. Then, a pair of isocyanates are provided, and the bisisocyanate is reacted with the first intermediate to form a second intermediate, wherein the molar ratio of the bisisocyanate to the first intermediate is 1: 1, such that the second intermediate formed has one isocyanate group. After forming the second intermediate as described above, providing a compound having at least three second reactive functional groups, and reacting a compound having at least three reactive functional groups with a second intermediate to form a third intermediate, Wherein the molar ratio of the compound having at least three second reactive functional groups to the second intermediate is 1:1, such that the third intermediate formed has at least two second reactive functional groups, and The at least two second reactive functional groups of the third intermediate may be reacted with a bisisocyanate used to form a hard segment of the polyurethane backbone, thereby forming a hydrophilic side chain. The first and second reactive functional groups described above are independently selected from one of the group consisting of a hydroxyl group, a carboxyl group and an amine group. Further, the above hydrophilic polymer having two first reactive functional groups further comprises one of the following groups: Page 11 of 22 1292407 (1) Polyether polyglycol compounds and copolymerization thereof For example, poly(ethylene oxide Glycol; PEG), poly(propylene oxide Glycol; PPG), polyoxytetramethyl glycol w Poly (tetramethylene oxide Glycol (PTMEG) 〇 (2) Polycarbonate type polyglycol compound and its copolymer, for example: Polycarbonate Glycol 〇 On the other hand, the above compound having at least three second reactive functional groups further comprises the following groups Towels: dimethyl (2,2-bis(hydroxymethyl) propionic acid; DMPA), 2,6-diaminohexanoic acid (Lysin-HC1), trimethylolpropane, glycerol, pentaerythritol In another preferred embodiment, the method for forming the hydrophilic side chain comprises the steps of: firstly, providing and reacting a compound having a single isocyanate group and a hydrophilic polymer having two reactive functional groups; Forming a first The molar ratio of the compound having a single isocyanato group to the hydrophilic oligomer having two reactive functional groups is 1:1, so that the first intermediate formed has a reaction Sex functional group. Next, a compound having at least three isocyanato groups is provided, and a compound having at least three isocyanato groups is reacted with the first intermediate to form a second intermediate having at least three isocyanato groups. The molar ratio of the compound to the first intermediate is 1:1, such that the second intermediate formed has at least two isocyanato groups, and at least two isocyanato groups of the second intermediate can be A polyalcohol which forms a soft segment of a polyurethane backbone on page 12 of 2292407 or a chain extender reaction for forming a hard segment of a polyurethane backbone, thereby forming a hydrophilic Sexual side chain. The above compound having a single isocyanate group further includes an alkyl isocyanate, an aryl isocyanate, and an arylalkyl isocyanate. Further, the above reactive functional group further comprises one of the following groups: a hydroxyl group, a carboxyl group and an amine group. In another aspect, the above compound having at least three isocyanato groups further comprises one of the following groups: trimethylbenzyl triisocyanate, triisothiocyanate, benzyl triiso(thio)cyanate, triphenylmethane-4,4 ' ,4 ” -triisocyanate , 1,2,4-benzene triisocyanate, triphenyl triisocyanate, benzene triisocyanate, toluene triisocyanate, 1,3,5-cyclohexane triisocyanate, lysine ester triisocyanate, hexamethylene 1,3,6-trisisocyanate, bicycloheptane triisocyanate,biuret triisocyanate o

In the above embodiment of the present invention, the water vapor permeability (Water Vapor Permeability, unit (g/m2/day)) and the degree of swelling of the above-mentioned polyurethane having a hydrophilic side chain are along with the hydrophilic side chain. The content increases and increases. In the present invention, by introducing a hydrophilic side chain into a polyurethane material, when the film is formed, the hydrophilic side chains are attracted to each other to aggregate, thereby forming a plurality of local hydrophilic regions on the film, and transmitting the hydrophilic region. Absorption-diffusion-desorption of water molecules to achieve moisture permeability. In addition, by designing the degree of polymerization and content of the hydrophilic side chain, the glass transition temperature (Tg) of the hydrophilic side chain of the hydrophilic page 13 is in a comfortable temperature range of the human body, so as to be suitable for the ambient temperature. When the Tg is higher than the hydrophilic side chain, the hydrophilic side chain produces a phase change - endotherm, while the hydrophilic side chain heat movement is intensified, so that the moisture permeability is increased, the heat wicking w is accelerated, and the person feels cool; when the ambient temperature When the Tg of the hydrophilic side chain is lower than that of the hydrophilic side chain, the hydrophilic side chain generates a phase change exotherm, and at the same time, the hydrophilic side chain thermal motion is reduced, the gas permeability is lowered, and the wind retaining effect is provided. Therefore, the material provided by the present invention can provide moisture permeability or wind-proof heat preservation function according to changes in ambient temperature, so that the human body feels comfortable under various environmental conditions. On the other hand, the present invention introduces a highly hydrophobic, hydrophobic polyol on the polyurethane backbone to enhance the mechanical properties (e.g., hardness, elasticity, tensile strength) of the material. Accordingly, the present invention can meet economic benefits and industrial applicability.

In summary, the present invention discloses a waterproof gas permeable material having a polyurethane having a hydrophilic side chain comprising a polyurethane backbone and a hydrophilic side chain. The polyurethane backbone further comprises a hard segment and a soft segment, wherein the hard segment is formed by the reaction of a bisisocyanate and a chain extender, and the soft segment is composed of a polyalcohol. Formed. Next, one end of the above hydrophilic side chain is covalently bonded to the polyurethane backbone, and the other end of the hydrophilic side chain is freely active. Obviously, the invention may have many modifications and differences in accordance with the description in the above system. It is therefore to be understood that within the scope of the appended claims, the invention may be The foregoing is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. It is intended to limit the scope of the present invention. The scope of the patent is not limited to the equivalent changes made without departing from the spirit of the present invention. Or modifications should be included in the scope of the following patent application. [Simple description of the map]

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Claims (1)

1292407 X. Patent application scope: 1. A polyaminophthalic acid ester having a hydrophilic side chain, the polyurethane having a hydrophilic side chain comprising a polyaminophthalic acid ester main chain, the polyaminocarbamide The acid ester backbone further comprises a hard segment and a soft segment, wherein the hard segment is formed by reacting a bisisocyanate with a chain extender, and the soft segment is formed by a polyalcohol; And a hydrophilic side chain, wherein one end of the hydrophilic side chain is covalently bonded to the polyaminophthalate backbone, and the other end of the hydrophilic side chain is φ freely active. 2. The polyurethane having a hydrophilic side chain according to claim 1, wherein the above-mentioned bisisocyanate further comprises one of the following groups or any combination thereof (1) aroma Aromatic polyisocyanates: toluene 2, 4 (or 2, 6)-diisocyanate (t〇lylene (1; ^3〇〇731^7, 01) (2,4-〇 factory 2, 6-butyl 1) 1), diphenylmethane 4,4' (or 2,4')-diphenylmethane diisocyanate (MDI) (4,4'- or 2,4'- MDI), polymeric MDI, xylylene diisocyanate (XDI), naphthalene diisocyanate (usually 1,5-naphthalene diisocyanate) (naph1:hylene diisocyanate) (NDI) (usually 1,5-NDI), paraphenylene diisocyanate (PPDI), tetramethylxylylene di isocyanate (TMXDI), tolidine diisocyanate (TODI) ), 3,3〆-dimercapto-4,4bi-bisphenyl isocyanate (3,3'-dimethoxy-4, 4'-biphenylene diisocyanate (2) alicyclic polyisocyanates: dicyclohexylmethane diisocyanate (HMDI) (4, 4,- or 2, 4'-HMDI), isophorone double page 16 / total 22 pages 1292407 isocyanate (isophorone diisocyanate, IPDI), isopropylene bis (4-cyclohexyl isocyanate SI) isopropylidene-bis- ( 4-cyclohexyl isocyanate) (IPC), hydrogenated xylylene di isocyanate (hydrogenated XDI), cyclohexylene diisocyanate (CHPI) (usually 1,4_CHPI), 1,5 -4 1,5-tetrahydonaphthalene diisocyanate 〇 (3) Ali iphatic poly isocyanates: hexamethylene diisocyanate (HDI), lysine diisocyanate (LDI), tetradecylbenzene diisocyanate _ ( Tetramethylene di isocyanate). 3. The polyaminophthalic acid ester having a hydrophilic side chain as described in claim 1, wherein the polyalcohol further comprises a polyester polyol and a copolymer thereof, for example: Polycaprolactone (PCL), Poly (butylene-adipate glycol (PBA), Poly (hexylene-adipate glycol (PHA). 4. Polyaminophthalate having a hydrophilic side chain as described in claim 1, wherein the hydrophilic side chain is The method for forming comprises an intermediate forming step of reacting a compound having a single isocyanate group with a hydrophilic oligomer having at least three reactive functional groups, wherein the single layer has a single The molar ratio of the isocyanate group compound to the hydrophilic oligomer having at least three reactive functional groups is 1:1, such that the intermediate has at least two reactive functional groups, and the intermediate At least two reactive functional groups may be reacted with a bisisocyanate used to form a hard segment of the polyurethane backbone, thereby forming the hydrophilic side bond. 5. As claimed in the fourth item Said having The water-soluble side chain of the polyaminol group 17 / 22 pages 1292407 acid ester, wherein the above reactive functional group further comprises one of the following groups: hydroxyl group, carboxyl group and amine group. The polyurethane having a hydrophilic side chain, wherein the method for forming the hydrophilic side chain comprises: providing and reacting a compound having a single isocyanate group and having two first reactive functional groups a hydrophilic oligomer to form a first intermediate, wherein the molar ratio of the compound having a single isocyanate group to the hydrophilic oligomer having the two first reactive functional groups is 1: 1 such that the first intermediate has a first reactive functional group; a double isocyanate is provided, and the bis-isocyanate is reacted with the first intermediate to form a second intermediate, wherein The molar ratio of the bis-isocyanate to the first intermediate is 1:1 such that the second intermediate has an isocyanate group; and the provision of at least three second reactive functional groups Compound, and reacts to have at least three a compound of a reactive functional group and the second intermediate to form a third intermediate, wherein the molar ratio of the compound having at least three second reactive functional groups to the second intermediate is 1:1 So that the third intermediate has at least two second reactive functional groups, and at least two second reactive functional groups of the third intermediate can be used to form the polyurethane backbone hard chain The bis-isocyanate reaction of the segment, thereby forming the hydrophilic side chain. 7. The polyurethane having a hydrophilic side chain according to claim 6, wherein the first and second The reactive functional groups are independently selected from one of the following groups: a hydroxyl group, a carboxyl group, and an amine group. 8. The polyurethane having a hydrophilic side chain according to claim 6, wherein the hydrophilic oligomer having the two first reactive functional groups further comprises one of the following groups (1) Polyether-based polyglycol compounds and copolymers thereof, for example, polyoxyethylene glycols, page 18 of 22 (Poly(ethylene oxide) Glycol; PEG), polyoxypropylene glycol ( Poly(propylene oxide) Glycol; PPG),? Tetraoxyethylene Glycol (PTMEG). (2) a polycarbonate type polyglycol compound and a copolymer thereof, for example: Polycarbonate Glycol 〇9. The polyaminophthalic acid ester having a hydrophilic side chain as described in claim 6 wherein the above has The compound of at least three second reactive functional groups further comprises one of the following groups: 2,2-bis(hydroxymethyl) propionic acid; DMPA, 2,6-dioxahexanoic acid (Lysin-HCl), a trimethylolpropane, a glycerol, a pentaerythritol, a polyurethane having a hydrophilic side chain as described in claim 1, wherein the method for forming the hydrophilic side chain comprises: Reacting a compound having a single isocyanate group and a hydrophilic oligomer having two reactive functional groups to form a first intermediate 'wherein the compound having a single isocyanate group has two reactions The hydrophilic polymerizable polymer has a molar ratio of 1:1 such that the first intermediate has a reactive functional group; and a compound having at least three isocyanate groups is provided and reacted a compound having at least three isocyanato groups and the first intermediate to form a second intermediate, wherein the molar ratio of the compound having at least three isocyanato groups to the first intermediate is 1 :1 such that the second intermediate has at least two isocyanato groups, and at least two isocyanato groups of the second intermediate may be used to form the polyurethane backbone soft segment. The chain extender reaction of the polyol or hydrazine to form the hard segment of the polyurethane backbone 'defects' forms the hydrophilic side chain. 11. The polyaminophthalic acid ester having a hydrophilic side chain according to claim 10, wherein the reactive functional group further comprises the following group of 19th page/22 pages 1292407: one basis , Wei Ke and amine base. 12. The polyaminophthalic acid ester having a hydrophilic side chain as described in claim 1, wherein the compound having at least three isocyanato groups further comprises one of the following groups: trimethyl Trimethylbenzyl triisocyanate, triisothiocyanate, benzyl triiso(thio)cyanate, benzotriene-4,4 ',4''-triisocyanate (triphenylmethane) -4,4 >,4"- tri isocyanate), 1,2,4-benzene triisocyanate, triphenyl tri isocyanate, trisocyanate benzene Isocyanate), toluene tri isocyanate, 1,3,5-cyclohexane triisocyanate, lysine ester tri isocyanate, six Hexylylene 1,3,6-triisocyanate, bicycloheptane triisocyanate, biuret triisocyanate . 13. The water vapor transmission rate of the hydrophilic side chain polyurethane of the hydrophilic side chain as described in claim 1 of the patent scope [Water Vapor Permeability, unit (g/) M2/day)] increases as the hydrophilic side chain content increases. 14. Polyurethane having a hydrophilic side chain as described in claim 1, wherein the polyurethane having a hydrophilic side bond increases in swelling degree as the hydrophilic side chain content increases. The polyurethane having a hydrophilic side chain as described in claim 1, wherein the polyaminophthalate backbone further comprises a hydrophilic segment. Page 20 of 22 1292407* 16. For the application of the surface water (4) polyurethane according to paragraph 15 of the above, wherein the hydrophilic segment is by one of the following groups Forming: (1) a polyether oxime polyol compound and a copolymer thereof, for example, poly(ethylene oxide Glycol; PEG), poly(propylene oxide glycol) (Poly(propylene oxide) Glycol; PPG), poly(tetramethylene oxide) Glycol (PTMEG) 〇 (2) Polycarbonate type polyglycol compound and its copolymer, for example: Polycarbonate Glycol 〇 Page 21 of 22 1292407 XI. Graphic: Page 22 of 22