Moisture-curing polyurethane resin composition, adhesive, and laminate

Abstract

The present invention provides a moisture-curable polyurethane hot melt resin composition containing a urethane prepolymer (i) having an isocyanate group that is a reaction product of a polyol (A) and a polyisocyanate (B), wherein the polyol (A) contains a biomass-derived polytetramethylene glycol or polycarbonate polyol (a1), a polyol (a2) having an aromatic ring, and a polyester polyol (a3) that is solid at room temperature other than (a2). The present invention also provides an adhesive characterized by containing said moisture-curable polyurethane resin composition. The present invention also provides a laminate characterized by having at least a substrate and a cured product of said moisture-curable polyurethane resin composition.

Description

Technical Field

[0001] The present invention relates to a moisture-curable polyurethane resin composition, an adhesive, and a laminate.

Background Art

[0002] A moisture-permeable and waterproof functional clothing having both moisture permeability and waterproofness is a structure in which a moisture-permeable film is bonded to a fabric with an adhesive. As the adhesive, a urethane-based adhesive is generally used because of its good adhesion to both the moisture-permeable film and the fabric. Among the urethane-based adhesives, the use amount of a solvent-free moisture-curable polyurethane resin composition is gradually increasing due to recent worldwide solvent emission regulations and residual solvent regulations (see, for example, Patent Document 1).

[0003] On the other hand, as the recent marine plastic problem has drawn attention, the attention to bio-based resins aiming at the elimination of petrochemical resources has been increasing day by day, and the moisture-curable polyurethane resin composition is no exception. However, there has been a pointed out that when the biomass content is increased, the texture and adhesiveness deteriorate, and the compatibility of these performances has been a major issue.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0005] The problem to be solved by the present invention is to provide a moisture-curable polyurethane resin composition having a high biomass content using biomass raw materials and excellent in texture and adhesiveness.

Means for Solving the Problems

[0006] The present invention provides a moisture-curing polyurethane hot-melt resin composition containing a urethane prepolymer (i) having an isocyanate group, which is a reaction product of a polyol (A) and a polyisocyanate (B), wherein the polyol (A) contains a biomass-derived polytetramethylene glycol or polycarbonate polyol (a1), a polyol (a2) having an aromatic ring, and a room-temperature solid polyester polyol (a3) other than the above (a2).

[0007] The present invention also provides an adhesive characterized by containing the above moisture-curing polyurethane resin composition. Further, the present invention provides a laminate characterized by having at least a substrate and a cured product of the above moisture-curing polyurethane resin composition.

Advantages of the Invention

[0008] The moisture-curing polyurethane resin composition of the present invention is highly biomass-based using biomass raw materials and is an environmentally friendly material. Further, the moisture-curing polyurethane resin composition of the present invention achieves both excellent texture and adhesiveness.

Embodiments for Carrying out the Invention

[0009] The moisture-curing polyurethane hot-melt resin composition used in the present invention contains a polyol (A) containing specific polyols and a urethane prepolymer (i) having an isocyanate group, which is a reaction product of the polyol (A) and a polyisocyanate (B).

[0010] The polyol (A) contains, as essential components, a biomass-derived polytetramethylene glycol or polycarbonate polyol (a1), a polyol (a2) having an aromatic ring, and a room-temperature solid polyester polyol (a3) other than the above (a2) in order to increase the biomass content of the resin and achieve both excellent texture and adhesiveness.

[0011] The polytetramethylene glycol or polycarbonate polyol (a1) derived from biomass is an essential component for increasing the biomass content of the resin and expressing basic physical properties such as excellent mechanical strength of the adhesive film.

[0012] As the polytetramethylene glycol derived from biomass, for example, "Bio PTMG" manufactured by Mitsubishi Chemical Corporation can be obtained as a commercially available product.

[0013] As the polycarbonate polyol derived from biomass, preferably, a polycarbonate polyol using glycol having 1 to 10 carbon atoms derived from biomass, more preferably 3 to 10 carbon atoms, can be used. For example, "Bene Bioll NL-2010DB" manufactured by Mitsubishi Chemical Corporation, "Bene Bioll NL-3010DB" manufactured by Mitsubishi Chemical Corporation, "Bene Bioll NL-2000D" manufactured by Mitsubishi Chemical Corporation, "PCDX222" manufactured by Asahi Kasei Corporation, etc. can be obtained as commercially available products. These polycarbonate polyols may be used alone or in combination of two or more.

[0014] The number average molecular weight of the polytetramethylene glycol or polycarbonate polyol (a1) derived from biomass is preferably 500 to 100,000, more preferably 700 to 50,000. The number average molecular weight of the polytetramethylene glycol or polycarbonate polyol (a1) derived from biomass indicates the value measured by the gel permeation chromatography (GPC) method.

[0015] The amount of the polytetramethylene glycol or polycarbonate polyol (a1) derived from biomass used is preferably 50 to 90% by mass, more preferably 60 to 80% by mass in the polyol (A).

[0016] The polyol (a2) having the aromatic ring provides excellent film flexibility, texture, and adhesiveness. For example, a polyether polyol having an aromatic ring, a polyester polyol having an aromatic ring, or the like can be used.

[0017] As the polyether polyol having the aromatic ring, for example, bisphenol A, bisphenol F, and their alkylene oxide adducts can be used. These polyols can be used alone or in combination of two or more. Among them, a polyether polyol which is an alkylene oxide adduct of bisphenol A is preferred. As the alkylene oxide, an alkylene oxide having 2 to 8 carbon atoms is preferred, and as the added molar number of the alkylene oxide, 2 to 10 moles is preferred, and 4 to 8 moles is more preferred.

[0018] As the polyester polyol having the aromatic ring, for example, a reaction product of a compound having the following hydroxyl group and a polybasic acid can be used.

[0019] As the compound having the hydroxyl group, for example, ethylene glycol, propylene glycol, 1,4 - butanediol, pentanediol, 2,4 - diethyl - 1,5 - pentanediol, 3 - methyl - 1,5 - pentanediol, hexanediol, neopentyl glycol, hexamethylene glycol, glycerin, trimethylolpropane, bisphenol A, bisphenol F, and their alkylene oxide adducts can be used. Among them, it is preferable to use an alkylene oxide adduct of bisphenol A. Also, as the alkylene oxide, an alkylene oxide having 2 to 8 carbon atoms is preferred, and as the added molar number of the alkylene oxide, 2 to 10 moles is preferred, and 4 to 8 moles is more preferred.

[0020] As the polybasic acid, adipic acid, glutaric acid, pimelic acid, suberic acid, dimer acid, sebacic acid, undecanedicarboxylic acid, hexahydroterephthalic acid, phthalic acid, phthalic anhydride, isophthalic acid, terephthalic acid, etc. can be used.

[0021] The number average molecular weight of the polyol (a2) having an aromatic ring is preferably 500 to 10,000, more preferably 500 to 5,000. The number average molecular weight of the polyol (a2) having an aromatic ring indicates a value measured by the gel permeation chromatography (GPC) method.

[0022] The amount of the polyol (a2) having an aromatic ring used is preferably 10 to 40% by mass, more preferably 20 to 30% by mass in the polyol (A).

[0023] The polyester polyol (a3) which is solid at normal temperature other than (a2) is an essential component for suppressing the penetration of the adhesive into the fabric and exhibiting excellent texture. The solid at normal temperature means that it does not show fluidity at 25°C.

[0024] As the polyester polyol (a3), preferably, a polyester polyol (a3-1) made from diethylene glycol and sebacic acid, a polyester polyol (a3-2) made from 1,3-propanediol and sebacic acid, a polyester polyol (a3-3) made from diethylene glycol, neopentyl glycol, and phthalic acid, and a polyester polyol (a3-4) made from diethylene glycol and phthalic acid, and one or more selected from the group consisting of them are preferred.

[0025] Furthermore, as the polyester polyol (a3), in terms of increasing the biomass content of the resin, a polyester polyol (a3-1) made from diethylene glycol and sebacic acid, and / or a polyester polyol (a3-2) made from 1,3-propanediol and sebacic acid are preferable. As the biomass raw materials for the polyester polyols described above, for example, biomass-derived sebacic acid ("Bio Seb" manufactured by Toyokuni Oil Co., Ltd.), biomass-derived 1,3-propanediol ("SUSTERRA Propanediol" manufactured by DuPont), biomass-derived diethylene glycol ("Bio DEG" manufactured by India Glycols) and the like are commercially available and can be obtained.

[0026] In addition, as the polyester polyol (a3), in terms of obtaining a more excellent texture, a polyester polyol (a3-3) made from diethylene glycol, neopentyl glycol, and phthalic acid, and / or a polyester polyol (a3-4) made from diethylene glycol and phthalic acid are preferable, and a polyester polyol (a3-3) made from diethylene glycol, neopentyl glycol, and phthalic acid is particularly preferable. The diethylene glycol may be derived from petrochemicals or biomass, but in order to increase the biomass content, it is preferable to use biomass-derived diethylene glycol.

[0027] The number average molecular weight of the polyester polyol (a3) is preferably 500 to 10,000, more preferably 800 to 5,000. The number average molecular weight of the polyester polyol (a3) indicates the value measured by the gel permeation chromatography (GPC) method.

[0028] The amount of the polyester polyol (a3) used is preferably 10 to 30% by mass, more preferably 10 to 20% by mass in the polyol (A).

[0029] The polyol (A) contains the components (a1) to (a3) described above as essential components, but may contain other polyols as necessary. The total content ratio of (a1) to (a3) in the polyol (A) is preferably 20% by mass or more, more preferably 50% by mass or more.

[0030] Examples of the other polyols include polyester polyols other than (a2) and (a3), polycarbonate polyols other than (a1), polyether polyols other than (a1), polybutadiene polyols, polyacrylic polyols, and the like. These polyols may be used alone or in combination of two or more. These polyols may be used alone or in combination of two or more.

[0031] Examples of the number average molecular weight of the other polyols include 500 to 100,000. The number average molecular weight of the other polyols indicates a value measured by the gel permeation chromatography (GPC) method.

[0032] Examples of the polyisocyanate (B) include aromatic polyisocyanates such as polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate, xylylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, naphthalene diisocyanate; aliphatic or alicyclic polyisocyanates such as hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, tetramethylxylylene diisocyanate, and the like. These polyisocyanates may be used alone or in combination of two or more. Among these, aromatic polyisocyanates are preferred, and diphenylmethane diisocyanate is more preferred, from the viewpoint of obtaining more excellent reactivity, mechanical strength, and adhesiveness.

[0033] As the amount of the polyisocyanate (B) used, 5 to 40% by mass, preferably 10 to 30% by mass, is preferable based on the total mass of the raw materials constituting the urethane prepolymer (i).

[0034] The hot melt urethane prepolymer (i) is obtained by reacting the polyol (A) and the polyisocyanate (B), and has isocyanate groups that can react with the moisture present in the air or in the substrate to which the moisture-curing type polyurethane hot melt resin composition is applied to form a crosslinked structure.

[0035] As the biomass content of the hot melt urethane prepolymer (i), 40% or more is preferable, and 50 to 80% by mass is more preferable. The biomass content of the hot melt urethane prepolymer (i) indicates the total weight ratio of the biomass-derived raw materials used in producing the hot melt urethane prepolymer (i) to the total weight of the hot melt urethane prepolymer (i).

[0036] As a method for producing the hot melt urethane prepolymer (i), for example, it can be produced by putting the polyisocyanate (B) into a reaction vessel containing the polyol (A) and reacting under the condition that the isocyanate groups of the polyisocyanate (B) are in excess with respect to the hydroxyl groups of the polyol (A).

[0037] Regarding the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate groups of the polyisocyanate (B) and the hydroxyl groups of the polyol (A) when producing the hot melt urethane prepolymer (i), from the viewpoint of obtaining more excellent mechanical strength, texture, and adhesiveness, 1.2 to 5 is preferable, and 1.5 to 3 is more preferable.

[0038] The isocyanate group content of the hot-melt urethane prepolymer (i) obtained by the above method (hereinafter abbreviated as "NCO%") is preferably 1.4 to 6, more preferably 1.8 to 4.0, from the viewpoint of obtaining further excellent mechanical strength, texture, and adhesiveness. The NCO% of the hot-melt urethane prepolymer (i) indicates the value measured by the potentiometric titration method in accordance with JIS K1603-1:2007.

[0039] The moisture-curable polyurethane hot-melt resin composition used in the present invention contains the urethane prepolymer (i) as an essential component, but other additives may be used as necessary.

[0040] Examples of the other additives include light resistance stabilizers, curing catalysts, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent brighteners, foam stabilizers, silane coupling agents, waxes, thermoplastic resins, and the like. These additives may be used alone or in combination of two or more.

[0041] Next, the laminate of the present invention will be described.

[0042] The laminate of the present invention has at least a fabric and a cured product of the moisture-curable polyurethane hot-melt resin composition.

[0043] Examples of the base material include plastic base materials; glass base materials; wood; non-woven fabrics, woven fabrics, knitted fabrics, etc. made of polyester fibers, polyethylene fibers, nylon fibers, acrylic fibers, polyurethane fibers, acetate fibers, rayon fibers, polylactic acid fibers, cotton, hemp, silk, wool, glass fibers, carbon fibers, and their blended fibers; those in which the non-woven fabric is impregnated with a resin such as a polyurethane resin; those in which a porous layer is further provided on the non-woven fabric, and the like can be used.

[0044] Examples of the method for applying the moisture-curing type polyurethane hot melt resin composition include methods using a roll coater, a knife coater, a spray coater, a gravure roll coater, a screen printing coater, a comma coater, a T-die coater, an applicator, a dispenser, etc.

[0045] After applying the moisture-curing type polyurethane hot melt resin composition, it can be aged and cured by a known method.

[0046] Examples of the coating amount of the cured product of the moisture-curing type urethane hot melt resin composition are in the range of, for example, 5 to 100 g / m 2 2.

[0047] It should be noted that the most preferred embodiment is that the moisture-curing type polyurethane hot melt resin composition of the present invention is used as an adhesive for moisture-permeable waterproof functional clothing. In such a case, the moisture-curing type polyurethane hot melt resin composition is preferably applied intermittently by a gravure roll coater, a rotary screen, or a dispenser, and the fabric and a known moisture-permeable film are bonded together. Examples of the coating amount of the moisture-curing type polyurethane hot melt resin composition in such a case are in the range of, for example, 5 to 100 g / m 2 2.

Examples

[0048] Hereinafter, the present invention will be described in more detail with reference to examples.

[0049] [Example 1] Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG, number average molecular weight: 2,000" manufactured by Mitsubishi Chemical Corporation), 20 parts by mass of a polyether polyol having an aromatic ring (a polyether polyol which is a 6-mole adduct of propylene oxide to bisphenol A, number average molecular weight: 508), and 10 parts by mass of a biomass-derived polyester polyol (a reaction product of biomass-derived sebacic acid ("Bio Seb" manufactured by Toyo Oil Co., Ltd., number average molecular weight: 2,000) and biomass-derived diethylene glycol ("Bio DEG" manufactured by India Glycols), number average molecular weight: 2,000) were charged, and dried under reduced pressure at 110 °C until the water content became 0.05% by mass or less. Then, after cooling to 60 °C, 33 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the reaction was carried out for 2 hours until the isocyanate group content became constant to obtain a urethane prepolymer (i-1) with NCO%: 3.32% by mass and biomass content: 60.2% by mass, which was made into a moisture-curing type polyurethane hot melt resin composition.

[0050] [Example 2] Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of polytetramethylene glycol derived from biomass (Bio PTMG manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of a polyester polyol having an aromatic ring (a reaction product of 6 moles of propylene oxide added to bisphenol A, isophthalic acid, and sebacic acid derived from biomass (Bio Seb manufactured by Toyo Oil Co., Ltd.), number average molecular weight: 2,000), and 10 parts by mass of a polyester polyol derived from biomass (a reaction product of sebacic acid derived from biomass (Bio Seb manufactured by Toyo Oil Co., Ltd.) and diethylene glycol derived from biomass (Bio DEG manufactured by India Glycols), number average molecular weight: 2,000) were charged, and dried under reduced pressure at 110 °C until the water content became 0.05% by mass or less. Then, after cooling to 60 °C, 23.5 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, to obtain a urethane prepolymer (i-2) with NCO%: 3.33% by mass and biomass content: 65.4% by mass, which was made into a moisture-curing type polyurethane hot melt resin composition.

[0051] [Example 3] Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of polytetramethylene glycol derived from biomass (Bio PTMG manufactured by Mitsubishi Chemical Corporation), 20 parts by mass of a polyester polyol having an aromatic ring (a reaction product of 6 moles of propylene oxide added to bisphenol A, isophthalic acid, and sebacic acid derived from biomass (Bio Seb manufactured by Toyokoku Oil Co., Ltd.), number average molecular weight; 2,000), and 10 parts by mass of a polyester polyol derived from biomass (a reaction product of 1,3-propanediol derived from biomass (SUSTERRA propanediol manufactured by Dupont) and sebacic acid derived from biomass (Bio Seb manufactured by Toyokoku Oil Co., Ltd.), number average molecular weight; 2,000) were charged, and dried under reduced pressure at 110 °C until the water content became 0.05% by mass or less. Then, after cooling to 60 °C, 23.5 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the reaction was carried out for 2 hours until the isocyanate group content became constant, thereby obtaining a urethane prepolymer (i-3) having an NCO% of 3.33% by mass and a biomass content of 65.4% by mass, and forming a moisture-curing type polyurethane hot melt resin composition.

[0052] [Example 4] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of an aromatic-ring-containing polyester polyol (a reaction product of 6 moles of propylene oxide added to bisphenol A, isophthalic acid, and biomass-derived sebacic acid ("Bio Seb" manufactured by Toyo Oil Co., Ltd.), number average molecular weight: 2,000), and 10 parts by mass of a biomass-derived polyester polyol (a reaction product of biomass-derived diethylene glycol ("Bio DEG" manufactured by India Glycols), neopentyl glycol, and orthophthalic acid, number average molecular weight: 1,000) were charged, and dried under reduced pressure at 110 °C until the water content reached 0.05% by mass or less. Subsequently, after cooling to 60 °C, 26.5 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the mixture was reacted for 2 hours until the isocyanate group content became constant to obtain a urethane prepolymer (i-4) with an NCO% of 3.39% by mass and a biomass content of 63.9% by mass, which was used as a moisture-curing type polyurethane hot melt resin composition.

[0053] [Example 5] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of biomass-derived polytetramethylene glycol (Bio PTMG manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of an aromatic ring-containing polyester polyol (a reaction product of 6 moles of propylene oxide added to bisphenol A, isophthalic acid, and biomass-derived sebacic acid (Bio Seb manufactured by Toyo Oil Co., Ltd.), number average molecular weight: 2,000), and 10 parts by mass of a biomass-derived polyester polyol (a reaction product of biomass-derived diethylene glycol (Bio DEG manufactured by India Glycols) and orthophthalic acid, number average molecular weight: 1,000) were charged, and dried under reduced pressure at 110 °C until the water content was 0.05% by mass or less. Then, after cooling to 60 °C, 23.5 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the reaction was carried out for 2 hours until the isocyanate group content became constant to obtain a urethane prepolymer (i-5) with NCO%: 3.33% by mass and biomass content: 65.4% by mass, which was made into a moisture-curing type polyurethane hot melt resin composition.

[0054] [Example 6] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of a biomass-derived polycarbonate polyol ("Venebiol NL2000D" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of a polyester polyol having an aromatic ring (a reaction product of 6 moles of propylene oxide added to bisphenol A, isophthalic acid, and biomass-derived sebacic acid ("Bio Seb" manufactured by Toyo Oil Co., Ltd.), number average molecular weight: 2,000), and 10 parts by mass of a biomass-derived polyester polyol (a reaction product of biomass-derived sebacic acid ("Bio Seb" manufactured by Toyo Oil Co., Ltd.) and biomass-derived diethylene glycol ("Bio DEG" manufactured by India Glycols), number average molecular weight: 2,000) were charged, and dried under reduced pressure at 110 °C until the water content was reduced to 0.05% by mass or less. Then, after cooling to 60 °C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the mixture was reacted for 2 hours until the isocyanate group content became constant to obtain a urethane prepolymer (i-6) with an NCO% of 3.36% by mass and a biomass content of 60.2% by mass, which was used as a moisture-curing type polyurethane hot melt resin composition.

[0055] [Example 7] In a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 60 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of a polyester polyol having an aromatic ring (a reaction product of 6 moles of propylene oxide added to bisphenol A, isophthalic acid, and biomass-derived sebacic acid ("Bio Seb" manufactured by Toyokoku Oil Co., Ltd.), number average molecular weight: 2,000), and 20 parts by mass of a biomass-derived polyester polyol (a reaction product of biomass-derived sebacic acid ("Bio Seb" manufactured by Toyokoku Oil Co., Ltd.) and biomass-derived diethylene glycol ("Bio DEG" manufactured by India Glycols), number average molecular weight: 2,000) were charged, and dried under reduced pressure at 110 °C until the water content became 0.05% by mass or less. Then, after cooling to 60 °C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the mixture was reacted for 2 hours until the isocyanate group content became constant to obtain a urethane prepolymer (i-7) having an NCO% of 3.36% by mass and a biomass content of 60.8% by mass, which was used as a moisture-curing type polyurethane hot melt resin composition.

[0056] [Example 8] Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 50 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000), 20 parts by mass of an aromatic-ring-containing polyester polyol (a reaction product of 6 moles of propylene oxide added to bisphenol A, isophthalic acid, and biomass-derived sebacic acid ("Bio Seb" manufactured by Toyo Oil Co., Ltd.), number average molecular weight: 2,000), and 30 parts by mass of a biomass-derived polyester polyol (a reaction product of biomass-derived sebacic acid ("Bio Seb" manufactured by Toyo Oil Co., Ltd.) and biomass-derived diethylene glycol ("Bio DEG" manufactured by India Glycols), number average molecular weight: 2,000) were charged, and dried under reduced pressure at 110 °C until the water content became 0.05% by mass or less. Then, after cooling to 60 °C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the reaction was carried out for 2 hours until the isocyanate group content became constant to obtain a urethane prepolymer (i-8) with NCO%: 3.36% by mass and biomass content: 64.6% by mass, which was made into a moisture-curing type polyurethane hot melt resin composition.

[0057] [Comparative Example 1] Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 100 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000) was charged, and dried under reduced pressure at 110 °C until the water content became 0.05% by mass or less. Then, after cooling to 60 °C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the reaction was carried out for 2 hours until the isocyanate group content became constant to obtain a urethane prepolymer (iR-1) with NCO%: 3.36% by mass and biomass content: 80% by mass, which was made into a moisture-curing type polyurethane hot melt resin composition.

[0058] [Comparative Example 2] Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000) and 30 parts by mass of a biomass-derived polyester polyol (a reaction product of biomass-derived sebacic acid ("Bio Seb" manufactured by Toyo Oil Co., Ltd.) and biomass-derived diethylene glycol ("Bio DEG" manufactured by India Glycols), number average molecular weight: 2,000) were charged, and dried under reduced pressure at 110 °C until the water content became 0.05% by mass or less. Subsequently, after cooling to 60 °C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the mixture was reacted for 2 hours until the isocyanate group content became constant to obtain a urethane prepolymer (iR-2) with NCO%: 3.36% by mass and biomass content: 80% by mass, and it was made into a moisture-curing type polyurethane hot melt resin composition.

[0059] [Comparative Example 3] Into a four-necked flask equipped with a thermometer, a stirrer, an inert gas inlet, and a reflux condenser, 70 parts by mass of biomass-derived polytetramethylene glycol ("Bio PTMG" manufactured by Mitsubishi Chemical Corporation, number average molecular weight: 2,000) and 30 parts by mass of a polyether polyol having an aromatic ring (a polyether polyol which is a propylene oxide 6-mol adduct of bisphenol A, number average molecular weight: 508) were charged, and dried under reduced pressure at 110 °C until the water content became 0.05% by mass or less. Subsequently, after cooling to 60 °C, 25.0 parts by mass of diphenylmethane diisocyanate was added, the temperature was raised to 110 °C, and the mixture was reacted for 2 hours until the isocyanate group content became constant to obtain a urethane prepolymer (iR-3) with NCO%: 3.36% by mass and biomass content: 56% by mass, and it was made into a moisture-curing type polyurethane hot melt resin composition.

[0060] [Measurement method of number average molecular weight] The number average molecular weights of the polyols used in the examples and comparative examples are the values measured under the following conditions by the gel permeation chromatography (GPC) method.

[0061] Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by Tosoh Corporation) Column: The following columns manufactured by Tosoh Corporation were connected in series and used. "TSKgel G5000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G4000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G3000" (7.8 mm I.D. × 30 cm) × 1 piece "TSKgel G2000" (7.8 mm I.D. × 30 cm) × 1 piece Detector: RI (Differential refractometer) Column temperature: 40 °C Eluent: Tetrahydrofuran (THF) Flow rate: 1.0 mL / min Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%) Standard sample: A calibration curve was created using the following standard polystyrene.

[0062] (Standard polystyrene) "TSKgel Standard Polystyrene A-500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-1000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-2500" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene A-5000" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-1" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-2" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-4" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-10" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-20" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-40" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-80" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-128" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-288" manufactured by Tosoh Corporation "TSKgel Standard Polystyrene F-550" manufactured by Tosoh Corporation

[0063] [Adhesion Evaluation Method] <Adhesion Evaluation 1 - Initial Adhesion Strength> In a thermo-hygrostat chamber adjusted to a temperature of 23°C and a humidity of 50 ± 5%, onto corona-treated PET with a thickness of 100 μm, using a 50-μm-thick bar coater, the moisture-curing type polyurethane hot melt resin compositions obtained in the examples and comparative examples, melted at 100°C, were applied over the entire surface, and the laminate with the corona-treated PET was cut into 1-inch widths under the conditions of a temperature of 23°C and a humidity of 50 ± 5%. Using a tensilon (Tensilon universal testing machine "RTC 1210A" manufactured by Orientec Co., Ltd.), the initial adhesion strength (N / inch) was measured under the condition of a crosshead speed of 200 mm / min. The initial adhesion strength was measured 1 minute, 10 minutes, and 30 minutes after the moisture-curing type polyurethane hot melt resin composition was applied over the entire surface.

[0064] <Adhesion Evaluation 2> In a thermo-hygrostat chamber adjusted to a temperature of 23°C and a humidity of 50 ± 5%, onto a moisture-permeable film ("VENTEX" manufactured by Kappei Co., Ltd.) using a gravure coater, the moisture-curing type polyurethane hot melt resin compositions obtained in the examples and comparative examples, melted at 100°C, were intermittently applied to a level of 17.5 ± 5 g / m 2 and laminated with a polyester fabric. The resulting processed fabric was aged for 24 hours under the conditions of a temperature of 23°C and a humidity of 50 ± 5% to obtain a processed fabric. This processed fabric was cut into 1-inch widths, and using a tensilon (Tensilon universal testing machine "RTC 1210A" manufactured by Orientec Co., Ltd.), the peel strength (kg / inch) was measured under the condition of a crosshead speed of 200 mm / min.

[0065] [Texture Evaluation Method] The flexibility when the processed fabric obtained in the above [Adhesion Evaluation 2] was bent by hand was evaluated as follows. "5": Rich in flexibility. "4": Sufficiently flexible. "3": Somewhat flexible. "2": Poor in flexibility. "1": Hard.

[0066] [Table 1]

[0067] [Table 2]

[0068] [Table 3]

[0069] It was found that the moisture-curable polyurethane hot melt resin composition of the present invention has a high biomass content and excellent adhesiveness and texture.

[0070] On the other hand, Comparative Example 1 is a mode in which components (a2) and (a3) are not used, but the adhesiveness and texture were poor.

[0071] Comparative Example 2 is a mode in which component (a2) is not used, but the adhesiveness and texture were poor.

[0072] Comparative Example 3 is a mode in which component (a3) is not used, but the adhesiveness and texture were poor.

Claims

1. It contains a urethane prepolymer (i) having an isocyanate group, which is a reaction product of a polyol (A) and a polyisocyanate (B). The polyol (A) is 50 to 70% by mass of a biomass-derived polytetramethylene glycol or polycarbonate polyol (a1) in the polyol (A), 20 to 30% by mass of a polyol (a2) having an aromatic ring in the polyol (A), and a room-temperature solid polyester polyol (a3) other than the above (a2). It contains The polyester polyol (a3) is at least one selected from the group consisting of a polyester polyol (a3-1) made from diethylene glycol and sebacic acid, a polyester polyol (a3-2) made from 1,3-propanediol and sebacic acid, a polyester polyol (a3-3) made from diethylene glycol, neopentyl glycol, and phthalic acid, and a polyester polyol (a3-4) made from diethylene glycol and phthalic acid. A moisture-curing type polyurethane hot-melt resin composition for an adhesive for moisture-permeable and waterproof functional clothing, characterized in that it is such.

2. The moisture-curing type polyurethane hot-melt resin composition for an adhesive for moisture-permeable and waterproof functional clothing according to Claim 1, wherein the polycarbonate polyol (a1) is made from a biomass-derived glycol having 1 to 10 carbon atoms.

3. An adhesive for moisture-permeable and waterproof functional clothing, characterized in that it contains the moisture-curing type polyurethane resin composition for an adhesive for moisture-permeable and waterproof functional clothing according to Claim 1.

4. A laminate, characterized by having at least a substrate and a cured product of the moisture-curing type polyurethane resin composition for an adhesive for moisture-permeable and waterproof functional clothing according to Claim 1.

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