JPWO2018116681A1 - Moisture curable urethane hot melt resin composition, laminate, and shoe - Google Patents

Abstract

  The present invention is a moisture curable urethane hot melt resin composition containing a urethane prepolymer having an isocyanate group which is a reaction product of the polyol (A) and the polyisocyanate (B), and the polyisocyanate (B) Is an aliphatic polyisocyanate and / or alicyclic polyisocyanate (B-1) and an aromatic polyisocyanate (B-2) in a mass ratio [(B-1) / (B-2)]. The present invention provides a moisture curable urethane hot melt resin composition characterized by being used in the range of 10/90 to 95/5. The polyol (A) preferably contains a crystalline polyol (A-1) and an amorphous polyol (A-2). The present invention provides a moisture curable urethane hot melt resin composition that provides excellent initial creep properties and initial strength even when rubber is used as a substrate.

Description

  The present invention relates to a moisture curable urethane hot melt resin composition and shoes.

  Conventionally, solvent-based and water-based adhesives have been the mainstream as adhesives for shoes, but a drying process is required and double-sided coating is required, so productivity is low. On the other hand, the moisture-curing urethane hot melt adhesive is solvent-free and therefore does not require a drying step, and can be applied on one side, and thus has excellent productivity.

  As the moisture curable urethane hot melt adhesive for shoe sole, for example, a moisture curable urethane hot melt adhesive obtained by reacting crystalline polyester, aromatic chain extender, polyisocyanate and the like is disclosed ( For example, see Patent Document 1.)

  However, since the adhesive has a low molecular weight immediately after bonding and low initial creep property and initial strength (initial peel strength), it is used for a shoe sole when a shoe sole having a complicated shape is bonded. There was a problem that the repulsive force of rubber could not be suppressed and peeling occurred.

JP 2004-323838 A

  The problem to be solved by the present invention is to provide a moisture-curing urethane hot melt resin composition capable of obtaining excellent initial creep properties and initial strength even when rubber is used as a substrate.

  The present invention is a moisture curable urethane hot melt resin composition containing a urethane prepolymer having an isocyanate group which is a reaction product of the polyol (A) and the polyisocyanate (B), and the polyisocyanate (B) Is an aliphatic polyisocyanate and / or alicyclic polyisocyanate (B-1) and an aromatic polyisocyanate (B-2) in a mass ratio [(B-1) / (B-2)]. The present invention provides a moisture curable urethane hot melt resin composition characterized by being used in the range of 10/90 to 95/5.

  The present invention also provides a laminate in which a cured product layer of the moisture curable urethane hot melt resin composition is formed on a rubber layer. Furthermore, the present invention provides a shoe characterized by having a shoe sole bonded with the moisture-curable urethane hot melt resin composition.

  The moisture curable urethane hot melt resin composition of the present invention can provide excellent initial creep properties and initial strength even when rubber is used as a substrate. Therefore, it can be used particularly suitably as an adhesive for shoes, and even when a shoe sole having a complicated shape is adopted, good bonding can be performed.

  The moisture-curable urethane hot melt resin composition of the present invention contains a urethane prepolymer having an isocyanate group which is a reaction product of a polyol (A) and a polyisocyanate (B), and the polyisocyanate (B ) Is an aliphatic polyisocyanate and / or alicyclic polyisocyanate (B-1) and an aromatic polyisocyanate (B-2) in a mass ratio [(B-1) / (B-2)]. It is used in the range of 10/90 to 95/5.

  Examples of the polyol (A) include polyester polyol, polyether polyol, polycarbonate polyol, polybutadiene polyol, polyhydrogenated butadiene polyol, dimer diol, and polyacryl polyol. In addition, as the polyol (A), it is excellent to use a crystalline polyol (A-1) and an amorphous polyol (A-2) in combination while maintaining excellent initial creep properties and initial strength. In addition, it is preferable to use these in combination since an open time (a time for bonding) can be obtained.

  As said polyol (A), when the said (A-1) and (A-2) are used together, as the mass ratio [(A-1) / (A-2)], an appropriate open time is used. From the point that even more excellent initial strength and initial creep properties can be obtained while maintaining, a range of 90/10 to 30/70 is preferable, and a range of 80/20 to 50/50 is more preferable.

  As said crystalline polyol (A-1), crystalline polyester polyol, crystalline polycarbonate polyol, crystalline polyether polyol etc. can be used, for example. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use a crystalline polyester polyol and / or a crystalline polycarbonate polyol, and a crystalline polyester polyol is more preferable from the viewpoint that a further excellent initial strength and initial creep property can be obtained.

  As the crystalline polyester polyol, for example, a reaction product of a compound having a hydroxyl group and a polybasic acid can be used.

Examples of the aliphatic compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, heptanediol, octanediol, nonanediol, decanediol, and dodecanediol. , Trimethylolpropane, trimethylolethane, glycerin, 2-methyl-1,3-propanediol, neopentyl glycol, 3-methyl-1,5-pentanediol, 2,4-diethyl-1,5-pentanediol 2-methyl-1,8-octanediol, 2-ethyl-2-butyl-1,3-propanediol, and the like can be used. These compounds may be used alone or in combination of two or more. Among these, since even better initial creep properties and initial strength can be obtained due to better crystallinity, 1 selected from the group consisting of ethylene glycol, butanediol, hexanediol, octanediol, decanediol, and dodecanediol. It is preferable to use more than one kind of compound. These preferable compounds are preferably used in an amount of 30% by mass or more, more preferably 50% by mass or more, in the aliphatic compound having two or more hydroxyl groups.

  Examples of the aliphatic polybasic acid include polybasic acids such as oxalic acid, malonic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, and dodecanedioic acid. These compounds may be used alone or in combination of two or more. Among these, since more excellent initial creep property and initial strength can be obtained due to better crystallinity, one or more selected from the group consisting of succinic acid, adipic acid, sebacic acid, and dodecanedioic acid should be used. Is preferred.

  As the crystalline polycarbonate polyol, for example, a condensate of a polyhydric alcohol having 3 to 9 carbon atoms and a dialkyl carbonate having an alkyl group having 1 to 6 carbon atoms can be used.

  Examples of the crystalline polycarbonate polyol include “ETERRNACOLL UH-200” (manufactured by Ube Industries Co., Ltd.), “Nipporan-981” (manufactured by Nippon Polyurethane Co., Ltd.), “Duranol T-6002” (Asahi Kasei Chemicals Corporation). Etc.) can be obtained as a commercial product.

  As the amorphous polyol (A-2), for example, polyether polyol, amorphous polyester polyol, amorphous polycarbonate polyol, acrylic polyol, dimer diol and the like can be used. These polyols may be used alone or in combination of two or more. Among these, it is preferable to use one or more polyols selected from the group consisting of polyether polyols, amorphous polyester polyols, and amorphous polycarbonate polyols, from the viewpoint that even better open time can be obtained.

  Examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polytetramethylene glycol, polyoxyethylene polyoxypropylene glycol, polyoxyethylene polyoxytetramethylene glycol, and the like. These polyether polyols may be used alone or in combination of two or more. Among these, it is preferable to use polypropylene glycol from the viewpoint that a much better open time can be obtained.

  As the amorphous polyester polyol, for example, a reaction product of a compound having a hydroxyl group and a polybasic acid can be used.

  Examples of the compound having a hydroxyl group include ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 2-methyl-1,3-propanediol, and 2-methyl-1,8-. Octanediol, 2,2-diethyl-1,3-propanediol, 2,2-diethyl-1,3-pentanediol, 2-ethyl-2-butyl-1,3-propanediol, 2,4-diethyl-1 , 5-pentanediol, 3-methyl-1,5-pentanediol, neopentyl glycol; bisphenol A, bisphenol F, these alkylene oxide adducts, and the like can be used. These compounds may be used alone or in combination of two or more.

  Examples of the polybasic acid include succinic 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. An acid or the like can be used. These polybasic acids may be used alone or in combination of two or more.

  As the amorphous polycarbonate polyol, for example, a reaction product obtained by a known method of carbonate ester and / or phosgene and a compound having two or more hydroxyl groups can be used.

  As the carbonate ester, for example, methyl carbonate, dimethyl carbonate, diethyl carbonate, cyclocarbonate, diphenyl carbonate and the like can be used. These compounds may be used alone or in combination of two or more.

  Examples of the compound having two or more hydroxyl groups include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, dipropylene glycol, 1,4-butanediol, 1, 3-butanediol, 1,5-pentanediol, 1,5-hexanediol, 1,6-hexanediol, 1,7-heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10 -Decanediol, 1,12-dodecanediol, 2-methyl-1,3-propanediol, 3-methyl-1,5-pentanediol, 2-butyl-2-ethylpropanoldiol, neopentyl glycol, 1,4 -Cyclohexanediol, 1,4-cyclohexanedimethanone Or the like can be used. These compounds may be used alone or in combination of two or more. Among these, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5 can be obtained because the glass transition temperature of the urethane prepolymer can be lowered and a better open time property can be obtained. It is preferable to use as a raw material at least one compound selected from the group consisting of -pentanediol, 2-methyl-1,8-octanediol, and 1,9-nonanediol. These preferable compounds are preferably used in an amount of 30% by mass or more, more preferably 50% by mass or more, in the compound having two or more hydroxyl groups.

  The number average molecular weight of the polyol (A) is preferably in the range of 300 to 10,000, more preferably in the range of 350 to 7,000, from the viewpoint that even better initial creep properties and initial strength can be obtained. The range of 400 to 5,000 is more preferable. In addition, the number average molecular weight of the said polyol (A) shows the value measured by the gel permeation chromatography (GPC) method.

  A chain extender may be used in combination with the polyol (A) as necessary.

  Examples of the chain extender include ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperazine, 2,5-dimethylpiperazine, isophoronediamine, 1,2-cyclohexanediamine, and 1,3-cyclohexane. Chain extenders having amino groups such as diamine, 1,4-cyclohexanediamine, 4,4′-dicyclohexylmethanediamine, 3,3′-dimethyl-4,4′-dicyclohexylmethanediamine, hydrazine; ethylene glycol, diethylene glycol, Triethylene glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, hexamethyle Glycol, 3-methyl-1,5-pentanediol, dimethylolheptane, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, saccharose, methylene glycol, glycerin, sorbitol, bisphenol A, A chain extender having a hydroxyl group such as 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, and trimethylolpropane can be used. These chain extenders may be used alone or in combination of two or more.

  When the chain extender is used, the amount used is preferably 0.1 to 30 parts by mass, more preferably 1 to 10 parts by mass with respect to 100 parts by mass of the polyol (A).

  As said polyisocyanate (B), aliphatic polyisocyanate and / or alicyclic polyisocyanate (B-1), and aromatic polyisocyanate (B-2) are made into mass ratio [(B-1) / ( B-2)], it is essential to use in the range of 10/90 to 95/5. By using (B-1) and (B-2) within such a range, good crystallinity can be obtained, excellent initial creep properties and initial strength can be obtained, and excellent manufacturing stability can be obtained. it can. Outside the above range, when rubber is used as a substrate, sufficient crystallinity that can suppress the repulsion of rubber cannot be obtained. The mass ratio is preferably in the range of 15/85 to 90/10, and more preferably in the range of 20/80 to 85/15, from the viewpoint that even better initial creep properties and initial strength can be obtained.

  Examples of the aliphatic polyisocyanate and / or alicyclic polyisocyanate (B-1) include hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, dicyclohexylmethane diisocyanate, and tetramethylxylylene diisocyanate. These aliphatic polyisocyanates may be used alone or in combination of two or more. Among these, it is preferable to use hexamethylene diisocyanate from the viewpoint of high crystallinity.

  Examples of the aromatic polyisocyanate (B-2) include polymethylene polyphenyl polyisocyanate, diphenylmethane diisocyanate, carbodiimide-modified diphenylmethane diisocyanate isocyanate, xylene diisocyanate, phenylene diisocyanate, tolylene diisocyanate, and naphthalene diisocyanate. These polyisocyanates may be used alone or in combination of two or more. Among these, it is more preferable to use diphenylmethane diisocyanate and / or xylene diisocyanate from the viewpoint of obtaining good reactivity and peel strength.

  The amount of the polyisocyanate (B) used is preferably in the range of 5 to 40% by mass, more preferably in the range of 10 to 35% by mass, based on the total mass of the raw materials constituting the urethane prepolymer.

  The urethane prepolymer is obtained by reacting the polyol (A) and the polyisocyanate (B), and reacts with moisture present in the air or in a substrate to which the urethane prepolymer is applied to crosslink. It has an isocyanate group capable of forming a structure.

  As a method for producing the urethane prepolymer, for example, a polyol (A) is put in a reaction vessel containing the polyisocyanate (B), and the isocyanate group of the polyisocyanate (B) is changed to that of the polyol (A). It can manufacture by making it react on the conditions which become excess with respect to the hydroxyl group which has.

  As the equivalent ratio (isocyanate group / hydroxyl group) between the isocyanate group of the polyisocyanate (B) and the hydroxyl group of the polyol (A) in producing the urethane prepolymer, even more excellent initial creep and initial From the viewpoint of obtaining strength, it is preferably in the range of 1.1 to 5, and more preferably in the range of 1.15 to 3.

  The isocyanate group content (hereinafter abbreviated as “NCO%”) of the urethane prepolymer obtained by the above method is 0.5 to 10 from the viewpoint of obtaining even better initial creep and initial strength. Is preferable, and the range of 1-8 is more preferable. In addition, NCO% of the said urethane prepolymer shows the value measured by the potentiometric titration method based on JISK1603-1: 2007.

  Further, the melt viscosity at 120 ° C. of the urethane prepolymer is preferably in the range of 1,000 to 200,000 mPa · s from the viewpoint of obtaining even better initial creep and initial strength, and is preferably 3,000. The range of ˜150,000 mPa · s is more preferable, and the range of 5,000 to 100,000 mPa · s is still more preferable. The melt viscosity was measured by melting the urethane prepolymer at 120 ° C. for 1 hour, sampling 1 ml, and measuring the melt viscosity with a cone plate viscometer (40P cone, rotor rotation speed: 50 rpm). Indicates.

  Moreover, as a manufacturing method of the said urethane prepolymer, when hexamethylene diisocyanate is used as aliphatic polyisocyanate and / or alicyclic polyisocyanate (B-1), hexamethylene diisocyanate and polyol (A ) To obtain a prepolymer having a hydroxyl group, and then reacting the aromatic polyisocyanate (B-2) to obtain a urethane prepolymer having an isocyanate group. According to this manufacturing method, even if highly volatile hexamethylene diisocyanate is used, a moisture-curable urethane hot melt resin composition having high crystallinity can be stably obtained.

  As the equivalent ratio (isocyanate group / hydroxyl group) in the reaction of hexamethylene diisocyanate and polyol (A) in the first stage when adopting this production method, the abundance of highly crystalline hexamethylene diisocyanate can be increased. From the point that even more excellent initial creep properties and initial strength are obtained, it is preferably 0.5 or more, more preferably in the range of 0.6 to 0.99, and in the range of 0.65 to 0.95. Further preferred.

  In addition, as the equivalent ratio (isocyanate group / hydroxyl group) in the reaction between the prepolymer having a second-stage hydroxyl group and the aromatic polyisocyanate (B-2), a further excellent initial creep property and initial strength can be obtained. Therefore, the range is preferably 1.1 to 5, and more preferably 1.2 to 4.

  The moisture curable urethane hot melt resin composition of the present invention contains the urethane prepolymer as an essential component, but may contain other additives as necessary.

  Examples of the other additives include a curing catalyst, an antioxidant, a tackifier, a plasticizer, a stabilizer, a filler, a dye, a pigment, a fluorescent brightening agent, a silane coupling agent, a wax, and a thermoplastic resin. Can be used. These additives may be used alone or in combination of two or more.

  As described above, the moisture-curable urethane hot melt resin composition of the present invention can provide excellent initial creep properties and initial strength even when rubber is used as a substrate. Therefore, it can be used particularly suitably as an adhesive for shoes, and even when a shoe sole having a complicated shape is adopted, good bonding can be performed.

  As a method for producing shoes using the moisture curable urethane hot melt resin composition of the present invention, for example, after a heat-cured moisture curable urethane hot melt resin composition is melted at 50 to 200 ° C., a rubber product is used. For example, a method of coating on an outsole or the like, and then bonding the upper part together.

  After the bonding, the moisture curable urethane hot melt resin composition may be dried and cured by a known method.

  The thickness of the cured product of the moisture curable urethane hot melt resin composition is, for example, in the range of 0.001 to 0.5 cm.

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

[Example 1]
In a 2 liter four-necked flask equipped with a stirrer and a thermometer, aliphatic polyester polyol (aliphatic polyester polyol reacted with 1,4-butanediol and adipic acid, number average molecular weight; 600, hereinafter “BG / AA” ) 73.3 parts by mass, 18.5 parts by mass of hexamethylene diisocyanate (hereinafter abbreviated as “HDI”) (NCO / OH = 0.9 in this case), mixed and mixed at 50 ° C. The mixture was dehydrated by heating under reduced pressure until the water content in the flask was 0.05% by mass.
Next, 8.2 parts by mass of xylene diisocyanate (hereinafter abbreviated as “XDI”) was added, and a urethane prepolymer (120) was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant. (Melting temperature at 50 ° C .; 50,000 mPa · s) was obtained as a moisture curable urethane hot melt resin composition.

[Example 2]
In a 2 liter four-necked flask equipped with a stirrer and a thermometer, aliphatic polyester polyol (aliphatic polyester polyol obtained by reacting 1,6-hexanediol and dodecanedioic acid, number average molecular weight; 1,000, hereinafter “ HG / DDA ”.) 82.3 parts by mass and 11.1 parts by mass of HDI (NCO / OH = 0.8 at this time) are mixed, mixed, and heated at 50 ° C. under reduced pressure. It dehydrated until the water | moisture content with respect to all the inside became 0.05 mass%.
Next, 6.6 parts by mass of XDI was added, and a urethane prepolymer (melting temperature at 120 ° C .; 60,000 mPa · s) was allowed to react at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant. A moisture curable urethane hot melt resin composition was obtained.

[Example 3]
In a 2 liter four-necked flask equipped with a stirrer and a thermometer, 70.5 parts by mass of aliphatic polyester polyol (BG / AA) and 16.8 parts by mass of HDI were added (NCO / OH = 0.85 at this time). ), And dehydrated by heating at 50 ° C. under reduced pressure until the water content in the flask became 0.05 mass%.
Next, 12.7 parts by mass of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”) is added, and the reaction is performed at 110 ° C. for about 3 hours until the isocyanate group content becomes constant in a nitrogen atmosphere. To obtain a urethane prepolymer (melting temperature at 120 ° C .; 70,000 mPa · s) to obtain a moisture-curable urethane hot melt resin composition.

[Example 4]
In a 2 liter four-necked flask equipped with a stirrer and a thermometer, 51.3 parts by mass of crystalline polyester polyol (BG / AA) and polypropylene glycol (number average molecular weight; 1,000, hereinafter abbreviated as “PPG”) 25.6 parts by mass and 16.8 parts by mass of HDI were added (NCO / OH = 0.9 at this time), mixed, and heated under reduced pressure at 50 ° C., so that the moisture relative to the total amount in the flask was 0.05. It dehydrated until it became the mass%.
Next, 6.3 parts by mass of XDI was added, and a urethane prepolymer (melting temperature at 120 ° C .; 70,000 mPa · s) was allowed to react at 110 ° C. for about 3 hours until the isocyanate group content became constant in a nitrogen atmosphere. A moisture curable urethane hot melt resin composition was obtained.

[Example 5]
In a 2 liter four-necked flask equipped with a stirrer and a thermometer, 51.7 parts by mass of crystalline polyester polyol (HG / DDA), 31 parts by mass of PPG, and 11.1 parts by mass of HDI (NCO / OH = 0.8), mixed, and heated under reduced pressure at 50 ° C. to dehydrate until the water content in the flask became 0.05% by mass.
Next, 6.2 parts by mass of XDI was added, and a urethane prepolymer (melting temperature at 120 ° C .; 75,000 mPa · s) was reacted at 110 ° C. for about 3 hours until the isocyanate group content became constant in a nitrogen atmosphere. A moisture curable urethane hot melt resin composition was obtained.

[Example 6]
In a 2 liter four-necked flask equipped with a stirrer and a thermometer, 49.5 parts by mass of BG / AA, 24.8 parts by mass of PPG, and 16.3 parts by mass of HDI were put (NCO / OH = 0 at this time). .9) was mixed and heated at 50 ° C. under reduced pressure to dehydrate until the water content in the flask was 0.05 mass%.
Next, 9.4 parts by mass of 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as “MDI”) is added and reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content becomes constant. A urethane prepolymer (melting temperature at 120 ° C .; 80,000 mPa · s) was obtained to obtain a moisture-curable urethane hot melt resin composition.

[Example 7]
In a 2 liter four-necked flask equipped with a stirrer and a thermometer, 58.5 parts by mass of BG / AA, an amorphous polyester polyol (reacted with neopentyl glycol and phthalic anhydride, number average molecular weight; 1 17,000 parts by mass and 17.4 parts by mass of HDI (NCO / OH = 0.9 at this time), mixed, and heated at 50 ° C. under reduced pressure. Thus, dehydration was performed until the water content in the flask became 0.05% by mass.
Next, 6.5 parts by mass of XDI was added, and a urethane prepolymer (melting temperature at 120 ° C .; 70,000 mPa · s) was allowed to react at 110 ° C. for about 3 hours until the isocyanate group content became constant in a nitrogen atmosphere. A moisture curable urethane hot melt resin composition was obtained.

[Comparative Example 1]
68.9 parts by mass of aliphatic polyester polyol (aliphatic polyester polyol obtained by reacting 1,4-butanediol and adipic acid, number average molecular weight; 600) in a 2 liter four-necked flask equipped with a stirrer and a thermometer Then, 5.8 parts by mass of hexamethylene diisocyanate is added (NCO / OH = 0.3 in this case), mixed, and heated at 50 ° C. under reduced pressure, so that the water content relative to the total amount in the flask becomes 0.05% by mass. Until dehydrated.
Next, 25.3 parts by mass of 4,4′-diphenylmethane diisocyanate was added, and a urethane prepolymer (melting temperature at 120 ° C .; 120 ° C .; reaction was performed at 110 ° C. for about 3 hours until the isocyanate group content was constant under a nitrogen atmosphere; 40,000 mPa · s) was obtained as a moisture curable urethane hot melt resin composition.

[Comparative Example 2]
In a 2 liter four-necked flask equipped with a stirrer and a thermometer, 68 parts by mass of aliphatic polyester polyol (aliphatic polyester polyol reacted with 1,4-butanediol and adipic acid, number average molecular weight; 600) was placed. The mixture was dehydrated by heating at 50 ° C. under reduced pressure until the water content in the flask became 0.05 mass%.
Subsequently, 32 parts by mass of 4,4′-diphenylmethane diisocyanate was added, and a urethane prepolymer (melting temperature at 120 ° C .; 70, 70 ° C.) was allowed to react at 110 ° C. for about 3 hours until the isocyanate group content became constant in a nitrogen atmosphere. 000 mPa · s) to obtain a moisture curable urethane hot melt resin composition.

[Comparative Example 3]
76.3 parts by mass of aliphatic polyester polyol (1,4-butanediol and aliphatic polyester polyol reacted with adipic acid, number average molecular weight; 600) in a 2 liter four-necked flask equipped with a stirrer and a thermometer , Mixed, and heated under reduced pressure at 50 ° C. until the water content in the flask was 0.05% by mass.
Subsequently, 23.7 parts by mass of hexamethylene diisocyanate was added, and a urethane prepolymer (melting temperature at 120 ° C .; 30,000 mPa's) was reacted at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became constant. S) to obtain a moisture curable urethane hot melt resin composition.

[Measurement method of number average molecular weight]
The number average molecular weights of polyols and the like used in Examples and Comparative Examples show values measured under the following conditions by gel permeation chromatography (GPC) method.

Measuring device: High-speed GPC device (“HLC-8220GPC” manufactured by Tosoh Corporation)
Column: The following columns manufactured by Tosoh Corporation were connected in series.
"TSKgel G5000" (7.8 mm ID x 30 cm) x 1 "TSKgel G4000" (7.8 mm ID x 30 cm) x 1 "TSKgel G3000" (7.8 mm ID x 30 cm) x 1 “TSKgel G2000” (7.8 mm ID × 30 cm) × 1 detector: RI (differential refractometer)
Column temperature: 40 ° C
Eluent: Tetrahydrofuran (THF)
Flow rate: 1.0 mL / min Injection amount: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4 mass%)
Standard sample: A calibration curve was prepared using the following standard polystyrene.

(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

[Evaluation method of initial creep property]
The moisture-curable urethane hot melt resin compositions obtained in the examples and comparative examples were each melted at 120 ° C. for 1 hour. The composition was applied to a rubber plate using an applicator so as to have a thickness of 50 μm. A polyethylene terephthalate sheet having a thickness of 100 μm was bonded onto the coating layer and pressure-bonded with a pressure roller. A test piece having a width of 25 mm is applied to a test piece having a width of 25 mm after 5 minutes from the press bonding, and a peeling length (mm) of polyethylene terephthalate after 15 minutes is measured after applying a load of 90 g, and evaluated as follows. did.
"T": Peeling length is less than 5 mm "F": Peeling length is 5 mm or more

[Measurement method of initial strength]
The moisture-curable urethane hot melt resin compositions obtained in the examples and comparative examples were each melted at 120 ° C. for 1 hour. The composition was applied on a rubber plate using an applicator so that the thickness was 50 μm. Polyethylene terephthalate was bonded onto the coating layer and pressure-bonded with a pressure roller. Tensileon (Tensilon Universal Testing Machine “RTC-1210A” manufactured by Orientec Co., Ltd.) is used for the laminate obtained 5 minutes after the press bonding, and the peel strength at a crosshead speed of 100 mm / min. (N / cm)) was measured and evaluated as follows.
“T”: 25 N / cm or more “F”: less than 25 N / cm

[Evaluation of open time]
The moisture-curable urethane hot melt resin compositions obtained in the examples and comparative examples were each melted at 120 ° C. for 1 hour. The composition was applied onto a polypropylene sheet having a thickness of 50 μm using an applicator so as to have a thickness of 50 μm, and left in a thermostatic bath at 23 ° C. Starting from this point, the time until the kraft paper did not adhere to the adhesive coating layer was measured and defined as the open time.
“T”; more than 30 seconds “F”; less than 30 seconds

  Abbreviations in Tables 1 and 2 indicate the following. Moreover, mass ratio [(B-1) / (B-2)] shows the value which rounded off after the decimal point.

  It has been found that the moisture curable urethane hot melt resin composition of the present invention has excellent initial creep properties and initial strength even when rubber is used as a substrate. Moreover, it turned out that Examples 4-7 which used polyol (A-1) and (A-2) together as a polyol are further excellent in an open time.

  On the other hand, Comparative Example 1 is an embodiment in which the mass ratio of aliphatic polyisocyanate and / or alicyclic polyisocyanate (B-1) is lower than the range defined in the present invention as polyol (B). Both initial creep property and initial strength were poor.

  Comparative Example 2 is an embodiment in which aromatic polyisocyanate (B-2) was used as polyisocyanate (B), but both initial creep properties and initial strength for the rubber substrate were poor.

  Although the comparative example 3 is an aspect using all aliphatic polyisocyanate and / or alicyclic polyisocyanate (B-1) as polyisocyanate (B), initial strength was unsatisfactory.

[Example 7]
In a 2 liter four-necked flask equipped with a stirrer and a thermometer, 58.5 parts by mass of BG / AA, an amorphous polyester polyol (reacted with neopentyl glycol and phthalic anhydride, number average molecular weight; 1 17,000 parts by mass and 17.4 parts by mass of HDI (NCO / OH = 0.9 at this time), mixed, and heated at 50 ° C. under reduced pressure. Thus, dehydration was performed until the water content in the flask became 0.05% by mass.
Next, 6.5 parts by mass of XDI was added, and a urethane prepolymer (melting temperature at 120 ° C .; 70,000 mPa · s) was allowed to react at 110 ° C. for about 3 hours until the isocyanate group content became constant in a nitrogen atmosphere. A moisture curable urethane hot melt resin composition was obtained.
However, Examples 1-3 are reference examples.

Claims (6)

A moisture curable urethane hot melt resin composition containing a urethane prepolymer having an isocyanate group which is a reaction product of a polyol (A) and a polyisocyanate (B),
The polyisocyanate (B) is
Aliphatic polyisocyanate and / or cycloaliphatic polyisocyanate (B-1) and aromatic polyisocyanate (B-2) in a mass ratio [(B-1) / (B-2)] of 10 / A moisture-curable urethane hot melt resin composition, which is used in the range of 90 to 95/5. The moisture-curable urethane hot melt resin composition according to claim 1, wherein the aliphatic polyisocyanate (B-1) is hexamethylene diisocyanate. The moisture-curable urethane hot melt resin composition according to claim 1 or 2, wherein the aromatic polyisocyanate (B-2) is diphenylmethane diisocyanate and / or xylene diisocyanate. The moisture-curable urethane hot according to any one of claims 1 to 3, wherein the polyol (A) contains a crystalline polyol (A-1) and an amorphous polyol (A-2). Melt resin composition. The laminated body in which the hardened | cured material layer of the moisture hardening type urethane hot-melt resin composition of any one of Claims 1-4 was formed on the rubber layer. A shoe having a shoe sole bonded with the moisture-curable urethane hot-melt resin composition according to any one of claims 1 to 4.