TW201825637A - Moisture-curable hot-melt urethane resin composition, laminate, and shoes - Google Patents

Abstract

The present invention provides a moisture-curable hot-melt urethane resin composition which contains an isocyanate-group-containing urethane prepolymer that is a product of the reaction of one or more polyols (A) with polyisocyanates (B), characterized in that the polyisocyanates (B) were (B-1) an aliphatic polyisocyanate and/or an alicyclic polyisocyanate and (B-2) an aromatic polyisocyanate in a (B-1)/(B-2) ratio by mass of from 10/90 to 95/5. It is preferable that the polyols (A) comprise (A-1) a crystalline polyol and (A-2) a noncrystalline polyol. Even when applied to bases made of rubber, the moisture-curable hot-melt urethane resin composition of the present invention can attain excellent initial creep characteristics and excellent initial strength.

Description

   Moisture-hardening urethane hot-melt resin composition, laminate, and shoe   

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

As the adhesive for shoes, solvent-based and water-based adhesives have been the mainstream until now. However, since a drying step is required and double-sided coating is required, productivity is low. On the other hand, moisture-curable urethane hot-melt adhesives are solvent-free, do not require a drying step, and can be coated on one side, so they are excellent in productivity.

As the moisture-curable urethane hot-melt adhesive for soles, for example, a moisture-curable amine group obtained by reacting a crystalline polyester, an aromatic chain extender, a polyisocyanate, etc. has been disclosed. Formate hot-melt adhesive (for example, refer to Patent Document 1).

However, with this adhesive, the molecular weight obtained immediately after bonding is low, and the initial latentity and initial strength (initial peel strength) are low. Therefore, when bonding a sole with a complicated shape, it may be impossible to suppress the use of the sole. A problem of peeling due to the rebound force of the rubber.

Prior art literature Patent literature

Patent Document 1 Japanese Patent Application Laid-Open No. 2004-323838

The problem to be solved by the present invention is to provide a moisture-curable urethane hot-melt resin composition that can obtain excellent initial latentness and initial strength even when a rubber is used as a substrate.

The present invention provides a moisture-curable urethane hot-melt resin composition, which is a urethane prepolymer having an isocyanate group containing a reactant of a polyol (A) and a polyisocyanate (B). , Characterized in that the polyisocyanate (B) is an aliphatic polyisocyanate and / or an alicyclic polyisocyanate (B-1) and an aromatic polyisocyanate (B-2), according to a mass ratio [(B-1) / (B-2)] Use in the range of 10/90 ~ 95/5.

The present invention also provides a laminated body characterized in that a hardened layer of the moisture-curable urethane hot-melt resin composition is formed on a rubber layer. Furthermore, the present invention provides a shoe having a sole followed by the moisture-curable urethane hot-melt resin composition.

The moisture-curable urethane hot-melt resin composition of the present invention can obtain excellent initial latentness and initial strength even when a rubber is used as a matrix. Therefore, in order to be particularly suitable for a user as an adhesive for shoes, even if a sole having a complicated shape is used, good adhesion can still be achieved.

The moisture-curable urethane hot-melt resin composition of the present invention is an isocyanate-containing urethane prepolymer containing a reactant of a polyol (A) and a polyisocyanate (B), and the polyisocyanate (B) is an aliphatic polyisocyanate and / or an alicyclic polyisocyanate (B-1) and an aromatic polyisocyanate (B-2), with a mass ratio [(B-1) / (B-2)] of 10 / 90 ~ 95/5.

As the polyol (A), for example, polyester polyol, polyether polyol, polycarbonate polyol, polybutadiene polyol, polyhydrobutadiene polyol, dimer diol, or polymer can be used. Acrylic polyols and the like. In addition, as the polyol (A), based on the combined use of the crystalline polyol (A-1) and the amorphous polyol (A-2), excellent initial latentness and initial strength can be maintained, and excellent Open time (open time), so it is preferable to use these in combination.

As the polyol (A), the mass ratio [(A-1) / (A-2)] when the (A-1) and (A-2) are used in combination is based on maintaining a moderate opening time and From the viewpoint of more excellent initial strength and initial latent change, a range of 90/10 to 30/70 is preferable, and a range of 80/20 to 50/50 is more preferable.

Examples of the crystalline polyol (A-1) include a crystalline polyester polyol, a crystalline polycarbonate polyol, and a crystalline polyether polyol. These polyols can 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 from the viewpoint of obtaining more excellent initial strength and initial latent properties, and more preferred is a crystalline polymer. Ester polyol.

As the crystalline polyester polyol, for example, a reactant 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, and octanediol. Alcohol, nonanediol, decanediol, dodecanediol, trimethylolpropane, trimethylolethane, glycerol, 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, etc. These compounds may be used alone or in combination of two or more. Among these, since more excellent initial latentity and initial strength can be obtained by more excellent crystallinity, it is preferable to use ethylene glycol, butanediol, hexanediol, and octanediol. One or more compounds selected from the group of decanediol and dodecanediol. These preferred compounds are preferably used in an amount of 30% by mass or more in the aliphatic compound having two or more hydroxyl groups, and more preferably 50% by mass or more.

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 latentity and initial strength can be obtained by more excellent crystallinity, the materials including succinic acid, adipic acid, sebacic acid, and dodecanedioic acid are used. One or more selected from the group is preferred.

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

Commercially available products of this crystalline polycarbonate polyol are "ETERNACOLL UH-200" (above, manufactured by Ube Industries, Ltd.), "Nipporan-981" (Japanese Polyurethane Co., Ltd.) Manufactured), "Duranol T-6002" (manufactured by Asahi Kasei Chemical Co., Ltd.), etc.

As the amorphous polyol (A-2), for example, a polyether polyol, an amorphous polyester polyol, an amorphous polycarbonate polyol, an acrylic polyol, a dimer diol, or the like can be used. These compounds may be used alone or in combination of two or more. Among these, one selected from the group consisting of a polyether polyol, an amorphous polyester polyol, and an amorphous polycarbonate polyol is used from the viewpoint that a better open time can be obtained. More than one kind of polyhydric alcohol is preferable.

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, the use of polypropylene glycol is preferred from the viewpoint that a better open time can be obtained.

As the amorphous polyester polyol, for example, a reactant 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, 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 , Such as alkylene oxide adducts. These compounds may be used alone or in combination of two or more.

As the polybasic acid, for example, 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, etc. These polybasic acids can be used alone or in combination of two or more.

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

As this carbonate, for example, methyl carbonate, dimethyl carbonate, diethyl carbonate, cyclic carbonate, 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, and 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-ethylpropanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like. These compounds may be used alone or in combination of two or more. Among these, from the viewpoint that the glass transition temperature of the urethane prepolymer can be lowered and a better open time can be obtained, it is preferable to use a solvent containing One or more compounds selected from the group consisting of hexanediol, 3-methyl-1,5-pentanediol, 2-methyl-1,8-octanediol and 1,9-nonanediol as raw materials . Among these preferred compounds, 30% by mass or more is preferably used in the compound having two or more hydroxyl groups, and more preferably 50% by mass or more.

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, and more preferably 400 in terms of obtaining more excellent initial latentity and initial strength. Range of ~ 5,000. The number average molecular weight of the polyol (A) indicates a value measured by a gel-permeation-chromatography (GPC) method.

The polyol (A) may be used in combination with a chain elongating agent if necessary.

As this chain elongating agent, for example, ethylenediamine, 1,2-propanediamine, 1,6-hexamethylenediamine, piperidine can be used. 2,5-dimethylpiperazine , Isophorone diamine, 1,2-cyclohexanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 4,4'-dicyclohexylmethanediamine, 3,3 '-Dimethyl-4,4'-dicyclohexylmethanediamine, 1,4-cyclohexanediamine, hydrazine and other chain extenders with amine groups; ethylene glycol, diethylene glycol, triethyl Glycol, propylene glycol, dipropylene glycol, 1,3-propanediol, 1,3-butanediol, 1,4-butanediol, 2-methyl-1,3-propanediol, neopentyl glycol, hexamethylene Diol, 3-methyl-1,5-pentanediol, dimethylol heptane, 1,9-nonanediol, 1,10-decanediol, 1,12-dodecanediol, sucrose , Methylene glycol, glycerol, sorbitan, bisphenol A, 4,4'-dihydrodiphenyl, 4,4'-dihydrodiphenyl ether, trimethylolpropane, etc. Chain extender and so on. These chain elongating agents may be used alone or in combination of two or more kinds.

The amount used when using this chain elongating agent is preferably in the range of 0.1 to 30 parts by mass, and more preferably in the range of 1 to 10 parts by mass, relative to 100 parts by mass of the polyol (A).

As the polyisocyanate (B), an aliphatic polyisocyanate and / or an alicyclic polyisocyanate (B-1) and an aromatic polyisocyanate (B-2) are necessary in a mass ratio [(B-1) / (B -2)] Use in the range of 10/90 ~ 95/5. By using (B-1) and (B-2) within this range, good crystallinity can be obtained, excellent initial latentness and initial strength can be obtained, and excellent manufacturing stability can be obtained. Outside this range, when rubber is used as a substrate, sufficient crystallinity that suppresses rubber rebound cannot be obtained. The mass ratio is more 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 of obtaining more excellent initial latentity and initial strength.

Examples of the aliphatic polyisocyanate and / or alicyclic polyisocyanate (B-1) include hexamethylene diisocyanate, cyclohexane diisocyanate, isophorone diisocyanate, and dicyclohexylmethane diisocyanate. , Tetramethylxylene diisocyanate, etc. 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, and xylene diisocyanate. , Phenylene diisocyanate, methylenediphenyl diisocyanate, naphthalene diisocyanate, etc. These polyisocyanates can be used alone or in combination of two or more. Among these, the use of diphenylmethane diisocyanate and / or xylene diisocyanate is more preferable 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, and more preferably in the range of 10 to 35% by mass in the total mass of the raw materials constituting the urethane prepolymer.

The urethane prepolymer is obtained by reacting the polyol (A) with the polyisocyanate (B), and is present in the air or in a matrix coated with a urethane prepolymer. The isocyanate group having a cross-linked structure can be formed by the reaction of water.

As a method for producing the urethane prepolymer, for example, it can be produced by adding a polyol (A) to a reaction container to which the polyisocyanate (B) has been added, The isocyanate group which the isocyanate (B) has with respect to the hydroxyl group which the said polyol (A) has is an excess condition, and it reacts.

When the urethane prepolymer is produced, the equivalent ratio (isocyanate group / hydroxyl group) of the isocyanate group of the polyisocyanate (B) to the hydroxyl group of the polyol (A) can be obtained based on From the viewpoint of excellent initial latentness and initial strength, the range of 1.1 to 5 is preferred, and the range of 1.15 to 3 is more preferred.

The isocyanate group content (hereinafter abbreviated as "NCO%") of the urethane prepolymer obtained by the above method is preferably from the viewpoint of obtaining more excellent initial latentity and initial strength. The range is from 0.5 to 10, more preferably from 1 to 8. The NCO% of the urethane prepolymer is a value measured by a potentiometric titration method in accordance with JISK1603-1: 2007.

The melt viscosity of the urethane prepolymer at 120 ° C is more preferably in the range of 1,000 to 200,000 mPa · s from the viewpoint of obtaining more excellent initial latentity and initial strength. The range is 3,000 to 150,000 mPa‧s, and the range of 5,000 to 100,000 mPa‧s is more preferable. In addition, the measurement method of the melt viscosity is that after melting the urethane prepolymer at 120 ° C. for 1 hour, 1 ml is sampled, and the melt is measured by a cone-plate viscosity meter (40P cone, number of rotor rotations; 50 rpm). The value of viscosity.

As a method for producing the urethane prepolymer, it is preferable to use a method in which hexamethylene diisocyanate is used as the aliphatic polyisocyanate and / or the alicyclic polyisocyanate (B-1) In this case, first, hexamethylene diisocyanate is reacted with polyol (A) to obtain a prepolymer having a hydroxyl group, and secondly, aromatic polyisocyanate (B-2) is reacted to obtain an amine group having an isocyanate group. Formate prepolymer. According to this manufacturing method, even if a highly volatile hexamethylene diisocyanate is used, a highly crystalline moisture-curable urethane hot-melt resin composition can be obtained stably.

In addition, the equivalent ratio (isocyanate group / hydroxyl group) of the reaction between the hexamethylene diisocyanate and the polyol (A) in the first stage when using this manufacturing method is based on the hexamethylene diisocyanate which can improve high crystallinity. And the viewpoint of obtaining more excellent initial latentity and initial strength, it is preferably 0.5 or more, more preferably in the range of 0.6 to 0.99, and still more preferably in the range of 0.65 to 0.95.

The equivalent ratio (isocyanate group / hydroxyl group) of the reaction between the prepolymer having a hydroxyl group and the aromatic polyisocyanate (B-2) in the second stage is based on the viewpoint that more excellent initial latentity and initial strength can be obtained. It is preferably in the range of 1.1 to 5, and more preferably in the range of 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 also contain other additives as necessary.

Examples of the other additives include hardening catalysts, antioxidants, tackifiers, plasticizers, stabilizers, fillers, dyes, pigments, fluorescent whitening agents, silane coupling agents, waxes, and thermoplastic resins. These additives may be used alone or in combination of two or more.

As described above, even if the moisture-curable urethane hot-melt resin composition of the present invention is based on rubber, excellent initial latentness and initial strength can be obtained. Therefore, in order to be particularly suitable for a user as an adhesive for shoes, even if a sole having a complicated shape is used, good adhesion can still be achieved.

Examples of a method for manufacturing shoes using the moisture-curable urethane hot-melt resin composition of the present invention include, for example, a moisture-curable urethane that has been heated and melted at 50 to 200 ° C. A method in which a hot-melt resin composition is melted and then applied to an outer bottom portion made of rubber or the like, and then a portion other than the sole is adhered.

After this bonding, the moisture-curable urethane hot-melt resin composition may be dried / maintained 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.

    [Example]    

Hereinafter, the present invention will be described in more detail using examples.

    [Example 1]    

In a 2-liter four-neck flask equipped with a stirrer and a thermometer, add an aliphatic polyester polyol (an aliphatic polyester polyol that reacts 1,4-butanediol with adipic acid, the number average molecular weight; 600, Hereinafter, it is abbreviated as "BG / AA") 73.3 parts by mass, hexamethylene diisocyanate (hereinafter, abbreviated as "HDI") 18.5 parts by mass (NCO / OH = 0.9 at this time), and mixed at 50 ° C. Heating was performed under reduced pressure to perform dehydration until the water content in the flask relative to the total amount became 0.05% by mass.

Next, 8.2 parts by mass of xylene diisocyanate (hereinafter abbreviated as "XDI") was added, and the reaction was carried out at 110 ° C for about 3 hours under a nitrogen atmosphere until the isocyanate group content became a fixed value, thereby obtaining aminomethyl Ester prepolymer (melting temperature at 120 ° C; 50,000 mPa · s) is used 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, add an aliphatic polyester polyol (an aliphatic polyester polyol that reacts 1,6-hexanediol with dodecanedioic acid, the number average molecular weight; 1,000, below, abbreviated as "HG / DDA") 82.3 parts by mass and 11.1 parts by mass of HDI (NCO / OH = 0.8 at this time), mixed, and heated under reduced pressure at 50 ° C to perform dehydration until the inside of the flask is relatively The amount of water in the total amount was 0.05% by mass.

Next, 6.6 parts by mass of XDI was added, and the reaction was performed at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became a fixed value, thereby obtaining a urethane prepolymer (melting temperature at 120 ° C.). 60,000 mPa‧s) as a moisture-curable urethane hot-melt resin composition.

    [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 (NCO / OH = 0.85 at this time) were added, and mixed at 50 Heating was carried out under reduced pressure at a temperature of 0 ° C. until the moisture in the flask relative to the total amount became 0.05% by mass.

Next, 12.7 parts by mass of 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") was added, and the reaction was carried out at 110 ° C for about 3 hours under a nitrogen atmosphere until the isocyanate group content became a constant value. Thus, a urethane prepolymer (melting temperature at 120 ° C; 70,000 mPa · s) was obtained as 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 25.6 parts by mass of polypropylene glycol (number average molecular weight; 1,000, abbreviated as "PPG") are added. 1. HDI 16.8 parts by mass (NCO / OH = 0.9 at this time), mixed, and heated under reduced pressure at 50 ° C. to perform dehydration until the moisture in the flask relative to the total amount becomes 0.05% by mass.

Next, 6.3 parts by mass of XDI was added, and the reaction was performed at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became a constant value, thereby obtaining a urethane prepolymer (melting temperature at 120 ° C.). 70,000 mPa‧s) as a moisture-curable urethane hot-melt resin composition.

    [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 at this time), The mixture was mixed and heated under reduced pressure at 50 ° C to perform dehydration until the moisture in the flask relative to the total amount became 0.05% by mass.

Next, 6.2 parts by mass of XDI was added, and the reaction was performed at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became a constant value, thereby obtaining a urethane prepolymer (melting temperature at 120 ° C.). 75,000 mPa · s) as a moisture-curable urethane hot-melt resin composition.

    [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 (NCO / OH = 0.9 at this time) were added, mixed, and carried out at 50 ° C. Heating was performed under reduced pressure until the water content in the flask relative to the total amount became 0.05% by mass.

Next, 9.4 parts by mass of 4,4'-diphenylmethane diisocyanate (hereinafter abbreviated as "MDI") was added, and the reaction was carried out at 110 ° C for about 3 hours under a nitrogen environment until the isocyanate group content became a fixed value. Thus, a urethane prepolymer (melting temperature at 120 ° C; 80,000 mPa · s) was obtained as 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; 1,000 (Hereinafter, abbreviated as "NPG / OPA") 17.6 parts by mass and 17.4 parts by mass of HDI (NCO / OH = 0.9 at this time), mixed, and heated under reduced pressure at 50 ° C to dehydrate until the inside of the flask The total moisture content was 0.05% by mass.

Next, 6.5 parts by mass of XDI was added, and the reaction was performed at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became a constant value, thereby obtaining a urethane prepolymer (melting temperature at 120 ° C.). 70,000 mPa‧s) as a moisture-curable urethane hot-melt resin composition.

    [Comparative Example 1]    

In a 2-liter four-neck flask equipped with a stirrer and a thermometer, add an aliphatic polyester polyol (an aliphatic polyester polyol that reacts 1,4-butanediol with adipic acid, the number average molecular weight; 600) 68.9 parts by mass and 5.8 parts by mass of hexamethylene diisocyanate (NCO / OH = 0.3 at this time) were mixed and heated under reduced pressure at 50 ° C to perform dehydration until the moisture in the flask relative to the total amount became 0.05 quality%.

Next, 25.3 parts by mass of 4,4′-diphenylmethane diisocyanate was added, and the reaction was performed at 110 ° C. for about 3 hours under a nitrogen environment until the isocyanate group content became a fixed value, thereby obtaining a urethane. The prepolymer (melting temperature at 120 ° C; 40,000 mPa · s) is used as a moisture-curable urethane hot-melt resin composition.

    [Comparative Example 2]    

In a 2-liter four-neck flask equipped with a stirrer and a thermometer, add an aliphatic polyester polyol (an aliphatic polyester polyol that reacts 1,4-butanediol with adipic acid, the number average molecular weight; 600) 68 parts by mass was heated under reduced pressure at 50 ° C to perform dehydration until the moisture in the flask relative to the total amount became 0.05% by mass.

Next, 32 parts by mass of 4,4'-diphenylmethane diisocyanate was added, and the reaction was performed at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became a constant value, thereby obtaining a urethane. A prepolymer (melting temperature at 120 ° C; 70,000 mPa · s) is used as a moisture-curable urethane hot-melt resin composition.

    [Comparative Example 3]    

In a 2-liter four-neck flask equipped with a stirrer and a thermometer, add an aliphatic polyester polyol (an aliphatic polyester polyol that reacts 1,4-butanediol with adipic acid, the number average molecular weight; 600) 76.3 parts by mass were mixed and heated under reduced pressure at 50 ° C. to perform dehydration until the moisture in the flask relative to the total amount became 0.05% by mass.

Next, 23.7 parts by mass of hexamethylene diisocyanate was added, and the reaction was performed at 110 ° C. for about 3 hours under a nitrogen atmosphere until the isocyanate group content became a fixed value, thereby obtaining a urethane prepolymer (120 Melting temperature at ℃; 30,000 mPa · s), as a moisture-curable urethane hot-melt resin composition.

    [Method for measuring number average molecular weight]    

The number average molecular weights of the polyhydric alcohols and the like used in the examples and comparative examples represent values measured by a gel-permeation-chromatography (GPC) method under the following conditions.

Measuring device: High-speed GPC device ("HLC-8220GPC" manufactured by TOSOH Corporation)

Column: Use the following Columns made by TOSOH Co., Ltd. in series

`` TSKgel G5000 '' (7.8mm I.D. × 30cm) × 1

`` TSKgel G4000 '' (7.8mm I.D. × 30cm) × 1

`` TSKgel G3000 '' (7.8mm I.D. × 30cm) × 1

`` TSKgel G2000 '' (7.8mm I.D. x 30cm) x 1

Detector: RI (differential refractometer)

Column temperature: 40 ℃

Eluent: Tetrahydrofuran (THF)

Flow rate: 1.0 ml / min

Injection volume: 100 μL (tetrahydrofuran solution with a sample concentration of 0.4% by mass)

Standard sample: Use the following standard polystyrene to make a calibration line.

    (Standard polystyrene)    

"TSKgel Standard Polystyrene A-500" 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" made by TOSOH Corporation

"TSKgel Standard Polystyrene F-550" by TOSOH Corporation

    [Evaluation method of initial latentity]    

The moisture-curable urethane hot-melt resin compositions obtained in the examples and comparative examples were each melted at 120 ° C. for 1 hour. This composition was applied with an applicator so that the thickness of the rubber plate became 50 μm. A 100 μm-thick polyethylene terephthalate sheet was attached to the coating layer, and pressure-bonded with a pressure-bonding roller. After 5 minutes after pressure bonding, a load of 200 g was applied to a 25 mm wide test piece in the 90 ° direction, and the peeling length (mm) of polyethylene terephthalate after 15 minutes was measured, and evaluated as follows .

"T": Peeling length is less than 5mm

"F": Peeling length is 5mm or more

    [Method for measuring 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. This composition was applied with an applicator so that the thickness of the rubber plate became 50 μm. Polyethylene terephthalate was adhered to the coating layer, and pressure-bonded with a pressure-bonding roller. After 5 minutes after the pressure-bonding, the obtained laminated body was measured for peeling strength using TENSILON (TENSILON universal testing machine "RTC-1210A" manufactured by Orientec Co., Ltd.) at a crosshead speed of 100 mm / min N / cm) and evaluated as follows.

"T": 25N / cm or more

"F": less than 25N / cm

    [Evaluation of opening hours]    

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 polypropylene sheet having a thickness of 50 μm with an applicator so that the thickness became 50 μm, and then placed in a constant temperature bath at 23 ° C. From this time point, the time until the kraft paper could not adhere to the adhesive coating layer was measured as the opening time.

"T": 30 seconds or more

"F": less than 30 seconds

The abbreviations in Tables 1 to 2 are as follows. The mass ratio [(B-1) / (B-2)] is a value rounded to the nearest decimal point.

It is understood that the moisture-curable urethane hot-melt resin composition system of the present invention can have excellent initial latentness and initial strength even if it is based on rubber. In addition, it can be seen that Examples 4 to 7 using polyols (A-1) and (A-2) as a polyol in combination are more excellent in the opening time.

On the other hand, Comparative Example 1 is a state in which the mass ratio of the aliphatic polyisocyanate and / or alicyclic polyisocyanate (B-1) in the polyol (B) is lower than the range specified in the present invention. Therefore, the initial latent properties and initial strength are not good relative to the rubber matrix.

Comparative Example 2 is a state in which an aromatic polyisocyanate (B-2) is used as the polyisocyanate (B), so the initial latentness and the initial strength with respect to the rubber substrate are not good.

Comparative Example 3 is a state in which an aliphatic polyisocyanate and / or an alicyclic polyisocyanate (B-1) is used as the polyisocyanate (B), so the initial strength is not good.

Claims (6)

    A moisture-curable urethane hot-melt resin composition, which is a urethane prepolymer having an isocyanate group containing a reactant of a polyol (A) and a polyisocyanate (B), and is characterized in that: The polyisocyanate (B) is an aliphatic polyisocyanate and / or an alicyclic polyisocyanate (B-1) and an aromatic polyisocyanate (B-2), according to the mass ratio [(B-1) / (B-2 )] Use in the range of 10/90 ~ 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-melt resin composition 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).         A laminated body characterized in that a hardened layer of a moisture-curable urethane hot-melt resin composition according to any one of claims 1 to 4 is formed on a rubber layer.         A shoe characterized by having a sole followed by passing through the moisture-curable urethane hot-melt resin composition according to any one of claims 1 to 4.