KR20120118657A - Polyurethane adhesive composition in improving bonding strength for nylon shoe material - Google Patents

Abstract

PURPOSE: A polyurethane adhesive composition is provided to have excellent initial adhesion, final adhesion and initial heat resistance and final heat resistance, and to reduce production cost by reduction of contact failure. CONSTITUTION: A polyurethane adhesive composition is formed by mixing followings: a polyester polyol mixture consisting of 100.0 parts by weight of polyester polyol with a number average molecular weight of 2,000-3,000 and 50-70 parts by weight of polyester polyol with a number average molecular weight of 4,000-5,000; 0.1-1.0 parts by weight of a monomer with an epoxy group; 1.0-1.5 parts by weight of a chain extender, 13-15 parts by weight of organic diisocyanate, 0.02-0.05 parts by weight of a catalyst, 0.1-2.0 parts by weight of a silane crosslinking agent, and 1.0-5.0 parts by weight of an adhesion reinforcing agent.

Description

Polyurethane adhesive composition in improving bonding strength for nylon shoe material}

The present invention relates to a polyurethane adhesive composition having improved adhesion to a nylon material, and more particularly, to a polyurethane adhesive composition characterized by improved adhesion to a material of a low polar shoe material such as nylon.

Recently, the shoes industry has been developing shoes of a complex configuration and various kinds of functional shoes due to the increasing interest in people's fashion and functionality. These shoes, as well as the development of a variety of designs, in particular, the functionality of the shoes is important, so many materials that require ultra-lightweight, such as nylon materials are used.

Such nylon materials are chain-shaped polymers connected by amide bonds, and have excellent durability and chemical resistance, but when the polyurethane adhesive is used due to low surface tension and hydrogen bonding between them, the adhesive force is very low, and thus the adhesive force is improved. Before the process, it is necessary to apply the primer to the nylon surface or to modify the surface as a pretreatment process, which causes problems such as waste of energy, increase of labor cost, and increase of production equipment and operating cost. Not maintained, there was a problem that the adhesive performance is lowered after a long time.

In order to solve the above problems, a variety of developments such as research on the surface modification and primer development suitable for nylon material, and looking at the patents of these technologies,

Korean Patent Laid-Open Publication No. 10-2008-0093513 relates to a one-component polyurethane resin for soft-package bonding, and is a blocking agent capable of curing by dissociating aliphatic and alicyclic isocyanates having different thermal properties from conventional polyurethane resins at low temperatures. In order to manufacture the blocked polyisocyanate synthesized by capping and reacting with the silane crosslinking agent, which is an adhesion promoter, by reacting with the solvent, it must be produced through a complicated manufacturing process. The adhesive has a problem, and since the blocking agent dissociation temperature for crosslinking is a high temperature (100 ° C. or higher), a dry shoe condition of a shoe factory usually has a problem to be used in a shoe adhesive that has a working process at a low temperature of 50 to 60 ° C. In addition, Korea Patent Publication No. 10-2008-0008523 relates to the coating material for automobile electrodeposition coating, the polychlorinated polyolefin resin, quick-drying acrylic resin, slow-drying acrylic resin, micronized silica dispersion having a micron particle size, talc-based It is known as a coating composition comprising a sieving pigment, a polysiloxane-based surface dispersant and an aromatic solvent. However, in the case of the above patent, the crosslinking of a composition containing an excess of chlorinated polyolefin resin at high temperature ( More than 90 ℃) drying and aromatic solvents can cause fatal problems to the human body, as well as poor initial adhesion, late adhesion, initial heat and late heat resistance to nylon materials. There was a problem such as increase.

In addition, it is known that in Korean Patent Application Publication No. 10-2004-0101650, X-rays are irradiated to plastic, that is, nylon material, thereby lowering the glass transition temperature of the surface of the nylon material to directly modify the material to increase adhesive strength. In the case of the above patent, it is a method of modifying the surface of a material other than the adhesive for shoes, and there is a problem of increasing the production cost by requiring an X-ray irradiation apparatus separately, and also in Korea Patent Publication No. 10-2007-0072280 It consists of two kinds of acrylic urethane water-dispersion resins having different molecular weights. The acrylic water-dispersion resin is prepared by reacting a polyurethane water-dispersion resin prepared by a general method with a chain extender and then polymerizing with an initiator and an acrylic monomer. The polyurethane water dispersion resin forms a polyurethane resin by polymerizing a compound having a polyol, an excess of isocyanate, and an anionic functional group. Water-soluble paints that improve adhesion to nylon materials obtained by neutralizing anion functional groups in polyurethane with an appropriate base and then water-dispersed in water are known, but in the case of the above patents, they are poorly hydrolyzed and applied as footwear adhesives. The following is a problem.

Therefore, the present invention is to solve the problems described above, the poly-polyol having two molecular weights having different molecular weight dissolved in a solvent with a solvent, a polyisomer synthesized by adding a diisocyanate, a chain extender, a silane crosslinking agent and a catalyst A polyurethane adhesive composition is prepared by mixing an urethane adhesive composition with an adhesive reinforcing agent comprising a monomer having a functional group selected from a halogen atom, a hydroxyl group and a carboxyl group to prepare a polyurethane adhesive composition, in particular, having good initial adhesion, late adhesion, initial heat resistance, and late heat resistance to a nylon material. An object of the present invention is to provide a polyurethane adhesive composition having improved adhesion to nylon materials.

The present invention for achieving the above object in the polyurethane adhesive composition,

100 parts by weight of a polyester polyol (a) having a number average molecular weight of 2,000 to 3,000,

Polyester polyol mixture consisting of 50 to 70 parts by weight of polyester polyol (b) having a number average molecular weight of 4,000 to 5,000,

Based on 100 parts by weight of the polyester polyol (a),

0.1 to 1.0 parts by weight of monomer having an epoxy group, 1.0 to 1.5 parts by weight of chain extender, 13 to 15 parts by weight of organic diisocyanate, 0.02 to 0.05 parts by weight of catalyst, 0.1 to 2.0 parts by weight of silane crosslinker and 1.0 to 5.0 parts by weight of adhesion modifier A polyurethane adhesive composition having improved adhesion to a nylon material, which is formed by mixing, is a problem solving means.

And the said polyester polyol (a) and polyester polyol (b) are 1, 4- butanediol / adipic acid polyester polyol which made 1, 4- butanediol and adipic acid react.

Moreover, the said organic diisocyanate is an aliphatic and aromatic diisocyanate, For example, hexamethylene diisocyanate, isopron diisocyanate, methyl cyclohexane diisocyanate, xylene diisocyanate, diphenyl methane diisocyanate, 1, 5- naphthalene diisocyanate, 2, One or more of 4-toluene diisocyanate and 2,6-toluene diisocyanate are selected and used.

In addition, the monomer having an epoxy group is characterized in that the glycidol having a structure of formula (1) below.

(Formula 1)

And the chain extender, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1, 4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol , 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 1,3-pentanediol, 2- Ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-hexyl-1,3-propanediol, 1,8-octanediol, 2-methyl-1, Aliphatic glycols such as 8-octanediol, 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, glycols having aromatic rings such as xylylene glycol, bishydroxyethoxybenzene, or the like Select and use the above.

Moreover, the said silane crosslinking agent is phenyl-3-aminopropyl triethoxysilane, phenyl-3-aminopropyl trimethoxysilane, cyclohexyl-3-amino protriethoxysilane, and cyclohexyl-3-aminopropyl triethoxy One or more of silane, 1,3-bisaminopropyltetraethylsiloxane, and polydimethylsiloxane are selected and used.

In addition, the catalyst is selected from one or more selected from an organometallic compound containing dibutyltin dilaurate, an organic amine containing triethylenediamine and salts thereof,

The adhesion enhancer. As a monomer having a functional group selected from a halogen atom, a hydroxyl group and a carboxyl group, naphthalic anhydride, phosphoric anhydride, maleic anhydride, phthalic anhydride, acetic anhydride, itaconic anhydride, It is characterized by using one or more selected from Chlorendic anhydride, boric anhydride, trimellitic anhydride.

The present invention has good initial adhesion, late adhesion, initial heat resistance, and late heat resistance to the nylon material, thereby contributing to the reduction of the adhesion failure rate and thereby reducing the manufacturing cost.

The present invention for achieving the above effect relates to a polyurethane adhesive composition with improved adhesion to a nylon material, only the parts necessary to understand the technical configuration of the present invention will be described, the description of other parts scatter the gist of the present invention. Note that it will be omitted so as not to fall short.

Hereinafter, the polyurethane adhesive composition having improved adhesion to a nylon material according to the present invention will be described in detail.

The present invention is a monomer having a functional group selected from a halogen atom, a hydroxyl group and a carboxyl group in a polyurethane adhesive composition synthesized by dissolving a monomer having a mixed polyol, an organic diisocyanate and an epoxy group in a solvent and adding a chain extender, a silane crosslinking agent and a catalyst. It relates to a polyurethane adhesive composition with improved adhesion to a nylon material, characterized in that it comprises an adhesive reinforcing agent.

Hereinafter, the components of the polyurethane prepolymer for synthesizing the polyurethane adhesive composition having improved adhesion to the nylon material according to the present invention will be described in detail.

The mixed polyester polyol used in the present invention is a poly-polyester consisting of 100 parts by weight of a polyester polyol (a) having a number average molecular weight of 2,000 to 3,000 and 50 to 70 parts by weight of a polyester polyol (b) having a number average molecular weight of 4,000 to 5,000. Preference is given to ester polyol mixtures.

In the present invention, the polyester polyol (a) and the polyester polyol (b) are polyester polyols having good adhesion and heat resistance durability, and specific examples of the polyester polyols include ethylene glycol (hereinafter, abbreviated as 'EG') and di Ethylene glycol, dipropylene glycol, 1,2-propanediol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol (hereinafter abbreviated as 'NPG') 1,2-pentanediol, 1,3-pentanediol, 1,4-pentanediol, 1,5-pentanediol, 2-methyl-1.5-pentanediol, 3-methyl-1,5-pentanediol , 1,6-hexanediol, 2,2,4-trimethyl-1,3-propanediol, 2-ethyl-1,3-hexanediol, 2,2-diethyl-1,3-propanediol, 2- So-called low molecular glycols such as n-butyl-2-ethyl-1,3-propanediol, ethylene oxide adducts of bisphenol A, and propylene oxide adducts of bisphenol A, and mixtures thereof and succinic acid, adipic acid, sebacic acid, azela Acid, Phthalic Acid, It is preferable that it is polyester which has both terminal hydroxyl groups obtained by the decarboxylation reaction of dicarboxyl, such as isophthalic acid, terephthalic acid, fumaric acid, maleic acid, oxalic acid, naphthylenedicarboxylic acid, these acid ester, and acid anhydride.

At this time, the polyester polyol (a) and the polyester polyol (b) is most preferably a polyester polyol of 1,4-butanediol / adipic acid reacted with 1,4-butanediol and adipic acid, respectively.

The polyester polyol (a) having a number average molecular weight of 2,000 to 3,000 has a hydroxyl value of 42 to 56, and has excellent adhesive strength and discoloration resistance, and the mixing amount thereof is based on 100 parts by weight. When the polyester polyol (a) has a number average molecular weight of less than 2,000, there is a concern that the adhesive strength may decrease due to the increase of hard segments, and when the number average molecular weight exceeds 3,000, the heat resistance may decrease due to the increase of the content of the soft segment. There is.

In addition, the polyol (b) of the polyester having a number average molecular weight of 4,000 to 5,000 has a hydroxyl value of 20 to 35 and gives an excellent initial tack, and the mixing amount thereof is preferably 50 to 70 parts by weight. When the amount of the polyester polyol b) is less than 50 parts by weight, it is difficult to exhibit the properties of the polymer. When the amount of the polyester polyol is greater than 70 parts by weight, the reaction rate is relatively faster due to the influence of high molecular weight, and thus there is a concern that the adhesive force is immediately lost. have. When the number average molecular weight of the polyester polyol (b) is less than 4,000, it will be difficult to exhibit the properties. If the polyester polyol is more than 5,000, there is a possibility of promoting the disappearance of adhesion immediately, deterioration of adhesion and heat resistance.

It is preferable that the organic diisocyanate used for this invention is 13-15 weight part with respect to 100 weight part of polyester polyols (a). When the usage-amount of organic diisocyanate is less than 13 weight part, sufficient polyurethane may not be synthesize | combined, and when it exceeds 15 weight part, there exists a possibility that unreacted organic diisocyanate may remain.

In addition, in the present invention, the organic diisocyanate is added stepwise to prevent a rapid increase in viscosity, and the first amount is about 95% of the organic diisocyanate amount compared to NCO / OH. . After that, the remaining amount of the organic diisocyanate added is divided into two to three times, and is added at intervals of two hours, and the solvent is also added in combination with the organic diisocyanate to prevent an overload on a sudden increase in viscosity.

Organic diisocyanates used in the present invention are aliphatic and aromatic diisocyanates, such as hexamethylene diisocyanate, isopron diisocyanate (hereinafter abbreviated as 'IPDI'), methyl cyclohexane diisocyanate, xylene diisocyanate, diphenyl methane diisocyanate , 1,5-naphthalene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, or the like is preferably used.

Although the monomer which has an epoxy group used by this invention uses a number average molecular weight of 100 or less, It is preferable that the mixing amount is 0.1-1.0 weight part with respect to 100 weight part of polyester polyols (a). When the amount of the monomer having an epoxy group is less than 0.1 part by weight, the increase in adhesion to the material is insignificant. When the amount of the monomer having an epoxy group is less than 1.0 part by weight, it is difficult to increase the viscosity by inhibiting the urethane reaction and strengthening the strength of the film after drying. There is a risk of deterioration in impact properties.

At this time, it is preferable to use a glycidol having a structure of Formula 1 below as the monomer having an epoxy group.

(Formula 1)

Since the elasticity of a polyurethane elastomer improves, the chain extender used by this invention is more preferable in physical property, and it is preferable that it is 1.0-1.5 weight part with respect to 100 weight part of polyester polyols (a). If the amount of the chain extender is less than 1.0 part by weight, there is a fear that sufficient chain extension reaction does not occur during the synthesis of polyurethane. If the amount of the chain extender exceeds 1.5 parts by weight, the chain extender acts as a hard segment so that the urethane and urea It is too hard to obtain the desired physical properties and there is a fear that it is not easily dissolved in the solvent.

Meanwhile, the chain extender usable in the present invention is ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3- Butanediol, 1,4-butanediol, 2,3-butanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1, 3-propanediol, 2-butyl-2-ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 1,3-pentane Diol, 2-ethyl-1,3-hexanediol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-hexyl-1,3-propanediol, 1,8-octanediol, 2- Aliphatic glycols such as methyl-1,8-octanediol, 1,9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, glycols having aromatic rings such as xylylene glycol and bishydroxyethoxybenzene It is preferable to select and use 1 type or more.

Although the number average molecular weight of the silane crosslinking agent used by this invention uses 300 or less, It is preferable that the mixing amount is 0.1-2.0 weight part with respect to 100 weight part of polyester polyols (a). If the amount of the silane crosslinking agent is less than 0.1 part by weight, the crosslinking effect is insufficient and may act as a powder, and the adhesion may be lowered. Tack) Induces annihilation, which may lower the adhesive strength.

Meanwhile, silane crosslinkers usable in the present invention include phenyl-3-aminopropyltriethoxysilane, phenyl-3-aminopropyltrimethoxysilane, cyclohexyl-3-aminoprotriethoxysilane, cyclohexyl-3- Aminopropyltriethoxysilane, 1,3-bisaminopropyltetraethylsiloxane, polydimethylsiloxane, and the like.

Known so-called polyurethane catalysts can be used to synthesize the polyurethane-based resin according to the present invention, and it is preferably 0.02 to 0.05 parts by weight based on 100 parts by weight of the polyester polyol (a). When the mixing amount of the catalyst is less than the range defined above, the reaction rate is slow, and when it exceeds the range defined above, there is a fear that the reaction yield is lowered due to a sudden reaction.

Specifically, catalysts used in the present invention include organic metal compounds such as dibutyltin dilaurate, organic amines such as triethylenediamine, salts thereof, and the like.

Since the adhesion | attachment adjuvant used for this invention improves adhesion | attachment to a nylon material, it is more preferable on a physical property.

It is preferable that the said adhesive reinforcing agent is 1.0-5.0 weight part with respect to 100 weight part of polyurethane adhesive compositions. When the mixed amount of the adhesive reinforcing agent is less than 1.0 part by weight, there is a fear that the effect of the adhesive reinforcement may not be exhibited. When the amount of the adhesive reinforcing agent is more than 5.0 parts by weight, the lowering of the adhesive force may be a factor that hinders the adhesive force.

The monomer having a functional group selected from a halogen atom, a hydroxyl group and a carboxyl group as an adhesion promoter in the polyurethane adhesive composition suitable for the present invention may be naphthalic anhydride, phosphoric anhydride, maleic anhydride, phthalic anhydride, Acetic anhydride, itaconic anhydride, clorendic anhydride, boric anhydride, trimellitic anhydride, and the like, and these may be used alone or in combination of two or more thereof.

Optionally, the urethane prepolymer may optionally be added an aliphatic solvent to form a urethane prepolymer diluted with an aliphatic solvent. The solvents are ester solvents such as ethyl acetate and butyl acetate, which are not aromatic solvents, which are the main causes of conventional environmental problems, alcohol solvents such as methanol, isopropanol and butanol, and acetone, methyl ethyl ketone, and methyl isobutyl ketone. It contains a ketone solvent, it can be used by mixing one or two or more selected from these solvents.

At this time, it is preferable that the solvent used to obtain the polyurethane adhesive composition suitable for the present invention is 90/10 to 40/60 (solvent / polyurethane resin adhesive composition) in a weight ratio with respect to the polyurethane resin adhesive composition, and 85 It is still more preferable that it is / 15-50 / 50 (solvent / polyurethane resin adhesive composition).

Although the present invention will be described in detail with reference to Examples, the present invention is not limited to Examples.

1. Preparation of polyurethane adhesive composition for nylon shoe material

(Example 1)

A four-necked flask equipped with a condenser, a stirrer, and a thermometer was used for 1,4-butanediol / adipic acid having a number average molecular weight of 4,000 based on 100 parts by weight of a polyester polyol of 1,4-butanediol / adipic acid having a number average molecular weight of 2,000. 50 parts by weight of polyester polyol, 0.1 parts by weight of glycidyl as a monomer including an epoxy substituent, 1.0 parts by weight of 1,4 butanediol as a chain extender, and 0.5 parts by weight of 1.6 hexanediol were added, and the temperature was 80-90 ° C under a nitrogen atmosphere. After stirring at an elevated temperature, 13 parts by weight of hexamethylene diisocyanate, an organic diisocyanate, and 0.02 part by weight of dibutyltin dilaurate as a catalyst were added thereto, followed by reaction at 85 ± 1 ° C. for 1 hour, and then 1,3-bisamino as a silane crosslinking agent. 0.1 parts by weight of propyltetraethylsiloxane was added and then reacted for 7 hours to prepare a polyurethane adhesive composition. After the addition of 1.0 parts by weight of chlorenic anhydride as an adhesive enhancer to complete the adhesive composition.

In the above, the above isocyanate is added in steps to prevent a sharp increase in viscosity, and the first input amount is 50 parts by weight of solvent within 1 hour after 12.3 parts by weight, which is about 95% of NCO / OH. After that, the remaining amount of isocyanate is divided into two and added at intervals of two hours, and the solvent is also added to the isocyanate to prevent an overload on a sharp increase in viscosity.

(Example 2)

A polyester of 1,4-butanediol / adipic acid having a number average molecular weight of 4,000 was added to 100 parts by weight of a polyester polyol of 1,4-butanediol / adipic acid having a number average molecular weight of 2,000 in the same apparatus as in Example 1. 70 parts by weight of polyol, 1.0 part by weight of glycidyl as a monomer including an epoxy tube, 1.0 part by weight of 1,4 butanediol as a chain extender, and 0.5 part by weight of 1.6 hexanediol were added and stirred at a temperature of 80 to 90 ° C. under a nitrogen atmosphere. Then, 15 parts by weight of hexamethylene diisocyanate, which is an organic diisocyanate, and 0.05 parts by weight of dibutyltin dilaurate, which is a catalyst, were reacted at 85 ± 1 ° C. for 1 hour, and then 1,3-bisaminopropyltetraethyl, a silane crosslinking agent. After the 2.0 parts by weight of the siloxane was reacted for 7 hours to prepare a polyurethane adhesive composition. In this case, 5.0 parts by weight of Chlorenic Anhydride was added as an adhesive enhancer to complete the adhesive composition.

(Comparative Example 1)

A polyester of 1,4-butanediol / adipic acid having a number average molecular weight of 4,000 was added to 100 parts by weight of a polyester polyol of 1,4-butanediol / adipic acid having a number average molecular weight of 2,000 in the same apparatus as in Example 1. 75 parts by weight of polyol, 0.8 parts by weight of 1,4 butanediol as a chain extender, and 0.7 parts by weight of 1.6 hexane diol were added, and 15 parts by weight of hexamethylene diisocyanate, which is an organic diisocyanate, after stirring at a temperature of 80 to 90 ° C. under a nitrogen atmosphere. 0.02 parts by weight of dibutyltin dilaurate as a catalyst was added thereto, followed by reaction at 85 ± 1 ° C. for 6 hours to prepare a polyurethane adhesive composition.

(Comparative Example 2)

A polyester of 1,4-butanediol / adipic acid having a number average molecular weight of 4,000 was added to 100 parts by weight of a polyester polyol of 1,4-butanediol / adipic acid having a number average molecular weight of 2,000 in the same apparatus as Comparative Example 1. 50 parts by weight of polyol, 0.3 parts by weight of glycidyl as a monomer containing an epoxy functional group, 0.5 parts by weight of 1,4 butanediol as a chain extender and 0.5 parts by weight of 1.6 hexanediol were added thereto, and the mixture was heated and stirred at a temperature of 80 to 90 ° C. under a nitrogen atmosphere. Thereafter, 13 parts by weight of hexamethylene diisocyanate, which is an organic diisocyanate, and 0.02 part by weight of dibutyltin dilaurate, which was a catalyst, were added and then reacted at 85 ± 1 ° C. for 6 hours to prepare a polyurethane adhesive composition.

2. Evaluation of Polyurethane Adhesive Compositions with Improved Adhesion to Nylon Materials

Polyurethane adhesive composition prepared by the method of Examples 1 and 2 and Comparative Examples 1 and 2, the results of comparing and evaluating the adhesive force to the nylon material according to the test method is as shown in Table 1 below.

end. Preparation of Adhesive Specimen

A nylon primer (PR 713 Hwaseung T & C) was applied to a nylon specimen having a size of 20100 mm three times using a brush and dried in a blow drying oven at 60 ° C. for 7 minutes.

Examples 1, 2 and Comparative Examples 1 to 3 were applied to the test specimen and the rubber test specimen three times using a brush, and then dried at 60 ° C. for 5 minutes, and then bonded to the adhesive surface of the dried rubber specimen and the nylon specimen to about 60 kg / The test piece was produced by crimping 25 mm rolls. In this case, the test specimens used in the same test were used for each of the four examples, each of the initial and late adhesive strength test items, each used one for each of the initial and late heat test items.

I. Early and late adhesion

The four adhesive specimens prepared by the method of 'A' were left to stand at room temperature for 30 minutes and 24 hours, and then peeled and bonded at 50 ± 10 mm / min tensile speed using a universal tensile tester (Instron model name 1011). The strength was measured, and the average value of the test results is shown in [Table 1] below.

                                               (Unit: unit kgf / 20mm) division Example Comparative example One 2 One 2 Initial adhesion 2.315 2.300 2.015 2.221 Late adhesion 4.556 4.223 3.541 3.556

As a result of testing the polyurethane adhesive composition with improved adhesion to the nylon material, Examples 1 and 2, as shown in the above [Table 1], it was found that the initial adhesion and the late adhesion is superior to Comparative Examples 1 and 2.

As described above, the polyurethane adhesive composition for nylon shoe material according to the present invention has been described through the above-described preferred embodiments, and confirmed the superiority, but those skilled in the art will have the idea of the present invention described in the following claims It will be understood that various modifications and variations can be made in the present invention without departing from the scope of the invention.

Claims (8)

In the polyurethane adhesive composition,
100 parts by weight of a polyester polyol (a) having a number average molecular weight of 2,000 to 3,000,
Polyester polyol mixture consisting of 50 to 70 parts by weight of polyester polyol (b) having a number average molecular weight of 4,000 to 5,000,
Based on 100 parts by weight of the polyester polyol (a),
0.1 to 1.0 parts by weight of monomer having an epoxy group, 1.0 to 1.5 parts by weight of chain extender, 13 to 15 parts by weight of organic diisocyanate, 0.02 to 0.05 parts by weight of catalyst, 0.1 to 2.0 parts by weight of silane crosslinker and 1.0 to 5.0 parts by weight of adhesion modifier Polyurethane adhesive composition with improved adhesion to the nylon material, characterized in that the mixture.
The method of claim 1,
The polyester polyol (a) and polyester polyol (b),
A polyurethane adhesive composition having improved adhesion to a nylon material, which is a polyester polyol of 1,4-butanediol / adipic acid reacted with 1,4-butanediol and adipic acid.
The method of claim 1,
The organic diisocyanate is,
As aliphatic and aromatic diisocyanate, hexamethylene diisocyanate, isoprene diisocyanate, methyl cyclohexane diisocyanate, xylene diisocyanate, diphenyl methane diisocyanate, 1,5-naphthalene diisocyanate, 2,4-toluene diisocyanate, 2 A polyurethane adhesive composition having improved adhesion to a nylon material, characterized in that one or more selected from among 6-toluene diisocyanate and the like.
The method of claim 1,
The monomer which has the said epoxy group,
Polyurethane adhesive composition with improved adhesion to the nylon material, characterized in that the glycidol having a structure of formula (1) below.

(Formula 1)

The method of claim 1,
The chain extender,
Ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, tripropylene glycol, 1,3-propanediol, 1,2-butanediol, 1,3-butanediol, 1,4-butanediol, 2,3 -Butanediol, 3-methyl-1,5-pentanediol, neopentylglycol, 2-methyl-1,3-propanediol, 2-methyl-2-propyl-1,3-propanediol, 2-butyl-2- Ethyl-1,3-propanediol, 1,5-pentanediol, 1,6-hexanediol, 2-methyl-2,4-pentanediol, 1,3-pentanediol, 2-ethyl-1,3-hexane Diol, 2,5-dimethyl-2,5-hexanediol, 2-butyl-2-hexyl-1,3-propanediol, 1,8-octanediol, 2-methyl-1,8-octanediol, 1, Aliphatic glycols such as 9-nonanediol, alicyclic glycols such as bishydroxymethylcyclohexane, glycols having aromatic rings such as xylylene glycol, bishydroxyethoxybenzene, etc. Polyurethane adhesive composition with improved adhesion to nylon material .
The method of claim 1,
The silane crosslinking agent,
Phenyl-3-aminopropyltriethoxysilane, phenyl-3-aminopropyltrimethoxysilane, cyclohexyl-3-aminoprotriethoxysilane, cyclohexyl-3-aminopropyltriethoxysilane, 1,3- A polyurethane adhesive composition having improved adhesion to a nylon material, characterized in that one or more selected from bisaminopropyltetraethylsiloxane and polydimethylsiloxane are used.
The method of claim 1,
The catalyst,
A polyurethane adhesive composition having improved adhesion to a nylon material, characterized in that one or more selected from among an organometallic compound including dibutyltin dilaurate, an organic amine including triethylenediamine, and salts thereof.
The method of claim 1,
The adhesion enhancer.
As a monomer having a functional group selected from a halogen atom, a hydroxyl group and a carboxyl group, naphthalic anhydride, phosphoric anhydride, maleic anhydride, phthalic anhydride, acetic anhydride, itaconic anhydride, Polyurethane adhesive composition with improved adhesion to nylon material, characterized in that one or more selected from the use of Chlorendic anhydride, boric anhydride, trimellitic anhydride.