KR101189868B1 - Aqueous polyurethane resin with excellent adhesive strength and workability and the method for manufacturing thereof, and aqueous hot-melt adhesive containing the same - Google Patents

Abstract

The present invention relates to an aqueous polyurethane resin having excellent adhesion and workability at a low temperature, a method for producing the same, and an aqueous hot melt adhesive including the same, and more specifically, 1) (a) a crystalline poly with a number average molecular weight of 2000 or more An NCO / OH equivalent ratio of 1.2 to 2.0 or less; a polyol having an ester polyol and (b) a nitrogen-containing polyol having a number average molecular weight of 100 to 500 or less; and (c) an organic polyisocyanate having an average molecular weight of 100 or more; Reacting with dilution with a low boiling organic solvent free of active hydrogen; 2) chain-extending the mixture of 1) with a polyamine having a sulfonate having a number average molecular weight of 600 or less and a primary 2-3 functional polyamine having a molecular weight of 200 or less, and then adding water to disperse it; And 3) distilling the mixture of 2) under reduced pressure to remove the organic solvent.

Polyurethane Adhesive * Hot Melt

Description

Aqueous polyurethane resin with excellent adhesive strength and workability and the method for manufacturing applications, and aqueous hot-melt adhesive containing the same}

The present invention relates to an aqueous polyurethane resin having excellent adhesion and workability at a low temperature, a method for producing the same, and an aqueous hot melt adhesive including the same, and more specifically, 1) (a) a crystalline poly with a number average molecular weight of 2000 or more An NCO / OH equivalent ratio of 1.2 to 2.0 or less; a polyol having an ester polyol and (b) a nitrogen-containing polyol having a number average molecular weight of 100 to 500 or less; and (c) an organic polyisocyanate having an average molecular weight of 100 or more; Reacting with dilution with a low boiling organic solvent free of active hydrogen; 2) chain-extending the mixture of 1) with a polyamine having a sulfonate having a number average molecular weight of 600 or less and a primary 2-3 functional polyamine having a molecular weight of 200 or less, and then adding water to disperse it; And 3) distilling the mixture of 2) under reduced pressure to remove the organic solvent. The present invention relates to an aqueous polyurethane resin, a method for preparing the same, and an aqueous hot melt adhesive including the same.

Until now, solvent-type polyurethane resins have been widely used as adhesives because of their excellent adhesion, heat resistance, oil resistance, cold resistance, and flexibility, but the organic solvents used in the manufacture of these solvent-type polyurethane resin adhesives are environmental pollution and worker's health. Adversely affects. Therefore, the development of the water-dispersed polyurethane water-based adhesive in place of such an oil-based polyurethane adhesive is rapidly made.

As an example of such an aqueous adhesive, Japanese Patent Laid-Open No. 59-30186 discloses a polyurethane resin obtained from an amorphous polyester polyol having a sulfonic acid metal base group and a polyisocyanate compound. In addition, it is disclosed that the adhesiveness and water resistance, etc. are improved when the PET film is bonded using the polyurethane resin, but the main component of the polyurethane resin is an aromatic polyester polyol, which is reactivated at 100 ° C. or higher, thereby exhibiting high adhesive strength. There is a possibility of damage to the adherend due to heat.

As another example of an aqueous adhesive, Korean Laid-Open Patent Publication No. 2005-0052833 discloses a polyurethane resin obtained from a compound of crystalline polyester polyol, bifunctional or higher polyol, and polyisocyanate. Although the initial adhesive strength, adhesive strength and heat resistance, etc. are excellent in the adhesive using this polyurethane resin, the polyurethane resin adhesive has a disadvantage in that the adhesive strength and workability at low temperatures are inferior.

Therefore, the present inventors have tried to develop an aqueous polyurethane adhesive composition having excellent adhesion and workability at low temperature, and as a result, a number average molecular weight of 2000 or more includes a crystalline polyester polyol and a nitrogen group and a number average containing a bifunctional or higher hydroxyl group. A polyamine having a molecular weight of 100 to 500 or less and an organic polyisocyanate having an average molecular weight of 100 or more to react with an NCO / OH equivalent ratio of 1.2 to 2.0 or less, diluted with a low boiling organic solvent free of active hydrogen, and then a polyamine having a number average molecular weight of 600 or less having a sulfonate and a molecular weight. When water-based polyamines of 1 to 2 functional triamines of 200 or less are dispersed and dispersed, and then distilled under reduced pressure, organic solvents are prepared.Aqueous polyurethane resins having excellent adhesion and workability at low temperatures without organic solvents are prepared. It has been found that the present invention has been completed.

Accordingly, it is an object of the present invention to provide an aqueous polyurethane resin excellent in adhesion and workability at low temperatures, a method for producing the same, and an aqueous hot melt adhesive including the same.

In order to achieve the above object, in the present invention

1) A polyol having a number average molecular weight of 2000 or more and a polyol having a number average molecular weight of 100 or more and 500 or less and an organic polyisocyanate having an average molecular weight of 100 or more and a NCO / Reacting with an OH equivalent ratio to dilute with a low boiling organic solvent free of active hydrogen;

2) chain-extending the mixture of 1) with a polyamine having a sulfonate having a number average molecular weight of 600 or less and a primary 2-3 functional polyamine having a molecular weight of 200 or less, and then adding water to disperse it; And

3) distilling the mixture of 2) under reduced pressure to remove the organic solvent;

And a method of producing an aqueous polyurethane adhesive.

The present invention also provides an aqueous hot melt adhesive comprising an aqueous polyurethane resin prepared by the above method.

The aqueous polyurethane adhesive composition according to the present invention was excellent in adhesion and workability at low temperatures, and excellent in initial adhesive strength and heat resistance, and thus could be applied to industries such as furniture, interior materials, and textiles.

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

The present invention relates to an aqueous polyurethane resin having excellent initial adhesive strength, adhesive strength and heat resistance, excellent adhesive strength and workability at low temperatures, and excellent adhesiveness to various substrates, and a method of manufacturing the same.

The process for preparing the aqueous polyurethane resin according to the invention comprises the following steps:

1) A polyol having a number average molecular weight of 2000 or more and a polyol having a number average molecular weight of 100 or more and 500 or less and an organic polyisocyanate having an average molecular weight of 100 or more and a NCO / Reacting with an OH equivalent ratio to dilute with a low boiling organic solvent free of active hydrogen;

2) chain-extending the mixture of 1) with a polyamine having a sulfonate having a number average molecular weight of 600 or less and a primary 2-3 functional polyamine having a molecular weight of 200 or less, and then adding water to disperse it; And

3) distilling the mixture of 2) under reduced pressure to remove the organic solvent.

The polyester polyol used in the step 1) is a polyol having a number average molecular weight of 2000 or more, a polycaprolactone polyol polycondensed with ε-caprolactone using a diol having 4 to 8 carbon atoms as an initiator; And polyols polycondensed with dicarboxylic acids having a linear structure having 6 to 10 carbon atoms and diols having a linear structure having 4 to 8 carbon atoms. At this time, it is preferable to use a diol having 4 to 8 carbon atoms selected from the group consisting of butanediol, pentane diol and hexanediol, adipic acid, azera as a dicarboxylic acid having a linear structure having 6 to 10 carbon atoms It is preferable to use one selected from the group consisting of Azelaic acid and sebacic acid, but is not limited thereto. The polyester polyol having such a number average molecular weight of 2000 to 3000 is preferably used at 65 to 75% based on the solid content weight percentage of the aqueous polyurethane resin.

In addition, the step 1) preferably comprises a polyol containing a nitrogen group and a number average molecular weight of 100 or more and 500 or less containing a secondary functional or primary, secondary hydroxyl value. Such a polyol is preferably a cationic polyol containing a nitrogen group in which an alkyl group such as an ethyl group, a methyl group or a butyl group is bonded to nitrogen, and containing a bifunctional or higher hydroxyl group.

Specific examples of the cationic polyol include polyols corresponding to the following Chemical Formula 1:

In the above formula, R is -C _n H _{n + 1} , and n is an integer of 1-3.

The aqueous polyurethane resin according to the present invention is prepared using a cationic polyol having a number average molecular weight of 100 or more and 500 or less containing a nitrogen group and containing a bifunctional or higher primary or secondary hydroxyl value, thereby forming film and adhesive force at low temperature. This is improved.

It is preferable that the polyol containing the said nitrogen group and having a number average molecular weight of 100 or more and 500 or less containing 2 or more functional hydroxyl groups is contained in 2 to 8% based on the solid content weight percentage of an aqueous polyurethane resin. When the cationic polyol is used in an excessive amount, the adhesion of the adherend is reduced, and when a small amount is used, there is a problem in that the film is not formed at a low temperature.

There is no restriction | limiting in particular as organic polyisocyanate which can be used at step 1), Aliphatic polyisocyanate, alicyclic polyisocyanate, and aromatic polyisocyanate which are used normally can be used individually or in mixture. For example, such organic polyisocyanate compounds include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodeca methylene diisocyanate, cyclohexane-1,3- or 1,4 -Diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), bis- (4-isocyanatocyclohexyl) methane ('hydrogenated MDI '), 2- or 4-isocyanatocyclohexyl-2'-isocyanatocyclohexyl methane, 1,3- or 1,4-bis (isocyanatomethyl) -cyclohexane, bis- ( 4-isocyanato-3-methylcyclohexyl) methane, 1,3- or 1,4-α, α, α ', α'-tetramethylxylene diisocyanate, 2,4- or 2,6-toluenedi Isocyanate, 2,2'-, 2,4'- or 4,4'-diisocyanatodiphenylmethane (MDI), 1,5-naphthalenediisocyanate, p- or m-phenylenediisocyanate, xylenedi Isocyanate and diphenyl-4,4'-diisocyanate, and the like, and preferably isomers having a ratio of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate 65:35 or 80:20; Mixtures of hexamethylene diisocyanate can be used.

Among these compounds, it is preferable to use an aromatic isocyanate compound from the viewpoint of mechanical properties and heat resistance. It is more preferable to use compounds of aromatic and cycloaliphatic isocyanates from the viewpoint of cohesion and adhesion. It is also preferable to use a bifunctional or lower polyisocyanate from the viewpoint of obtaining a linear polyurethane resin having more suitable cohesion and adhesion.

The isocyanate content with respect to the final aqueous polyurethane resin solids is preferably in the range of 10 to 25% by weight. Within this range, the polyol properties in the polyurethane molecules are suitably maintained, and thermal activity is preferably exerted at low temperatures, thereby providing excellent initial adhesion. Can be obtained. That is, when the content of isocyanate is out of the above range, the initial adhesive strength is lowered.

The organic solvent that can be used in step 1) is benzene, toluene, ethyl acetate, acetone, methyl ethyl ketone, diethyl ether, tetrahydrofuran, methyl acetate, acetonitrile, chloroform, methylene chloride, carbon tetrachloride, 1,2- Dichloroethane, 1,1,2-trichloroethane, tetrachloroethylene, N-methylpyrrolidone, etc. can be used individually or in mixture. In particular, among these organic solvents, it is preferable to use acetone or methyl ethyl ketone as a solvent having high solubility with a polyurethane resin.

In addition, the aqueous polyurethane resin of the present invention contains 0.1 to 5% of sulfonic acid ion groups based on the solids weight% of the polyurethane resin obtained by the reaction of an isocyanate terminated prepolymer and a polyamine chain extender having a sulfonate. In addition, the polyurethane resin may be included in a ratio of 40% or more of the solid content, more preferably 50 to 60%.

Examples of the polyamine having a sulfonate having a number average molecular weight of 600 or less used in step 2) include α, ω-polypropylene glycoldiamine-sulfonated and derivatives thereof containing metals such as Na, K, Li and Ca. Preferably, α, ω-polypropylene glycol diamine-sulfonated sodium salt having a number average molecular weight of 550 may be used. The content of the polyamine is preferably a content of sulfonic acid ion groups in a ratio of 0.1 to 5% based on the solid content weight% of the aqueous polyurethane resin. More preferably, it is contained in 0.1 to 4% of ratio. If it is used in a smaller amount than it is difficult to accept the resin, when used in excess of the viscosity may increase the result that the desired solid content is lowered.

The primary 2-3 functional polyamine having a molecular weight of 200 or less used in the step 2) serves as a chain extender for the low molecular weight polyurethane resin obtained above. In this way, when the above-mentioned chain extender made of a polyamine having a molecular weight of 200 or less can be used, the cohesive force of the polyurethane resin can be improved by increasing the molecular weight, and the thermal activity of the polyurethane resin can be improved. In addition, in order to improve the cohesive force of the polyurethane resin, it is necessary to adjust the molecular weight of the polyamine having a molecular weight of 200 or less to 100 or less. In addition, when used in excess, the solids may be lowered or the thermal activity temperature may be increased due to the increase in molecular weight.

Particularly typical examples of the polyamine having a molecular weight of 200 or less include 1,2-diaminoethane, 1,2- or 1,3-diaminopropane, 1,2-, 1,3- or 1,4-diaminobutane, 1 , 5-diaminopentane, 1,6-diaminohexane, piperazine, N-N'-bis- (2-aminoethyl) piperazine, 1-amino-3-aminomethyl-3,5,5-trimethyl -Cyclohexane (isophoronediamine), bis- (4-aminocyclohexyl) methane, bis- (4-amino-3-butylcyclohexyl) methane, 1,2-, 1,3- or 1,4- Diamines such as diaminocyclohexane and 1,3-diaminopropane; Polyamines such as diethylenetriamine and triethylenetetramine; And hydrazine derivatives such as hydrazine and adipic acid hydrazide, and hydrazine or 1,2-diaminoethane and the like are preferable. The polyamine is preferably contained at 0.05 to 2%, more preferably 0.1 to 1%, based on the solids content of the aqueous polyurethane resin.

When preparing the aqueous polyurethane resin according to the present invention, an emulsifier may be used in addition to the main components. Typical examples of such emulsifiers are polyoxyethylene polyoxypropylene glycol ether type, polyoxyethylene nonylphenyl ether type, polyoxyethylene octylphenyl ether type, polyoxyethylene lauryl ether type, polyoxyethylene laurate type, polyoxyethylene And nonionic emulsifiers such as alkyl ether type, sorbitan derivative type, polyoxyethylene polycyclic phenyl ether type, anionic emulsifiers such as alkylbenzene sulfonate type and dialkyl succinate sulfonate type, and cationic emulsifiers. Among these emulsifiers, it is preferable to use nonionic emulsifiers and anionic emulsifiers. The said emulsifier can be added 0 to 5 weight% with respect to a polyurethane resin in solid content ratio. In the case of using such an emulsifier, it is preferable to add it to water in the emulsion dispersion step in advance and then emulsify and disperse it. However, you may add an emulsifier after completion | finish of an emulsion dispersion process. These emulsifiers can be used individually or in mixture.

Moreover, when manufacturing the aqueous polyurethane resin by this invention, the catalyst for urethane formation can be used as needed. Representative examples of the catalyst for forming a urethane include various nitrogen-containing compounds such as triethylamine, triethylenediamine and N-methylmorpholine, various metal salts such as potassium acetate, zinc stearate and tin octylate, dibutyltin dilaurate, and the like. And various organometallic compounds.

The water-based polyurethane resin of this invention manufactured by the said method is characterized by the thermal activity temperature of 50-70 degreeC.

The aqueous polyurethane resin according to the present invention can be used alone or in combination with a bifunctional or higher polyisocyanate compound serving as a crosslinking agent. Typical examples of such bifunctional or higher polyisocyanate compounds include 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 4,4'-diisocyanatodiphenyl methane (MDI), xylene diisocyanate, iso Polyisocyanate compounds consisting of trimers such as poron diisocyanate and low molecular weight activities such as polyisocyanate compounds and ethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, polyoxyethylene glycol and long chain higher alcohols The compound which has a terminal isocyanate comprised from a hydrogen compound and which can be water-soluble is mentioned.

When the crosslinking agent is used, the aqueous polyurethane resin can exhibit excellent heat resistance and durability when used as an adhesive.

The aqueous polyurethane resin according to the present invention can be used as an adhesive for wooden furniture, automobiles, and textile industries. Since these water-based polyurethane resin adhesives have a long tag-free time, they can be adhere | attached at 50-60 degreeC reactivation temperature after apply | coating these water-based polyurethane resin adhesives to a base material. In addition, these aqueous polyurethane resin adhesives can be used as adhesives in various industries because of their excellent adhesion and heat resistance.

The aqueous hot melt adhesive according to the present invention contains the aqueous polyurethane resin obtained above.

The aqueous hot melt adhesive according to the present invention may further contain other resin in addition to the aqueous polyurethane resin. At this time, other resins that may be added include emulsion polymers such as ethylene vinyl acetate emulsion and polyvinylacetate emulsion, and when used with these additional resins, the content of the polyurethane resin of the present invention is from 10 to about the total solids. 50% by weight, preferably 10 to 30% by weight can be used.

The aqueous hot melt adhesive according to the present invention may further contain adhesive resins and additives commonly used for adhesives within a range that does not impair the heat-activated adhesion of the adhesives. More specific examples include adhesive resins such as rosin resin, rosin ester resin, terpene resin, terpene phenol resin, petroleum resin and coumarone resin; And additives such as fillers, dyes, thickeners, antioxidants, ultraviolet absorbers and flame retardants.

The aqueous adhesive according to the present invention can be suitably used for bonding substrates such as shoes, films, metals, foams, rubbers, fibers, and various plastics.

Hereinafter, the present invention will be described more specifically with reference to examples and test examples. These examples are provided only for understanding the contents of the present invention, and the scope of the present invention is not limited to these examples, and modifications, substitutions, and insertions commonly known in the art may be performed. This is also included in the scope of the present invention. Unless otherwise specified, all parts are based on the weight%, and “parts” means “parts by weight”.

Example 1

173.2 parts of polyester polyol (A) having a number average molecular weight of 2000, polycondensed with 1,4-butanediol and adipic acid; 177.8 parts of a polyester polyol (B) having a number average molecular weight of 2000 condensed with 1,6-hexanediol and adipic acid; And 11.7 parts of 3- (diethylamino) propane-1,2-diol (D) were dehydrated under 105 ° C vacuum and cooled to 50 ° C. Subsequently, 48.7 parts of toluene diisocyanate (the ratio of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate 80:20) and 47.0 parts of hexamethylene diisocyanate were added, and it was made to react at 70-75 degreeC for 3 hours. Then slowly 600 parts of acetone was added to dissolve the prepolymer. The temperature was adjusted to 40 ° C. and 15.9 parts of α, ω-polypropylene glycoldiamine-sulfonated sodium salt and 6.5 parts of 80% aqueous hydrazine solution were added diluted by 80 parts of water. Then 413.9 parts by weight of water was slowly added to emulsify and disperse. The emulsion thus obtained was desolvated with a vacuum pump at 40 to 50 ° C. to obtain an aqueous polyurethane resin having a nonvolatile content of 50% (based on solids content of SO ₃ ⁻ content of 0.46%).

[Example 2]

140.4 parts of polyester polyol (A) having a number average molecular weight of 2000 condensed with 1,4-butanediol and adipic acid; 210.5 parts of polycaprolactone diol (C) having a number average molecular weight of 2000 which is polycondensed by ring opening ε-caprolactone using 1,4-butanediol as an initiator; And 11.7 parts of 3- (diethylamino) propane-1,2-diol (D) were dehydrated under 105 ° C vacuum and cooled to 50 ° C. Subsequently, 48.7 parts of toluene diisocyanate (the ratio of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate 80:20) and 47.0 parts of hexamethylene diisocyanate were added, and it was made to react at 70-75 degreeC for 3 hours. Then slowly 600 parts of acetone was added to dissolve the prepolymer. The temperature was adjusted to 40 ° C. and 15.9 parts of α, ω-polypropylene glycoldiamine-sulfonated sodium salt and 6.5 parts of 80% aqueous hydrazine solution were added diluted by 80 parts of water. Then 413.9 parts by weight of water was slowly added to emulsify and disperse. The emulsion thus obtained was desolvated with a vacuum pump at 40 to 50 ° C. to obtain an aqueous polyurethane resin having a nonvolatile content of 50% (based on solids content of SO ₃ ⁻ content of 0.46%).

[Example 3]

210.6 parts of polyester polyol (B) having a number average molecular weight of 2000 condensed with 1,6-hexanediol and adipic acid; 140.4 parts of polycaprolactone diol (C) having a number average molecular weight of 2000 which is polycondensed by ring opening ε-caprolactone using 1,4-butanediol as an initiator; And 11.7 parts of 3- (diethylamino) propane-1,2-diol (D) were dehydrated under 105 ° C. vacuum and cooled to 50 ° C. Subsequently, 48.7 parts of toluene diisocyanate (the ratio of 2,4-toluene diisocyanate and 2,6-toluene diisocyanate 80:20) and 47.0 parts of hexamethylene diisocyanate were added, and it was made to react at 70-75 degreeC for 3 hours. Then slowly 600 parts of acetone was added to dissolve the prepolymer. The temperature was adjusted to 40 ° C. and 15.9 parts of α, ω-polypropylene glycoldiamine-sulfonated sodium salt and 6.5 parts of 80% aqueous hydrazine solution were added diluted by 80 parts of water. Then 413.9 parts by weight of water was slowly added to emulsify and disperse. The emulsion thus obtained was desolvated with a vacuum pump at 40 to 50 ° C. to obtain an aqueous polyurethane resin having a nonvolatile content of 50% (based on solids content of SO ₃ ⁻ content of 0.46%).

Example 4

140.4 parts of polyester polyol (A) having a number average molecular weight 2000 polycondensed with 1,4-butanediol and adipic acid and a polyester polyol (B) having a number average molecular weight of 2000 polycondensed with 1,6-hexanediol and adipic acid An aqueous polyurethane resin was obtained in the same manner as in Example 1 except that 210.5 parts were used (SO ₃ ⁻ content was 0.46% based on solids).

[Example 5]

210.6 parts of polyester polyol (A) of the number average molecular weight 2000 condensation-polymerized by 1, 4- butanediol and adipic acid and 1, 4- butanediol as an initiator, ring-opening epsilon caprolactone, and the number average molecular weight of 2000 An aqueous polyurethane resin was obtained in the same manner as in Example 2 except that 140.4 parts of polycaprolactone diol (C) was used (SO ₃ ⁻ content is 0.46% based on solids).

[Example 6]

173.2 parts of polyester polyol (B) of the number average molecular weight 2000 condensation-polymerized with 1, 6- hexanediol and adipic acid and 1, 4- butanediol as an initiator, ring-opening epsilon caprolactone, and the number average molecular weight 2000 An aqueous polyurethane resin was obtained in the same manner as in Example 3 except that 177.8 parts of polycaprolactone diol (C) was used (SO ₃ ⁻ content was 0.46% based on solid content).

[Example 7]

210.6 parts of polyester polyol (A) of number average molecular weight 2000 condensation-polymerized by 1, 4- butanediol and adipic acid, and polyester polyol (B) of number average molecular weight 2000 by polycondensation of 1, 6- hexanediol and adipic acid An aqueous polyurethane resin was obtained in the same manner as in Example 1 except that 140.4 parts were used (SO ₃ ⁻ content was 0.46% based on solids).

[Example 8]

173.2 parts of polyester polyol (A) of number average molecular weight 2000 condensation-polymerized by 1, 4- butanediol and adipic acid, and the number average molecular weight 2000 of polycondensation which ring-opened epsilon caprolactone using 1, 4- butanediol as an initiator An aqueous polyurethane resin was obtained in the same manner as in Example 2 except that 177.8 parts of polycaprolactone diol (C) was used (SO ₃ ⁻ content was 0.46% based on solids).

[Example 9]

Number average molecular weight 2000 polycondensed by ring opening of epsilon -caprolactone using 140.4 parts of polyester polyols (B) of the number average molecular weight 2000 condensation-polymerized by 1, 6- hexanediol and adipic acid as an initiator, and 1, 4- butanediol An aqueous polyurethane resin was obtained in the same manner as in Example 3 except that 210.5 parts of polycaprolactone diol (C) was used (SO ₃ ⁻ content was 0.46% based on solids).

Comparative Example 1

290.7 parts of the polyester polyol (C) used in Example 2 were dehydrated under 110 ° C. vacuum and cooled to 50 ° C. Subsequently, 47.4 parts of toluene diisocyanate (the ratio of 2,4-toluene diisocyanate to 2,6-toluene diisocyanate is 80:20) was added and reacted at 50 to 60 ° C for 2 hours, followed by 1.6 parts of trimethylolpropane and Tegomer D. 43.6 parts of -3403 were added and reacted further at 60 degreeC for 1 hour. Then slowly 700 parts of acetone was added to dissolve the prepolymer. The temperature was adjusted to 40 ° C., and 13 parts of α, ω-polypropylene glycoldiamine-sulfonated sodium salt and 3.6 parts of ethylenediamine were added diluted by 80 parts of water. Then 519.8 parts by weight of water was slowly added to emulsify and disperse. In this way de-solvent of the obtained emulsion with a vacuum pump at 40 ~ 50 ℃, to obtain an aqueous polyurethane resin of the non-volatile content of 40% (based on solids SO ₃ ^- content is 0.47%).

Comparative Example 2

292.0 parts of the polyester polyol (A) used in Example 1 were dehydrated under 110 ° C. vacuum and cooled to 50 ° C. Subsequently, 47.6 parts of toluene diisocyanate (the ratio of 2,4-toluene diisocyanate to 2,6-toluene diisocyanate is 80:20) was added and reacted at 50 to 60 ° C. for 2 hours, followed by 1.6 parts of trimethylolpropane and Tegomer D. 43.8 parts of -3403 were added and reacted further at 60 degreeC for 1 hour. Then slowly 700 parts of acetone was added to dissolve the prepolymer. The temperature was adjusted to 40 ° C. and 13 parts of α, ω-polypropylene glycoldiamine-sulfonated sodium salt and 2.4 parts of 80% aqueous hydrazine aqueous solution were added diluted by 80 parts of water. Then 519.3 parts by weight of water was slowly added to emulsify and disperse. In this way de-solvent of the obtained emulsion with a vacuum pump at 40 ~ 50 ℃, to obtain an aqueous polyurethane resin of the non-volatile content of 40% (based on solids SO ₃ ^- content is 0.47%).

[Comparative Example 3]

292.0 parts of the polyester polyol (B) used in Example 1 were dehydrated under 110 ° C. vacuum and cooled to 50 ° C. Subsequently, 47.6 parts of toluene diisocyanate (the ratio of 2,4-toluene diisocyanate to 2,6-toluene diisocyanate is 80:20) was added and reacted at 50 to 60 ° C. for 2 hours, followed by 1.6 parts of trimethylolpropane and Tegomer D. 43.8 parts of -3403 were added and reacted further at 60 degreeC for 1 hour. Then slowly 700 parts of acetone was added to dissolve the prepolymer. The temperature was adjusted to 40 ° C. and 13 parts of α, ω-polypropylene glycoldiamine-sulfonated sodium salt and 2.4 parts of 80% aqueous hydrazine aqueous solution were added diluted by 80 parts of water. Then 519.3 parts by weight of water was slowly added to emulsify and disperse. In this way de-solvent of the obtained emulsion with a vacuum pump at 40 ~ 50 ℃, to obtain an aqueous polyurethane resin of the non-volatile content of 40% (based on solids SO ₃ ^- content is 0.47%).

The compositions of the aqueous urethane resins prepared in Examples 1 to 9 and Comparative Examples 1 to 3 are shown in Table 1 below.

Example Comparative Example One 2 3 4 5 6 7 8 9 One 2 3 Polyol 1 (A) 173.2 140.4 140.4 210.6 210.6 173.2 292.0 (B) 177.8 210.6 210.5 173.2 140.4 140.4 292.0 (C) 210.5 140.4 140.4 177.8 177.8 210.5 290.7 Polyol 2 (D) 11.7 11.7 11.7 11.7 11.7 11.7 11.7 11.7 11.7 Trimethylolpropane 1.6 1.6 1.6 Tegomer D-3403 43.6 43.8 43.8 Isocyanate Toluene diisocyanate 48.7 48.7 48.7 48.7 48.7 48.7 48.7 48.7 48.7 47.4 47.6 47.6 Hexamethylene diisocyanate 47.0 47.0 47.0 47.0 47.0 47.0 47.0 47.0 47.0 Diluent Solvent: Acetone 600 600 600 600 600 600 600 600 600 700 700 700 Ionomer: α, ω-polypropylene
Glycoldiamine-Sulfonated Sodium Salt 15.9 15.9 15.9 15.9 15.9 15.9 15.9 15.9 15.9 13 13 13 Polyamine: 80%
Hydrazine solution 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 6.5 2.4 2.4 Ethylenediamine 3.6 water 493.9 493.9 493.9 493.9 493.9 493.9 493.9 493.9 493.9 599.8 599.3 599.3

Formulation Examples 1-9 and Comparative Formulation Examples 1-3 Preparation of Water-Based Polyurethane Adhesives

Formulation Examples 1-9 and Comparative Formulation Example 1 were prepared by mixing 5 parts of a water-soluble polyisocyanate (trade name: Desmodur DA, Bayer) with 100 parts of the aqueous polyurethane resin solution prepared in Examples 1-9 and Comparative Examples 1-3. The aqueous polyurethane adhesive of -3 was manufactured.

Test Example 1 Mechanical Property Evaluation

The mechanical properties of the aqueous polyurethane adhesives prepared in Formulation Examples 1 to 9 and Comparative Formulation Examples 1 to 3 were evaluated by the following methods, and the results are shown in Table 2 below.

<Initial Adhesion Test>

0.2 mm (thickness) x 25 mm (width) x 100 mm (length) of PVC was washed with acetone and dried by hot air at 60 ° C, and the adhesive composition prepared by mixing the crosslinking agent was used with two wire coating bars. 90 g / ㎡ on PVC specimen The amount was applied, dried for 30 seconds in an 80 ° C. hot air dryer, taken out, and the two specimens were pressed for 15 seconds at a pressure of 4 kg / cm 2 between the surfaces with adhesive, mounted on a tensile strength tester, and subjected to a T-shaped peeling test. The peeling rate was measured at 100 mm / min and measured within 1 minute after pressing (however, the number of samples was 3 and the average value was taken).

<Adhesion Test>

0.2 mm (thickness) x 25 mm (width) x 100 mm (length) of PVC was washed with acetone and dried by hot air at 60 ° C. The adhesive composition prepared by mixing the crosslinking agent was used as two wire coating bars. 90 g / ㎡ on PVC specimen The amount was applied and dried at room temperature for 1 hour. Two dried specimens were thermally activated at 60 ° C. in a hot air dryer for 90 seconds, and the surfaces with adhesive were pressed for 15 seconds at a pressure of 4 kg / cm 2, mounted on a tensile strength tester, and subjected to a T-shaped peeling test. The peel rate was 100 mm / min in the peel strength measurement (however, the number of samples was 3 and the average value was taken).

<Heat resistance test>

Specimens were prepared in the same manner as the method for measuring the adhesion physical properties, and left to stand at room temperature for 24 hours. The specimen was allowed to stand for 30 minutes with a load of 500 g on the specimen in an 80 ° C x 50% (relative humidity) dryer, and then the peeled length of the adhesive surface was measured as a ruler. Taken).

<Film formation test at low temperature>

0.3 mm (thickness) × 30 mm (width) × 150 mm (length) steel specimens were washed with acetone and dried on the surface, and were prepared in each of Formulation Examples 1-9 and Comparative Formulation Examples 1-3. The urethane adhesive was applied to the specimen with a wire coating bar in an amount of 90 g / m 2 and dried at 0 ° C. After drying, the shape (cracking and adhesion state) of the formed film was confirmed (however, the number of samples was three and the average state was taken).

Formulation Example Comparative formulation example One 2 3 4 5 6 7 8 9 One 2 3 Initial Adhesion
(kg _f / ㎠) 2.8 2.7 2.7 2.6 2.7 2.5 2.7 2.6 2.5 2.6 2.5 2.6 Adhesion
(kg _f / ㎠) Destruction 6.5 6 Destruction 7 5 Destruction 5 Destruction materials
Destruction 6 materials
Destruction Heat resistance
(Mm) 0.15 0.3 0.2 0.2 0.3 0.2 0.2 0.2 0.15 0.3 0.2 0.2 0 ℃ film formation state Good Good Good Good Good Good Good Good Good crack/
Film peeling crack/
Film peeling crack

In the results of Table 2, the aqueous polyurethane adhesive of Formulation Examples 1 to 9 according to the present invention was superior to the initial adhesive strength and heat and moisture resistance compared to Comparative Formulation Examples 1-3.

Moreover, the adhesive force of the adhesive agent of Formulation Examples 1-9 was the level more than the adhesive agent of Comparative Formulation Examples 1-3. In the adhesion test results, "substrate destruction" means that the adhesion test specimen PVC breaks during the T-shaped peeling test. That is, when the PVC specimen is bonded with the water-based polyurethane adhesive of the present invention, the two bonded PVC specimens are not peeled from each other due to the strong adhesive force, but the PVC specimen is broken in the middle.

Finally, as a result of observing the film formation state at 0 ℃, the water-based polyurethane adhesives of Formulation Examples 1 to 9 according to the present invention formed a good film at a low temperature, whereas the water-based polyurethane adhesives of Comparative Formulation Examples 1 to 3 cracked And it was confirmed that film peeling occurred.

Claims (10)

1) A polyol having a number average molecular weight of 2000 or more and a polyol having a number average molecular weight of 100 or more and 500 or less and an organic polyisocyanate having an average molecular weight of 100 or more and a NCO / Reacting with an OH equivalent ratio to dilute with a low boiling organic solvent free of active hydrogen; 2) chain-extending the mixture of 1) with a polyamine having a sulfonate having a number average molecular weight of 600 or less and a primary 2-3 functional polyamine having a molecular weight of 200 or less, and then adding water to disperse it; And 3) distilling the mixture of 2) under reduced pressure to remove the organic solvent; Going through, The crystalline polyester polyol having a number average molecular weight of 2000 or more includes a polycaprolactone polyol condensation-polymerized with ε-caprolactone using a diol having 4 to 8 carbon atoms as an initiator; And a crystalline polyol polycondensed with a dicarboxylic acid having a linear structure having 6 to 10 carbon atoms and a diol having a linear structure having 4 to 8 carbon atoms, A polyol having a number average molecular weight of 100 to 500 or less containing the nitrogen group and containing a bifunctional or higher hydroxyl group is 3- (diethylamino) propane-1,2-diol, The polyamine having a sulfonate having a number average molecular weight of 600 or less is α, ω-polypropylene glycol diamine-sulfonated sodium salt The manufacturing method of the water-based polyurethane resin for adhesives in which an adhesive film is formed at 10-5 degreeC. delete delete The method of claim 1, wherein the organic polyisocyanate having an average molecular weight of 100 or more is 1,4-tetramethylene diisocyanate, 1,6-hexamethylene diisocyanate, 1,12-dodeca methylene diisocyanate, cyclohexane-1,3- or 1,4-diisocyanate, 1-isocyanato-3-isocyanatomethyl-3,5,5-trimethylcyclohexane (isophorone diisocyanate, IPDI), bis- (4-isocyanatocyclohexyl) methane , 2- or 4-isocyanatocyclohexyl-2'-isocyanatocyclohexyl methane, 1,3- or 1,4-bis (isocyanatomethyl) -cyclohexane, bis- (4-isocyanato -3-methylcyclohexyl) methane, 1,3- or 1,4-α, α, α ', α'-tetramethylxylene diisocyanate, 2,4- or 2,6-toluene diisocyanate, 2,2 '-, 2,4'- or 4,4'-diisocyanatodiphenylmethane (MDI), 1,5-naphthalenediisocyanate, p- or m-phenylenediisocyanate, xylenediisocysi Process for producing a water-based polyurethane resin, characterized in that the carbonate and di least one member selected from the group consisting of biphenyl-4,4'-diisocyanate. delete A primary 2- to 3-functional polyamine having a molecular weight of 200 or less is 1,2-diaminoethane, 1,2- or 1,3-diaminopropane, 1,2-, 1,3- or 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, piperazine, N-N'-bis- (2-aminoethyl) piperazine, 1-amino-3-amino Methyl-3,5,5-trimethylcyclohexane (isophoronediamine), bis- (4-aminocyclohexyl) methane, bis- (4-amino-3 butylcyclohexyl) methane, 1,2-, 1, Aqueous, characterized in that at least one selected from the group consisting of 3- or 1,4-diaminocyclohexane, 1,3-diaminopropane, diethylenetriamine, triethylenetetramine, hydrazine and adipic acid hydrazide Method of producing a polyurethane resin. Aqueous polyurethane resin for adhesives by which an adhesive film is formed at -10-5 degreeC manufactured by the method of any one of Claims 1, 4, and 6. 8. The aqueous polyurethane resin according to claim 7, wherein the aqueous polyurethane resin contains 0.1 to 5% of sulfonic acid ionic groups based on the weight% of solids. 8. The aqueous polyurethane resin according to claim 7, wherein the aqueous polyurethane resin has a thermal activity temperature of 50 to 70 deg. An aqueous hot melt adhesive comprising the aqueous polyurethane resin according to claim 7.