JPH11349915A - Aqueous emulsion adhesive composition - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an aqueous emulsion adhesive composition satisfying required performance such as flexibility, having improved adhesivity to various adherends in contrast with conventional aqueous emulsion polyurethane resin and emitting extremely low odor in hygienic environment. SOLUTION: The objective aqueous emulsion adhesive composition contains a polyurethane resin produced by reacting a polyol, a diisocyanate compound and a chain extender as a base polymer. A lactone-based polyester polyol subjected to deodorizing treatment especially comprising water treatment and dehydration treatment and having a water-content of <=0.03 wt.% after the dehydration treatment is used as >=40 wt.% of the polyol component.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to an aqueous emulsion type adhesive composition. More specifically, the present invention relates to an aqueous emulsion-type adhesive composition having excellent adhesion and flexibility to various substrates such as synthetic leather, fiber, and plastic, and having a low odor.

[0002]

2. Description of the Related Art In recent years, conventional organic solvent-based adhesive compositions have been shifted to water-based resins from the viewpoints of resource saving, no pollution, and safety and health. In particular, aqueous emulsion-type polyurethane resins have been actively studied in terms of their excellent flexibility and elasticity, and are used for treating artificial leather and fibers.

[0003] However, compared with organic solvent-based polyurethane resin adhesives, the performance has not yet reached a satisfactory level in terms of adhesiveness. The odor of the adhesive composition in a sanitary environment has been improved to some extent by shifting from an organic solvent system to an aqueous system, but measures have been taken to reduce the odor of the adhesive composition caused by the resin composition. There is no actual situation. In particular, in a high-temperature work environment in summer, the work environment due to the odor of the adhesive component from the base material to which the adhesive is applied as well as the aqueous emulsion-type adhesive composition is not satisfactory.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to eliminate the disadvantages of conventional aqueous emulsion type polyurethane resins. In other words, not only satisfying the required performance such as flexibility, but also improving the adhesiveness to various substrates which have been considered as a drawback of the aqueous emulsion type polyurethane resin, and the aqueous emulsion having extremely low odor in a sanitary environment. It is an object to provide a mold adhesive composition.

[0005]

Means for Solving the Problems The present inventors have achieved the above object by using a specific polyester polyol, that is, a deodorized lactone-based polyester polyol, in an aqueous emulsion-type polyurethane resin composition. The inventors have found that various problems can be solved, and have completed the present invention.

That is, the present invention relates to an aqueous emulsion-type adhesive composition comprising a polyurethane resin obtained by reacting a polyol, a diisocyanate compound and a chain extender as a base polymer, wherein at least 40% by weight of a polyol component is deodorized. The present invention relates to an aqueous emulsion type adhesive composition characterized by using a lactone-based polyester polyol. In addition, the present invention relates to the aqueous emulsion-type adhesive composition, wherein the deodorization is performed by a water treatment and a dehydration treatment. Furthermore, the present invention relates to the above aqueous emulsion type adhesive composition, wherein the water content in the lactone-based polyester polyol after the dehydration treatment is 0.03% by weight or less.

[0007]

DETAILED DESCRIPTION OF THE INVENTION The base polymer of the composition of the present invention is a polyurethane resin, which is obtained by reacting a polyol, a diisocyanate compound and a chain extender. This polyurethane resin can be emulsified by an appropriate means described later and used as an adhesive composition. Hereinafter, the polyurethane resin according to the present invention will be specifically described.

The polyol used for the polyurethane resin as the base polymer of the composition of the present invention is a polyol having a molecular weight of about 400 to 5,000. Examples of such polyols include polyether polyols, bifunctional polyester diols having terminal hydroxyl groups obtained by a condensation reaction of diol and dicarboxylic acid, lactone-based polyester polyols, polycarbonate polyols, silicone polyols, polybutadiene polyols, polyolefin-based polyols, and the like. Is mentioned. Examples of the polyether polyol include polytetramethylene ether glycol, polypropylene glycol, polyethylene glycol and the like. Examples of the bifunctional polyester diol having a terminal hydroxyl group obtained by a condensation reaction of a diol and a dicarboxylic acid include polyethylene adipate, polyethylene butylene adipate, polybutylene adipate, polypropylene adipate, polyhexamethylene adipate, polyneopentyl adipate, and polyneopentylene adipate. -3-
Methyl-1,5-pentylene adipate, 2,4,4-
Trimethyl-1,6-hexanediol and / or condensate of 2,2,4-trimethyl-1,6-hexanediol with adipic acid, terephthalic acid alone or 1,6-hexane using isophthalic acid or adipic acid in combination Examples thereof include condensation products with diols, 3-methyl-1,5-pentanediol, and the like. As the lactone-based polyester polyol, ε-
Examples thereof include ring-opening addition-polymerized lactones such as caprolactone, γ-butyrolactone, and δ-valerolactone.

The short-chain polyols include diols,
Triols, polyols and mixtures thereof can be used. Examples of the diols include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, 1,6-hexanediol, 1,6-hexanediol, , 2,4
-And / or 2,4,4-trimethyl-1,6-hexanediol, 2,2,4-trimethyl-1,5-pentanediol, 1,10-decanediol, 1,12-dodecanediol, 1, 4-cyclohexanedimethanol, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, dimethylolheptanoic acid, dimethyloloctanoic acid, dimethyloloctanoic acid, and the like. Triols include glycerin, trimethylolethane, and trimethylolpropane, and tetrols include pentaerythritol.

In these polyols, 40% by weight or more, preferably 50% by weight or more of the polyol used for the polyurethane resin as the base polymer must use the deodorized lactone-based polyester polyol described above. When the amount of the deodorized lactone-based polyester polyol used is less than 40% by weight, the adhesive effect of the obtained aqueous emulsion type adhesive composition to various substrates is reduced, and the odor of the aqueous emulsion type adhesive composition is reduced. The effect is not satisfactory. Of course, a lactone-based polyester polyol, all of which has been deodorized, may be used as the polyol used for the polyurethane resin as the base polymer.

[0011] The deodorized lactone-based polyester polyol used in the present invention is not particularly limited in deodorizing method, and those obtained by treating by a known deodorizing method can be used. For example, a lactone-based polyester polyol obtained by ring-opening addition polymerization of lactones such as ε-caprolactone, γ-butyrolactone, and δ-valerolactone using a short-chain polyol as an initiator is previously heated to a temperature of 40 to 10 ° C.
The mixture was heated to 5 ° C., and water or steam 15 to 2 parts per 100 parts by weight of the lactone-based polyester polyol was added at normal pressure.
00 parts by weight are added or blown, mixed with the polyester polyol by stirring or the like, the odorous substance is dissolved in water as much as possible, and the water is separated. During and / or after the addition of water or the like to the lactone-based polyester polyol, the system is preferably placed in a stirring state. Water separation is natural separation,
Sedimentation, centrifugation, distillation, thin film evaporation, adsorption or a combination thereof can be performed. The lactone-based polyester polyol from which water has been separated in this way can further remove odorous substances at the stage of distilling residual water to 0.03% by weight or less. Odorants can be separated and removed by azeotropic distillation with water, steam distillation, single distillation, or a combination thereof. The water may be distilled off at normal pressure, but preferably under reduced pressure, more preferably 1 to 500 m
Performed at mHg. The distillation of water may be carried out at normal temperature, but is preferably carried out under heating, more preferably at 50 to 150 ° C.

For example, a lactone-based polyester polyol obtained by ring-opening addition polymerization of a lactone such as ε-caprolactone, γ-butyrolactone, δ-valerolactone using a short-chain polyol as an initiator is preliminarily heated to a temperature of 85 to 105 ° C. After the pressure was adjusted to 20 to 500 mmHg, for example, 45 parts by weight of water was added to 100 parts by weight of the lactone-based polyester polyol, the pressure was reduced to 10 to 50 mmHg, and then the temperature was increased to 110 to 115 ° C. A method is preferred in which water is distilled off to 0.03 parts by weight or less and deodorized under the conditions. In this case, the rate of water addition is preferably 2
5-38 ml / min · kg polyester polyol. Further, a lactone-based polyester polyol is placed under normal temperature and normal pressure, water is added thereto, and then the temperature is adjusted to 90 to 90.
The temperature is raised to 100 ° C, and then the pressure is increased to 20 to 500 mmHg.
The water can be distilled off under reduced pressure for deodorization. Furthermore,
The lactone-based polyester polyol is heated to 90 ° C under normal pressure.
After heating to ~ 110 ° C and adding 1 to 10 parts by weight of water to 100 parts by weight of the lactone-based polyester polyol, the pressure was set to 20 to 500 mmHg to distill off water,
The operation of adding water under normal pressure, heating, and evaporating water under reduced pressure is as follows.
Deodorization can be carried out by repeating up to 5 times.

In the deodorizing method in which the water is added, it is preferable to dehydrate the water in the lactone-based polyester polyol to 0.03% by weight or less. The smaller the residual water, the better. However, if the residual water exceeds 0.03% by weight, the degree of deodorization becomes insufficient, and the quality of the obtained lactone-based polyester polyol is not preferable.

The diisocyanate compound which is another component of the polyurethane resin of the present invention is an aromatic, aliphatic or alicyclic diisocyanate. Examples of diisocyanates include 1,5-naphthylene diisocyanate,
4,4′-diphenylmethane diisocyanate, 4,
4'-diphenyldimethylmethane diisocyanate,
4,4′-dibenzyl diisocyanate, dialkyl diphenyl methane diisocyanate, tetraalkyl diphenyl methane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, butane-1,4-diisocyanate, hexamethylene diisocyanate, 2,
2,4-trimethylhexamethylene diisocyanate,
2,4,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, cyclohexane-1,4
-Diisocyanate, xylylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-
Typical examples thereof include 4,4′-diisocyanate, 1,3-bis (isocyanatomethyl) cyclohexane, and methylcyclohexane diisocyanate.
These diisocyanates may be used alone or in combination of two or more.

The diisocyanate compound which is a component of the polyurethane resin of the present invention has an equivalent ratio of 2.0 to 1.0, and preferably 1.5 to
1.05 is used. When the amount of the diisocyanate compound is less than the above range, it is difficult to produce a self-emulsifying polyurethane emulsion, and when the amount is more than the above range, physical properties of the obtained adhesive deteriorate.

As the chain extender, for example, ethylenediamine, propylenediamine, hexamethylenediamine, diethylenetriamine, triethylenetetramine, isophoronediamine, dicyclohexylmethane-
4,4′-diamine and the like. Further, a water-soluble alicyclic polyamine such as piperazine can be used in the same manner. One of these polyamines may be used,
Two or more kinds may be used in combination.

The method for producing the aqueous polyurethane resin used in the present invention is not particularly limited, and can be obtained by a known method. For example, when obtaining a self-emulsifying type aqueous polyurethane resin, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolpentanoic acid, dimethylolheptanoic acid, dimethyloloctanoic acid, dimethylolnonanoic acid are used as a part of the polyol component. It is preferable to introduce a carboxyl group into the polyurethane resin using polycaprolactone polyol (carboxyl group-containing polyol) obtained by ring-opening addition polymerization of ε-caprolactone using dimethylolalkanoic acid as an initiator. The use of these polyol components used for imparting self-emulsifying properties is usually carried out when the acid value of the polyurethane resin solids is 5-6.
0 KOHmg / g, preferably 10-40 KOHmg / g
It is good to use it so as to be in the range of g. If the acid value of the polyurethane resin solid content is less than 5 KOH mg / g, self-emulsification of the resin is difficult, and if the acid value exceeds 60 KOH mg / g, the water resistance of the obtained polyurethane resin adhesive composition decreases.

More specifically, one example of the method for producing the self-emulsifying aqueous urethane resin in the present invention is as follows: a polyol which is a lactone-based polyester polyol in which at least 40% by weight or more of the polyol component has been deodorized; After further reacting with a diisocyanate compound to synthesize a urethane prepolymer having a terminal isocyanate group, if necessary, further neutralizing the carboxyl groups of the urethane prepolymer with a basic compound and dispersing in water. Alternatively, there is a method of producing an aqueous polyurethane resin by dissolving and elongating the chain with a chain extender. The urethane prepolymer obtained by this method can be obtained without a solvent, but in order to facilitate the operation of adding water and emulsifying and dispersing the oil-in-water type later, a small amount of acetone, methyl ethyl ketone, tetrahydrofuran,
It is more desirable to reduce the viscosity of the urethane prepolymer by diluting with an organic solvent such as dimethylformamide or N-methylpyrrolidone or reacting in advance with a solution of a small amount of an organic solvent. In this case, the equivalent ratio of the diisocyanate compound to the polyol component is usually NCO / OH = 1.1 to
It is preferable to react as 4/4.

The organic solvent used in the reaction for obtaining the urethane prepolymer is usually removed after the resin is converted to an aqueous solution, and preferably has a boiling point of 100 ° C. or less for ease of removal. , Methyl ethyl ketone, tetrahydrofuran and the like. Among the solvents used, acetone and methyl ethyl ketone are preferred, and acetone is most preferred.

The basic compounds used for neutralizing the carboxyl group include ammonia, triethylamine, trimethylamine, tripropylamine, triethanolamine, monoethanolamine, N-methylmorpholine, morpholine, 2,2- Examples include amines such as dimethylmonoethanolamine and N, N-dimethylmonoethanolamine, and sodium hydroxide and potassium hydroxide.

As another method for producing an aqueous polyurethane resin, a polyol which is a lactone-based polyester polyol in which at least 40% by weight or more of the polyol component is deodorized, and if necessary, other polyols are used in combination with a diisocyanate compound. A prepolymer having isocyanate groups at both ends by preparing a prepolymer having isocyanate groups at both ends, and then reacting the prepolymer with a chain extender in an appropriate low boiling point solvent, as well as a polymer polyol component and a diisocyanate compound. Any one-step method in which a chain extender is reacted at once in a suitable solvent may be employed, but in order to obtain a uniform polymer solution, the two-step method is preferably employed. Examples of the solvent used in these production methods include, for example, aromatic solvents such as benzene, toluene, and xylene; ester solvents such as ethyl acetate and butyl acetate; and ketone solvents such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Alone or a mixture thereof.

When the polyurethane resin used in the present invention is produced by a two-step method, it is preferable to add a chain extender to the prepolymer according to the following criteria. That is, the equivalent of the amino group in the chain extender is 0.9 to 1.3 with respect to 1 equivalent of the free isocyanate group at both ends of the prepolymer.
It is within the range of 0 equivalent. When the amino group becomes more than 1.30 equivalents, the chain extender remains unreacted, which is not preferable in terms of odor.

There is no particular limitation on the aqueous emulsion of the polyurethane resin obtained above, and various known methods can be employed. For example, various ionic emulsifiers and water are added to the polyurethane resin diluted with the organic solvent to forcibly disperse the mixture, or the polyurethane resin is not diluted with the organic solvent, and is stirred in the presence of the emulsifier and a small amount of water. After obtaining a water-in-oil emulsion in advance, a predetermined amount of water is further added and the mixture is vigorously stirred to invert the phase to obtain an emulsion. Examples of the emulsifier include anionic emulsifiers such as sodium alkyl sulfate, sodium alkylbenzene sulfonate, polyoxyethylene alkyl phenyl ether sulfosuccinate, rosin soap, and nonionic emulsifiers such as polyoxyethylene alkyl phenyl ether and polyoxyethylene alkyl ether. Emulsifiers include cationic emulsifiers such as quaternary ammonium salts and the like, and these emulsifiers are used alone or in combination. The amount of the emulsifier used is determined in consideration of water resistance, dispersion stability, particle size and the like, and is usually 1 to 30 parts by weight, preferably 3 to 12 parts by weight, based on 100 parts by weight of the solid content of the polyurethane resin. The water used in the present invention is preferably demineralized water that has been treated by ion-exchange resin treatment or the like in both the deodorization step and the aqueous emulsification step.

When a water-soluble component such as polyoxyethylene glycol is used as a resin component in the polyether polyol-based urethane resin, a self-emulsifying property is imparted, so that an emulsifier must be used at the time of emulsification. There is no.

The molecular weight of the polyurethane resin used in the present invention obtained as described above is usually 20,000.
It is preferred to be in the range of ~ 90,000. When the molecular weight is less than 20,000, the cohesive strength and heat resistance of the obtained adhesive are inferior. On the other hand, when the molecular weight is more than 90,000, the viscosity of the polyurethane resin solution becomes high, and the handling workability is lowered. Is not preferred because the stability of the polymer becomes poor. The solid content concentration of the polyurethane resin emulsion is not particularly limited, and is appropriately determined in consideration of workability at the time of bonding, and is usually 5 to 50% by weight, and has a viscosity of several tens to several thousand cP (25 ° C). ) Is practically suitable.

[0026]

EXAMPLES Hereinafter, the aqueous emulsion type adhesive composition of the present invention will be described in detail with reference to Production Examples, Examples and Comparative Examples, but the present invention is not limited to only these Examples. In addition, in each example, all parts and percentages are by weight unless otherwise specified.

Production Example 1 A reactor equipped with a stirrer, a thermometer and a cooling pipe was charged with a hydroxyl value of 56.9 KOH mg / g manufactured by Daicel Chemical Industries, Ltd.
Of polycaprolactone diol, and stirred under stirring.
After the temperature was raised to 300 ° C, the pressure was reduced to 300 mmHg. To this, 45 parts by weight of water was added with stirring at a rate of 25 m1 / min · kg polycaprolactone diol based on 100 parts by weight of the charged amount of polycaprolactone diol. After the addition of water was completed, the degree of pressure reduction was increased to 20 mmHg. Subsequently, the temperature was raised to 110 ° C., and dehydration was performed until the water content became 0.03% or less, to obtain deodorized polycaprolactone diol 1.

Production Example 2 A reactor equipped with a stirrer, a thermometer and a cooling pipe was charged with a hydroxyl value of 115.0 KOHmg / Daicel Chemical Industry Co., Ltd.
g of polycaprolactone diol and 9 g under stirring.
After the temperature was raised to 0 ° C., the pressure was reduced to 300 mmHg. To this, 45 parts by weight of water was added with stirring at a rate of 25 m1 / min · kg polycaprolactone diol based on 100 parts by weight of the charged amount of polycaprolactone diol. After the addition of water was completed, the degree of pressure reduction was increased to 20 mmHg. Subsequently, the temperature was raised to 110 ° C., and dehydration was performed until the water content became 0.03% or less, to obtain deodorized polycaprolactone diol 2.

EXAMPLE 1 Isophorone diisocyanate was placed in a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer.
6 g and acetone 40 g were charged, and then, while stirring under a nitrogen stream, 237.4 g of deodorized polycaprolactone diol 1 heated and melted at 60 ° C., 5.4 g of 1,4-butanediol, and 20 g of dimethylolpropionic acid. 6g
Was added and reacted at a temperature of 60 ° C. with stirring for 4 hours,
A homogeneous solution of the NCO-terminated urethane prepolymer was obtained. This NCO-terminated urethane prepolymer 159.1
g was added to 230 g of demineralized water to which 6.2 g of triethylamine had been previously added while stirring with a homomixer, and an aqueous solution in which 3.2 g of hexamethylenediamine was dissolved in 20 g of demineralized water was added. Then, at 60 ° C. under reduced pressure,
The acetone was distilled off for a period of time to obtain a milky white aqueous emulsion-type adhesive composition 1 having a solid content of 35%.

Example 2 Isophorone diisocyanate 13 was placed in a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer.
2.1 g and acetone 40 g were charged, and then, while stirring under a nitrogen stream, 198.2 g of deodorized polycaprolactone diol 2 heated and melted at 60 ° C., 9.2 g of 1,4-butanediol 2, and dimethylolpropionic acid 20.
6 g was added and reacted while stirring at a temperature of 60 ° C. for 4 hours to obtain a uniform solution of an NCO-terminated urethane prepolymer. The NCO-terminated urethane prepolymer 159.
While stirring with a homomixer, 1 g was added to 230 g of demineralized water to which 6.2 g of triethylamine had been added in advance,
Further, an aqueous solution in which 4.4 g of hexamethylenediamine was dissolved in 20 g of demineralized water was added. Next, acetone was distilled off under reduced pressure at 60 ° C. for 3 hours to obtain a milky white aqueous emulsion type adhesive composition 2 having a solid content of 35%.

Example 3 Isophorone diisocyanate 13 was placed in a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer.
1.1 g and acetone 40 g were charged, and then 99.1 g of deodorized polycaprolactone diol 2 heated and melted at 60 ° C. while stirring under a nitrogen stream, and a hydroxyl value of 112 KOHm comprising 1,6-hexanediol and adipic acid.
g / g of polyester diol 101.8 g, 1,4-
9.1 g of butanediol and 20.5 g of dimethylolpropionic acid were added and reacted while stirring at a temperature of 60 ° C. for 4 hours to obtain a uniform solution of an NCO-terminated urethane prepolymer. This NCO-terminated urethane prepolymer 1
While stirring with a homomixer, 59.1 g was added to 230 g of deionized water to which 6.2 g of triethylamine had been previously added, and 4.3 g of hexamethylenediamine was further added to the deionized water 2.
An aqueous solution dissolved in 0 g was added. Then, under reduced pressure 6
Acetone was distilled off at 0 ° C. for 3 hours to obtain a milky-white aqueous emulsion-type adhesive composition 3 having a solid content of 35%.

Comparative Example 1 Isophorone diisocyanate 13 was placed in a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer.
2.1 g and acetone 40 g were charged, and then heated and melted at 60 ° C. while stirring under a nitrogen stream, and the unmodified deodorized ordinary hydroxyl value 11 manufactured by Daicel Chemical Industries, Ltd. was used.
198.2 g of 5.0 KOH mg / g of polycaprolactone diol, 9.2 g of 1,4-butanediol and 20.6 g of dimethylolpropionic acid were added, and the temperature was adjusted to 60.
The mixture was reacted with stirring at 4 ° C. for 4 hours to obtain a uniform solution of an NCO-terminated urethane prepolymer. An aqueous solution in which 159.1 g of this NCO-terminated urethane prepolymer was added to 230 g of demineralized water to which 6.2 g of triethylamine had been previously added while stirring with a homomixer, and 4.4 g of hexamethylenediamine was dissolved in 20 g of demineralized water. Was added. Then, acetone was distilled off under reduced pressure at 60 ° C. for 3 hours,
A milky white aqueous emulsion type adhesive composition having a solid content of 35% was obtained. This aqueous emulsion type adhesive composition is referred to as Comparative composition 1.

Comparative Example 2 Isophorone diisocyanate 13 was placed in a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer.
1.1 g and acetone 40 g were charged, and then heated and melted at 60 ° C. while stirring under a nitrogen stream, and the undeodorized ordinary hydroxyl value of 11 produced by Daicel Chemical Industries, Ltd. was used.
99.1 g of 5.0 KOH mg / g of polycaprolactone diol, 101.8 g of polyester diol composed of 1,6-hexanediol and adipic acid having a hydroxyl value of 112 KOH mg / g, and 9.1 g of 1,4-butanediol
And 20.5 g of dimethylolpropionic acid were added thereto, and reacted while stirring at a temperature of 60 ° C. for 4 hours to obtain a uniform solution of an NCO-terminated urethane prepolymer. This NCO
159.1 g of the base-terminal urethane prepolymer was added to 230 g of demineralized water to which 6.2 g of triethylamine had been previously added while stirring with a homomixer, and an aqueous solution in which 4.3 g of hexamethylenediamine was dissolved in 20 g of demineralized water was added. did. Then, acetone was distilled off under reduced pressure at 60 ° C. for 3 hours to obtain a milky white aqueous emulsion type adhesive composition having a solid content of 35%. This aqueous emulsion type adhesive composition is referred to as Comparative composition 2.

Comparative Example 3 Isophorone diisocyanate 13 was placed in a four-necked flask equipped with a nitrogen inlet tube, a thermometer, a condenser and a stirrer.
0.2 g and acetone 40 g were charged, and then a hydroxyl value of 112 KOH consisting of 1,6-hexanediol and adipic acid heated and melted at 60 ° C. while stirring under a nitrogen stream.
mg / g of polyester diol 200.5 g, 1,4
-9.0 g of butanediol and 20.3 g of dimethylolpropionic acid were added and reacted while stirring at a temperature of 60 ° C for 4 hours to obtain a uniform solution of an NCO-terminated urethane prepolymer. 159.1 g of this NCO-terminated urethane prepolymer was added to 230 g of demineralized water to which 6.1 g of triethylamine had been previously added while stirring with a homomixer, and 4.3 g of hexamethylene diamine was further added to 2 ml of demineralized water.
An aqueous solution dissolved in 0 g was added. Then, under reduced pressure 6
Acetone was distilled off at 0 ° C. for 3 hours to obtain a milky-white aqueous emulsion-type adhesive composition having a solid content of 35%. This aqueous emulsion type adhesive composition is referred to as Comparative composition 3.

The compositions of Examples 1 to 3 and Comparative Examples 1 to 3 were evaluated by the methods described below.
Shown in

Adhesion Test The aqueous emulsion-type adhesive compositions of Examples and Comparative Examples of the present invention were treated with a corona-treated biaxially stretched polyethylene terephthalate film (manufactured by Toyobo Ester Co., Ltd .; product number: E
5100, thickness: 50 μm), corona-treated biaxially stretched polypropylene film (manufactured by Toyobo Pyrene Co., Ltd .; product number: P2161, thickness: 50 μm), acrylic plate (manufactured by Nitto Jushi Kogyo Co., Ltd .; product number: CRALEX S) ), Aluminum plate (manufactured by Nippon Test Panel Industries, Ltd .; product number: A
No. 5052P (specification: Ryusan alumite)) and veneer plywood (general commercially available product). 5 and dried at room temperature for one day and night, and then a cellophane tape peeling test was performed. The coating conditions were set so that the coating thickness after drying was in the range of 3 to 5 μm, and 5 (100% remaining), 4 (100% remaining)
(90% or more remaining), 3 (70% or more remaining), 2 (50
% Or more) and 1 (less than 50% remaining).

Odor Test The aqueous emulsion adhesive compositions of Examples and Comparative Examples of the present invention were evaluated for the degree of odor. Five testers (A,
B, C, D, E), the samples were arranged in the order of the odor degree, and the higher the degree, the lower the score of 1 to 1.
A score of 6 was given, and the average score was used to evaluate the degree of odor. The odor degree of the aqueous emulsion adhesive composition was evaluated by smelling the odor immediately after opening the sample at room temperature.

[0038]

[Table 1]

As is clear from the examples and comparative examples, the aqueous emulsion type adhesive composition of the present invention has excellent adhesiveness to various substrates having significantly different surface polarities,
It turns out that it is an aqueous emulsion type adhesive composition with extremely little odor in a sanitary environment.

[0040]

Industrial Applicability The aqueous emulsion type adhesive composition of the present invention has excellent adhesiveness to various substrates having significantly different polarities on the surface of various plastics, metals, woods, etc.
An aqueous emulsion-type adhesive composition having extremely low odor in a sanitary environment, and is extremely useful in industry.

Claims (3)

[Claims] 1. An aqueous emulsion-type adhesive composition comprising a polyurethane resin as a base polymer obtained by reacting a polyol, a diisocyanate compound and a chain extender, wherein a lactone-based composition in which at least 40% by weight of a polyol component is deodorized. An aqueous emulsion type adhesive composition, which is a polyester polyol. 2. The aqueous emulsion type adhesive composition according to claim 1, wherein the deodorization is performed by a water treatment and a dehydration treatment. 3. The water content in the lactone-based polyester polyol after the dehydration treatment is 0.03% by weight or less.
The aqueous emulsion type adhesive composition as described in the above.