KR20170131769A - Polyurethane adhesive composition having excellent water dispersible - Google Patents

Abstract

The present invention relates to a polyurethane adhesive composition having excellent water dispersibility, and more specifically, to a polyurethane adhesive composition having excellent water dispersibility, the polyurethane adhesive composition which is harmless to the human body, is environmentally friendly, expresses remarkably improved adhesive force, and is excellent in water resistance at the same time. The polyurethane adhesive composition of the present invention comprises 160 to 250 parts by weight of a polyol with respect to 100 parts by weight of a diisocyanate-based component, wherein the polyol includes a bio polyol obtained by performing an epoxidation reaction of one or more compounds selected from the group consisting of lesquerella oil, castor oil, and soybean oil.

Description

[0001] The present invention relates to a polyurethane adhesive composition having excellent water dispersibility,

More particularly, the present invention relates to a polyurethane adhesive composition which is harmless to the human body, is environmentally friendly, exhibits remarkably improved adhesion, is excellent in water resistance, and excellent in water dispersibility.

Polyurethanes are manufactured in a wide variety of articles such as rigid foams, flexible foams, films, soft and hard elastomers and fibers, and the like. These polyurethane industries have developed in the domestic market until the 1980s, centering on daily necessities such as clothing, shoes, bags, toys, sofas and beds related to everyday life, and now they are also used as materials for automobiles, electronics, civil engineering and shipbuilding The market continues to grow as it is being used.

In addition, polyurethane resins are widely used as adhesives because of their excellent adhesiveness, flexibility and mechanical strength.

As such a polyurethane adhesive, an organic solvent-based polyurethane adhesive in which a polyurethane resin is dissolved in an organic solvent has been conventionally used. However, the organic solvent does not necessarily have a good effect on the human body or the environment, Recently, as interest in the sanitary environment increases, the development of an aqueous polyurethane adhesive composed of a polyurethane resin aqueous dispersion in which a polyurethane resin is dispersed in water has been rapidly developed instead of such an organic solvent-based polyurethane adhesive .

As a part of this development, Korean Patent Registration No. 10-0807649 discloses a method of reacting a polyisocyanate, a polycaprolactone polyol containing a polycaprolactone polyol having a number average molecular weight of 3,000 or more and an active hydrogen group-containing compound having an anionic group To prepare an isocyanate-terminated prepolymer, and reacting the resultant isocyanate-terminated prepolymer with a polyamine in water to obtain a polyurethane resin aqueous dispersion, and a polyurethane adhesive containing the polyurethane resin aqueous dispersion.

However, the polyurethane adhesives disclosed in the prior art do not achieve water-dispersibility to a desired level and have poor coatability. When the solvent is merely changed to water, there is a problem that the environmental friendliness is deteriorated. There was a difficult problem to make.

Disclosure of the Invention The present invention has been devised to solve the problems described above, and it is an object of the present invention to provide a polyurethane adhesive composition which achieves water dispersibility to a desired level, significantly improves film properties, is environmentally friendly, It is for this reason.

It is another object of the present invention to provide a polyurethane adhesive composition which is improved in flexibility and is prevented from being degraded in dispersibility due to gelation of the composition.

In order to solve the above-mentioned problems, the present invention provides a polyisocyanate composition comprising 160 to 250 parts by weight of a polyol with respect to 100 parts by weight of a diisocyanate component, wherein the polyol is at least one selected from the group consisting of Lesquerella Oil, Castor Oil and Soybean Oil ) Comprises at least one polyol selected from the group consisting of Lesquerella oil, castor oil and soybean oil, wherein the at least one polyol comprises a biopolyol obtained by epoxidizing at least one compound selected from the group consisting of Lesquerella oil, castor oil and soybean oil A polyurethane adhesive composition having excellent water dispersibility is provided.

According to a preferred embodiment of the present invention, the polyol is selected from the group consisting of tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, , 6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, Diol, 1,12-dodecanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, trimethyl Polytetramethylene glycol (PTMG), polycaprolactone (PCL), polypropylene glycol (PPG), polyethylene glycol (polyethyleneglycol), polyethyleneglycol , PEG), and polycarbonatediol (PCDL).

According to another preferred embodiment of the present invention, the diisocyanate component is selected from the group consisting of methylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, Isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 4,4'-diisocyanato-dicyclohexyl-methane, 4,4'-diisocyanate (2,2), 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanine And an aliphatic diisocyanate such as 2,2'- and 2,4'-diisocyanato-diphenylmethane, tetramethyl xylene diisocyanate, p-xylene diisocyanate and p-isopropylidene diisocyanate, And may include one or more.

According to another preferred embodiment of the present invention, the polyol includes polyethylene glycol, and the polyethylene glycol includes a first polyethylene glycol having a weight average molecular weight of 1200 to 1500 and a second polyethylene glycol having a weight average molecular weight of 3500 to 4000 can do.

According to another preferred embodiment of the present invention, the polyol may further comprise a polyol having three or more hydroxyl groups in at least one of glycerin, pentaerythritol and dipentaerythritol.

According to another preferred embodiment of the present invention, the polyol having three or more hydroxy groups may be contained in an amount of 70 to 80 parts by weight based on 100 parts by weight of polyethylene glycol.

According to another preferred embodiment of the present invention, the second polyethylene glycol may be included in an amount of 30 to 35 parts by weight based on 100 parts by weight of the first polyethylene glycol.

According to another preferred embodiment of the present invention, the polyol further comprises polyethylene glycol and pentaerythritol,

Wherein the polyethylene glycol comprises 30 to 35 parts by weight of a second polyethylene glycol having a weight average molecular weight of 3,500 to 4,000 based on 100 parts by weight of the first polyethylene glycol having a weight average molecular weight of 1200 to 1,500 and the pentaerythritol is a mixture of 100 parts by weight of polyethylene And 70 to 80 parts by weight based on 100 parts by weight of the resin.

According to another preferred embodiment of the present invention, the adhesive composition further comprises 30 to 80 parts by weight of chain extender relative to 100 parts by weight of the first component, and the chain extender is selected from the group consisting of ethanolamine, N-methylethanolamine (2-hydroxyethyl) -ethylenediamine, N, N-bis (2-hydroxyethyl) -ethylenediamine and 2, 3-diamino- (2-hydroxyethyl) -ethylenediamine, N, N-bis (2-hydroxyethoxy) ethylenediamine, N-methylpyrrolidone, At least one selected from the group consisting of (2-hydroxyethyl) -ethylenediamine and 2-propanolamine, Piperazine, ethylene diamine (EDA) and diethylenetriamine (DETA) .

Further, the present invention can be applied to a cured molded article by incorporating the above-described polyurethane adhesive composition according to the present invention, and the main material of the molded article is suitable for bonding metals, plastics, polymer materials, inorganic materials, paper and wood For example, automobile interior materials and the like can be widely used for various articles.

The adhesive composition according to one preferred embodiment of the present invention is excellent in water-dispersibility and satisfactory in film properties, and has remarkably excellent coatability and adhesive strength. Further, flexibility can be improved without deteriorating the water dispersibility due to gelation, and the adhesive component itself can be widely used for various molded articles which are environmentally friendly and thus harmless to the human body and directly or indirectly contacted with the human body.

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

First, the diisocyanate component will be described.

The diisocyanate-based component may be an organic compound containing at least two isocyanate groups, preferably diisocyanate Y (NCO) 2, wherein Y is a bivalent aliphatic hydrocarbon radical having 4 to 12 carbon atoms, A bivalent alicyclic hydrocarbon radical having 6 to 15 carbon atoms, a bivalent aromatic hydrocarbon radical having 6 to 15 carbon atoms or a bivalent aliphatic hydrocarbon radical having 7 to 15 carbon atoms.

Examples of such diisocyanate-based components which are preferably used are methylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, 1- Diisocyanoate-dicyclohexyl-methane, 4,4'-diisocyanato-dicyclohexyl-4,4'-diisocyanato-cyclohexane, Propane- (2,2), 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanato-diphenyl Methane, 2,2'- and 2,4'-diisocyanato-diphenylmethane, tetramethyl xylene diisocyanate, p-xylene diisocyanate, p-isopropylidene diisocyanate and mixtures of such compounds.

According to a preferred embodiment of the present invention, in order to achieve a more improved adhesion performance, a diisocyanate component having a weight average molecular weight of 1200 to 1400 is contained in an amount of 7 to 12% by weight of the total diisocyanate component . If the diisocyanate component having a weight average molecular weight of 1,200 to 1,400 is less than 7% by weight and / or the weight average molecular weight is less than 1,200 with respect to the total diisocyanate component, the desired level of adhesion performance can not be achieved , And if it contains more than 12% by weight and / or a weight average molecular weight of more than 1400, the water-dispersibility is remarkably lowered, and when water is used as a solvent due to the difficulty of using water as a solvent, There is a problem.

The diisocyanate-based component having a weight average molecular weight of 1200 to 1400 is preferably a diisocyanate-based component having a hetero atom in a radical connecting an isocyanate group and / or having a functionality of two or more isocyanate groups in each molecule. Isocyanurate, isocyanurate, urethane, allophanate, biuret, carbodiimide, iminooxadiazinedione, and / or oxazolidinone obtained by modifying simple aliphatic, alicyclic, araliphatic and / or aromatic diisocyanates. Polyisocyanates containing at least two diisocyanates having a diazathrone structure can be mentioned as examples. As a specific example, it may be 4-isocyanatomethyl-1,8-octane diisocyanate, which is a non-modified polyisocyanate having two or more isocyanate groups in each molecule.

At this time, the diisocyanate component may be a component of any one of dodecamethylene diisocyanate and hexamethylene diisocyanate as a main component, and further includes 4-isocyanatomethyl-1,8-octane diisocyanate In order to attain further increased physical properties and to satisfy even higher physical properties, it is preferable to include both dodecamethylene diisocyanate and hexamethylene diisocyanate as diisocyanate, wherein dodecamethylene diisocyanate And hexamethylene diisocyanate may be contained in a weight ratio of 1: 0.6 to 0.8.

Next, the polyol component contained in the bonding composition according to the present invention will be described.

The polyol component includes a bio-polyol. By including the bio-polyol, a more environmentally friendly and harmless adhesive composition can be realized. The biopolyol is a polyol modified from vegetable oils such as soybean oil, castor oil, palm oil, rapeseed oil or sunflower oil. In general, the vegetable oil is triacylglycerol glyceride structure as a main chain and has a side chain structure including multiple hydroxyl groups in various fatty acids derived from a carboxylic acid. The above vegetable oil is subjected to epoxidation reaction and synthesized with a polyol to produce a bio polyol can do.

Specifically, the epoxidation reaction is a reaction for synthesizing an epoxy ring in a vegetable oil. The plant oil, acetic acid, purified amberlite, and toluene are stirred, and the amberlite is filtered, washed with distilled water, And the residual water is removed by using sodium sulfate in the oil layer. Thereafter, toluene is removed using a distillation concentrator or the like to obtain an epoxidized vegetable oil.

In order to synthesize the epoxidized vegetable oil with a polyol, ethylene glycol, distilled water, isopropanol, and tetrafluoroboric acid are mixed in the epoxidized vegetable oil, the hydroxyl group is controlled by the amount of the tetrafluoroboric acid, After completion of the reaction, the isopropanol was removed using a distillation concentrator. The oil layer was filtered using a separatory funnel, toluene was added to the oil layer to dissolve it, and then sodium sulfate And the toluene is removed by using a distillation concentrator or the like to synthesize a bio-polyol. An epoxidation reaction of castor oil, Lesquerella Oil or Soybean Oil, Compounds. ≪ / RTI >

On the other hand, the bio polyol may be contained in 18 to 23 wt% of the polyol. If the bio polyol is contained in an amount less than 18% by weight based on the total amount of the polyol, there is a problem in that flexibility and adhesive strength are lowered. When the content is more than 23% by weight,

The polyol component may further include, without limitation, a polyol component containing two or more hydroxy groups contained in a conventional polyurethane adhesive composition, preferably tetrapropylene glycol, 1,3-propanediol, 1, Butanediol, 2,3-butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, 1,4-dihydroxy 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, neopentyl glycol, 1,4-cyclohexanediol, 1,4- But are not limited to, polytetramethylene glycol (PTMG), dipentaerythritol tetramethylene glycol, dipentaerythritol tetramethylene glycol, cyclohexanedimethanol, 1,4-dihydroxybenzene, Polycaprolactone (PCL), polypropylene glycol (PPG), polyethyleneglycol (PEG) , And polycarbonatediol (PCDL).

According to a preferred embodiment of the present invention, polyethylene glycol having a weight average molecular weight difference of not less than 2000 may be included in the polyol in order to exhibit excellent physical properties such as improved flexibility and water resistance, Preferably a first polyethylene glycol having a weight average molecular weight of 1200 to 1500 and a second polyethylene glycol having a weight average molecular weight of 3500 to 4000 and still more preferably a second polyethylene The glycol may be contained in an amount of 30 to 35 parts by weight.

Among the polyols used in the polyurethane compositions disclosed so far, polyols having a large weight average molecular weight are likely to gel when incorporated into the composition, and gelation initiated before the coating film may have a problem of significantly reducing the film-forming property. However, when a low molecular weight polyol is used in order to solve this problem, there is a problem that the mechanical properties of the cured polyurethane, in particular, flexibility and elasticity are lowered. An example of the present invention is polyethylene glycol having a weight average molecular weight of at least 2000 in order to have good mechanical properties without deteriorating water dispersibility. If the weight average molecular weight difference between polyethylene glycols is less than 2000, The appearance of physical properties may be weak.

On the other hand, when the difference in the weight average molecular weight is 2000 or more, the polyethylene glycol preferably has a weight average molecular weight of 1,200 to 1,500 and 3,500 to 4,000, respectively, in order to further improve the physical properties of the desired polyethylene glycol And they are mixed at a specific weight ratio, thereby realizing a polyurethane composition which exhibits the desired physical properties more easily.

If the amount of the second polyethylene glycol is less than 30 parts by weight based on 100 parts by weight of the first polyethylene glycol, there is a problem that improvement in mechanical strength, such as flexibility, to be obtained by incorporating polyethylene glycol having a relatively large molecular weight may be insufficient. In addition, if the second polyethylene glycol is contained in an amount exceeding 35 parts by weight, gelation of the composition rapidly occurs and the coating film may be very weak.

However, as described above, when polyethylene glycol having a relatively high molecular weight is included in order to improve mechanical properties such as flexibility, gelation may occur partially in the composition, which may cause a problem of lowering water dispersibility. In order to solve this problem, according to a preferred embodiment of the present invention, the polyol further comprises a polyol having at least three hydroxyl groups in glycerin, pentaerythritol and dipentaerythritol, The polyol having three or more hydroxy groups may be pentaerythritol. At this time, the polyol containing three or more hydroxy groups may be contained in an amount of 70 to 80 parts by weight based on 100 parts by weight of polyethylene glycol, thereby achieving a composition having an excellent coating property by preventing gelation to the maximum and increasing water dispersibility .

If the amount of the polyol having three or more hydroxyl groups is less than 70 parts by weight based on 100 parts by weight of the polyethylene glycol, there is a problem that the inhibition of gelation may be reduced. When the amount of the polyol exceeds 80 parts by weight, the content of the polyethylene glycol in the limited amount of the polyol in the composition is reduced, so that the mechanical properties such as flexibility through the polyethylene glycol may be insufficient.

On the other hand, the polyol component is contained in 160 to 250 parts by weight based on 100 parts by weight of the diisocyanate component. If the polyol component is contained in an amount of less than 160 parts by weight, the polyol component may not be polymerized to exhibit adhesive properties, There is a problem that the adhesive force is remarkably lowered.

Next, the chain extender included in the adhesive composition according to the present invention will be described.

The chain extenders can be used without limitation in chain extenders included in conventional polyurethane adhesive compositions and are preferably selected from the group consisting of ethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine, 1,3-diamino Propanol, N, N-bis (2-hydroxyethyl) -ethylenediamine and 2-propanolamine, ethanolamine, N-methylethanolamine, diethanol Amine, diisopropanolamine, 1,3-diamino-2-propanol, N- (2-hydroxyethyl) -ethylenediamine, N, N-bis (2-hydroxyethyl) (Piperazine), ethylene diamine (EDA), and diethylenetriamine (DETA). In order to exhibit improved physical properties, N-methyl Ethanolamine.

The chain extender may be included in an amount of 30 to 80 parts by weight based on 100 parts by weight of the first component. If the chain extender is contained in an amount of less than 30 parts by weight, the mechanical properties may deteriorate. If the chain extender is contained in an amount exceeding 80 parts by weight, the elasticity and flexibility may be significantly lowered, .

Meanwhile, according to a preferred embodiment of the present invention, the composition may further comprise a water dispersibility improving component. The water dispersibility improving component has an advantage that the adhesive composition can be dispersed more remarkably in water used as a solvent, and the advantage that the adhesion failure occurring due to the positioning of the adhesive composition only in a specific portion at the time of coating can be remarkably reduced . The water dispersibility improving component is preferably selected from the group consisting of N- (2-aminoethyl) -2-aminoethanesulfonic acid, N- (3-aminopropyl) -2-aminoethanesulfonic acid, N- A diamine compound further containing a sodium, lithium, potassium, tertiary amine salt, sulfonate and / or carboxylate group of 3-aminopropane sulfonic acid, N- (2-aminoethyl) A sulfonate or carboxylate group such as a dihydroxyl compound, more preferably sodium 3,5-dicarbomethoxybenzenesulfonate, still more preferably sodium 3, 5-dicarbomethoxybenzenesulfonate may be included in an amount of 3 to 5 parts by weight based on 100 parts by weight of the first component.

If the sodium 3,5-dicarbomethoxybenzenesulfonate is contained in an amount of less than 3 parts by weight, there is a problem that the water-dispersibility can not be improved to the desired level. If sodium 3,5-dicarbomethoxybenzenesulfonate When the content of the nate is more than 5 parts by weight, the cured adhesive of the adhesive composition is weak in moisture resistance, and the adhesive force can easily be weakened by moisture.

On the other hand, the present invention includes a cured molded article containing the polyurethane adhesive composition according to the present invention. The molded article may be an automobile interior material, a building material, or an interior material, but is not limited thereto, and may be applied to various items to which the adhesive composition can be coated.

Hereinafter, a method of manufacturing the molded article will be described. However, the present invention is not limited by the following description.

(1) coating an article with an adhesive composition according to the present invention; (2) removing water contained in the adhesive composition; (3) irradiating the adhesive composition with actinic radiation and / or heat; And (4) contacting the article itself or another article with the adhesive composition irradiated with actinic radiation and / or heat.

The material of the article can be of any material, and as a non-limiting example thereof, an ethylene vinyl acetate copolymer (EVA) such as a Phylon, a pressed EVA or a dye cut, EVA as well as rubbers such as SBR (styrene / butadiene rubber), NBR (nitrile / butadiene rubber), TR (thermoplastic rubber), natural rubber, EPDM (ethylene / propylene / diene rubber), polyolefins and other thermoplastics, Lt; / RTI >

In the step (1), it is possible to apply the adhesive composition according to the present invention to the entire surface of the article or at least one part of the surface of the article.

In step (1), one or more pretreatments may optionally be performed before the surface of the article is coated with the adhesive composition according to the present invention. By way of non-limiting example, it is desirable to wash any attachment mold release agent resulting from dust, dirt, grease, and substrate fabrication of the surface to be joined. Here, such cleaning may be performed by cleaning and / or machining. For cleaning, a solvent or preferably an aqueous washing solution can be used. The cleaning is considerably more effective in combination with mechanical intervention such as wiping, brushing, radiation or ultrasonic treatment. Additional processing of the surface by high-energy radiation, especially ionizing radiation such as plasma, or activation of the surface by ozone or mechanical lubrication may be a particularly advantageous method. Needless to say, it is possible to use a primer, but the adhesive composition according to the present invention may not require a primer, so that the application of the primer may be uneconomical.

Meanwhile, the adhesive composition according to the present invention may be applied to various types of substrates such as roller coating, blade coating, flow coating, casting, printing, transfer, brushing, dipping, (1) can be carried out by a known coating method such as spray drying. On the other hand, the use of radiation that can cause early reaction of the photoinitiator or polymerization of the double bonds should be excluded from step (1).

In step (2), water may be removed. Preferably, water can be removed by drying at elevated temperatures in an oven (convection oven, jet dryer) and thermal radiation (IR, NIR) that moves with the air and is optionally dehumidified. Microwave can also be used to remove water. Further, the water removal method described above may be carried out by using two or more of them in plural.

On the other hand, the conditions for the drying may be selected to maintain the maximum temperature at which the article is shaped, deformed in an uncontrolled manner on the surface of the article, or reached below a limit causing other damage.

Next, in (3), the article to which the adhesive composition is applied can be irradiated with actinic radiation and / or heat, and more preferably, actinic radiation and heat can be irradiated at the same time.

The actinic radiation may preferably be performed under the action of high-energy radiation, i.e. UV radiation or sunlight, preferably light having a wavelength of from 200 nm or more to 750 nm or less. As a radiation source or a UV light source, for example, a medium pressure or high pressure mercury vapor, etc., the vapor vapor can be modified by the administration of another element such as gallium or iron. A laser, a pulsed lamp (termed a UV flash lamp), a halogen lamp or an excimer radiation means may also be used. The radiation means may be installed in a fixed position and the article to be irradiated may move past the radiation source by means of a mechanical device or the radiation means may be movable and the article to be irradiated is not displaced during curing. Typically sufficient radiation doses for curing by UV curing are in the range of 80 mJ / cm ² to 5000 mJ / cm ² with a radiation intensity of 80 mW / cm ² to 3000 mW / cm ² .

The radiation may also optionally be carried out, for example, in the presence of an insoluble gas atmosphere or an oxygen-depleted atmosphere, with the exception of oxygen. Suitable insoluble gases are preferably nitrogen, carbon dioxide, inert gases or combustion gases. The irradiation may also be performed by coating a dry layer having a medium that transmits radiation. Examples of such are synthetic films, glass or liquids such as water.

Depending on radiation dosage, radiation intensity, distance and other curing conditions, the type and concentration of photoinitiator used should be varied or optimized in a manner known to the ordinarily skilled artisan using preliminary tests as a guide. In order to cure the dried adhesive composition on the three-dimensional surface of the complex form, it may be advantageous to perform the curing using a plurality of radiation means. The arrangement of the radiation means may also be selected such that an optimal dose and intensity of radiation for curing is given at each coating point. In particular, it is desirable that the unexposed area (shade) is not present. For the most complete polymerization possible of the double bonds in the dried dispersant, the highest possible temperature and the highest possible strength and dose possible during irradiation are advantageous, but depending on the article used, the heat load on the article is not too great It may be advantageous to select the irradiation conditions. In particular, thin articles or articles made of materials having a low glass transition temperature can cause unregulated deformations if the irradiation generates an excessive specific temperature. In this case, it is advantageous to make use of a suitable filter or construction of the radiation means to allow some infrared radiation to act on the article. It is also possible to correspond to an unregulated strain by reducing the corresponding dose of radiation. However, for the most complete polymerization possible, irradiation can be performed at a specific dose and intensity. In this case, it is particularly advantageous to cure under insoluble or oxygen-depleted conditions, since the amount of oxygen in the atmosphere that exceeds the dried adhesive composition is reduced, since the dosage required for curing is reduced.

It is particularly preferable to use a mercury radiation means fixedly provided for curing. To cure such a coating, it is preferably 100 mW / cm ² or more to 2000 mW / cm ² or more ² 200 mJ / cm with an intensity of the radiation or less to use a dosage of 2000mJ / cm ² or less.

The heat may then be simultaneously irradiated to activate the crystals or some crystalline constituents of the dried adhesive composition. It is also possible that the heat is irradiated after the irradiation of the radiation or simultaneously the irradiation of the radiation is performed. Preferably by a short dwell time in the oven of a high temperature (convection oven, jet dryer) and / or by heat irradiation (IR, NIR), and microwaves can also be used.

Next, in step (4), the adhesive composition may include contacting the dried or hardened article itself or another article, and the step of contacting the article may be performed by simultaneously applying a certain level of pressure or more .

The present invention will now be described more specifically with reference to the following examples. However, the following examples should not be construed as limiting the scope of the present invention, and should be construed to facilitate understanding of the present invention.

≪ Example 1 >

35 parts by weight of polyisocyanate (weight average molecular weight 1,250) of 4-isocyanatomethyl-1,8-octane diisocyanate (weight average molecular weight 1,250) was added to 100 parts by weight of diisocyanate which is hexamethylene diisocyanate as a middle diisocyanate- Respectively. The polyol was contained in an amount of 220 parts by weight based on 100 parts by weight of the mixed first component. The polyol contained 17% by weight of the compound obtained by epoxidizing the castor oil at the total weight of the polyol, the first polyethylene glycol (PEG1350, (PEG 3500, weight average molecular weight: about 3500) 11.52 wt%, and pentaerythritol 35.48 wt% (74.66 parts by weight relative to 100 parts by weight of polyethylene glycol). Also, 40 parts by weight of diethanolamine as a chain extender with respect to 100 parts by weight of the diisocyanate component was dispersed in water to prepare a polyurethane adhesive composition as shown in Table 1 below.

≪ Examples 2 to 10 >

The composition and / or composition ratio of the polyurethane adhesive composition were changed as shown in the following Table 1 or 2 to prepare a polyurethane adhesive composition as shown in Table 1 or Table 2 below.

≪ Comparative Examples 1 and 2 &

The composition and / or composition ratio of the polyurethane adhesive composition were changed as shown in Table 2 below to prepare a polyurethane adhesive composition as shown in Table 2 below.

<Experimental Example 1>

To measure the water dispersibility of the polyurethane adhesive composition prepared through the above Examples and Comparative Examples, the adhesive composition was dispersed in water in the polyurethane adhesive compositions produced in each of the Examples and Comparative Examples and stored at 50 ° C for 7 days And then visually observed to observe the dispersibility. At this time, the dispersibility of the adhesive composition of Comparative Example 1 was set at 0, the degree of dispersibility of the remaining samples was changed from 0 to 5 as the dispersibility became better, The results are shown in Tables 1 to 2 below.

<Experimental Example 2>

After the polyurethane adhesive composition prepared in the above Examples and Comparative Examples was dispersed in water, the following specimens were prepared using the dispersed adhesive composition, and the following physical properties were measured and shown in the following Tables 1 to 2 .

Manufacture of specimens

A first specimen of polycarbonate having a width of 15 cm, a length of 15 cm and a height of 0.5 cm was formed, and after the curing, the adhesive composition according to the examples and the comparative examples dispersed in water so as to have a thickness of 0.5 cm was applied, Sized specimen, pressed with a 50 kg / 25 mm roll, and dried at 80 ° C for 2 hours to prepare a specimen.

1. Coating property

The filmability was evaluated as follows. After drying the adhesive composition for 2 hours at a temperature of 80 占 폚 for the first specimen on which the polyurethane adhesive composition before the bonding of the second specimen of the specimen was applied, bubbles were generated in the film or the surface became uneven 5, no change was observed on the surface of the coating film, 4 ~ 0 as the degree of bubble or haze appeared or dissolved and the stickiness occurred.

2. Evaluation of adhesion

After peeling the specimen with a width of 1 inch, the first specimen was placed on a jig and peel strength was measured using a UTM at a speed of 50 mm / min and a peel angle of 90 °. The results of measurement in Examples and Comparative Examples are shown relative to the adhesive strength of the remaining Examples and Comparative Examples based on the peel strength of Example 1 as 100%. The higher the peeling force, the better the adhesion.

3. Evaluation of moisture resistance

The specimen was observed for 100 hours at intervals of 10 hours in a reliability chamber set at 85 ° C and 85% relative humidity, and the interfacial separation and lifting of the first specimen / adhesive layer / second specimen were observed through an optical microscope To evaluate moisture resistance. When there is no abnormality in the evaluation result, any abnormality occurs in 5, interface separation, etc.

4. Flexibility assessment

The specimen was held at both ends and bent and stretched 50 times up and down repeatedly. Thereafter, the adhesive layer was cross-cut with a knife so as to be spaced apart by 1 mm. The scratched tape is then attached to the cut surface and pulled at an angle of 60 ° to confirm that the adhesive layer is peeled off. Evaluation criteria were evaluated according to ISO 2409. (5B: 0%, 4B: 5% or less, 3B: 5-15%, 2B: 15-35%, 1B: 35-65%, 0B: 65%

[Table 1]

[Table 2]

Specifically, as can be seen from Tables 1 and 2,

In Example 2, the content of the diisocyanate component having a weight average molecular weight of 1200 to 1400 was small and water dispersibility and film-forming property were excellent, but adhesive strength and flexibility were remarkably lowered than in Example 1.

It was confirmed that the content of the diisocyanate component having a weight average molecular weight of 1200 to 1400 in the case of Example 3 exceeded the preferable range and the water dispersibility was remarkably lower than that of Example 1 and the coating film property, moisture resistance, flexibility and the like were also remarkably poor .

Further, in the case of Example 4, the diisocyanate component includes hexamethylene diisocyanate, dodecamethylene diisocyanate, and 4-isocyanatomethyl-1,8-octane diisocyanate, Therefore, it can be confirmed that excellent adhesion performance is exhibited as compared with Examples 1 to 3.

On the other hand, in Example 8 in which the difference in the weight average molecular weight of the polyethylene glycol as the polyol component is less than 2000, it can be confirmed that the flexibility is poor as compared with Example 4. [

In the case of Example 7 in which the weight average molecular weights of the first polyethylene glycol and the second polyethylene glycol do not fall within a preferable range even when the first polyethylene glycol and the second ethylene glycol each having a weight average molecular weight difference of 2000 or more are included, And flexibility are not significantly better than in Example 4.

Further, in the case of Example 5 in which the content of the second polyethylene glycol exceeds the preferable range, even when the first polyethylene glycol and the second ethylene glycol each having a weight-average molecular weight difference of not less than 2000 and each having a weight average molecular weight falling within a preferred range It can be confirmed that the water-dispersibility and the film-forming property are remarkably lower than those of Example 4. Further, it can be confirmed that in Example 6, in which the content of the second polyethylene glycol is less than the preferable range, the flexibility is significantly lower than that in Example 4.

On the other hand, in Comparative Example 1 using a polyol having two hydroxyl groups instead of a polyol having three or more hydroxy groups without containing a biopolymer as a polyol component, water dispersibility, film-formability and adhesiveness were remarkably decreased Can be confirmed.

Claims (10)

And 160 to 250 parts by weight of a polyol with respect to 100 parts by weight of a diisocyanate component,
The polyurethane adhesive composition according to any one of claims 1 to 3, wherein the polyol comprises a biopolyol obtained by epoxidizing at least one compound selected from the group consisting of Lesquerella oil, castor oil and soybean oil. The method according to claim 1,
The polyol may be selected from the group consisting of tetrapropylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 2,3-butanediol, 1,5-pentanediol, 1,3-propanediol, 1,4-dihydroxycyclohexane, 1,4-dimethylolcyclohexane, 1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, 1,4-cyclohexanedimethanol, 1,4-dihydroxybenzene, 1,3-dihydroxybenzene, trimethylolpropane, glycerin, pentaerythritol, Polytetramethylene glycol (PTMG), polycaprolactone (PCL), polypropylene glycol (PPG), polyethyleneglycol (PEG), and polycarbonatediol, PCDL). &Lt; / RTI &gt; The method according to claim 1,
The diisocyanate component may be at least one selected from the group consisting of methylene diisocyanate, methylpentamethylene diisocyanate, hexamethylene diisocyanate, dodecamethylene diisocyanate, 1,4-diisocyanato-cyclohexane, 1-isocyanato- 5-trimethyl-5-isocyanatomethyl-cyclohexane, 4,4'-diisocyanato-dicyclohexyl-methane, 4,4'-diisocyanato-dicyclohexylpropane- (2,2 ), 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, 2,6-diisocyanatotoluene, 4,4'-diisocyanato-diphenylmethane, 2,2 ' - and polyurethane having excellent water-dispersibility, containing at least one of 2,4'-diisocyanato-diphenylmethane, tetramethylxylene diisocyanate, p-xylene diisocyanate and p-isopropylidene diisocyanate Adhesive composition. 3. The method of claim 2,
Wherein the polyol comprises polyethylene glycol,
Wherein the polyethylene glycol comprises a first polyethylene glycol having a weight average molecular weight of 1200 to 1500 and a second polyethylene glycol having a weight average molecular weight of 3500 to 4000. The polyurethane adhesive composition according to claim 1, 5. The method of claim 4,
Wherein the polyol further comprises a polyol having three or more hydroxyl groups in at least one of glycerin, pentaerythritol and dipentaerythritol. 6. The method of claim 5,
Wherein the polyol having three or more hydroxy groups is contained in an amount of 70 to 80 parts by weight based on 100 parts by weight of polyethylene glycol. 6. The method of claim 5,
Wherein the second polyethylene glycol is contained in an amount of 30 to 45 parts by weight based on 100 parts by weight of the first polyethylene glycol. The method according to claim 1,
Wherein the polyol further comprises polyethylene glycol and pentaerythritol,
Wherein the polyethylene glycol comprises 30 to 45 parts by weight of a second polyethylene glycol having a weight average molecular weight of 3500 to 4000 based on 100 parts by weight of the first polyethylene glycol having a weight average molecular weight of 1200 to 1500,
Wherein the pentaerythritol is contained in an amount of 70 to 80 parts by weight based on 100 parts by weight of polyethylene.
The method according to claim 1,
The adhesive composition further comprises 30 to 80 parts by weight of the chain extender relative to 100 parts by weight of the first component,
The chain extender may be selected from the group consisting of ethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine, 1,3-diamino-2-propanol, N- (2- hydroxyethyl) Bis (2-hydroxyethyl) -ethylenediamine and 2-propanolamine, ethanolamine, N-methylethanolamine, diethanolamine, diisopropanolamine, (2-hydroxyethyl) -ethylenediamine, 2-propanolamine, Piperazine, ethylene diamine (EDA) and diethylenetriamine amine, DETA). The polyurethane adhesive composition according to claim 1, A cured molded article comprising the polyurethane adhesive composition according to any one of claims 1 to 9.