KR100555177B1 - Polyurethane UV Curable Adhesive Primer Emulsion and Manufacturing Method Thereof - Google Patents

Abstract

 The present invention relates to a polyurethane-based UV (ultraviolet) curable adhesive primer emulsion and a method for preparing the same, according to the present invention, a molecular weight of 500 to 8000 polyol having a molar ratio of 1-3 in a solvent, dimethylol propionic acid and a molar ratio of 1.5 to 4.5 in a molar ratio. 0.5 to 5 weight ratio of polyurethane prepolymer formed by cooling an isocyanate type prepolymer having isocyanate end groups formed by reacting an isocyanate mixture of 3.5 to 10.5 in the presence of a catalyst and neutralizing by adding 50 to 100% of a tertiary amine equivalent to a carboxyl group. ; ii) 2 to 8 weight ratio of acrylates; iii) 0.3 to 3 weight ratio of chlorinated polyolefin (CPO) iv) 0.35 to 4 weight ratio of surfactant; And v) a polyurethane-based UV (ultraviolet) curing adhesive primer emulsion obtained by sufficiently mixing 0.15 to 1.5 weight ratio of photoinitiators and adding vi) residual water with stirring. The polyurethane-based water-based UV (ultraviolet) primer emulsion of the present invention is appropriately diluted and applied to a molded EVA foam, and then subjected to UV (ultraviolet) curing to exert its effect as a primer (pretreatment agent). Compared to the modified EVA UV (ultraviolet) primer, the primer exhibits excellent adhesion even under low energy UV (ultraviolet) curing against aqueous and oil-based adhesives.

Polyurethane, photocurable, adhesive primer

Description

Polyurethane adhesive primer composition for UV curing and preparing method

The present invention relates to a polyurethane UV (ultraviolet ray) curable adhesive primer emulsion and a method for manufacturing the same, and more particularly, to an aqueous emulsion type UV (ultraviolet) curing polyurethane primer emulsion and its preparation used as a primer of an adhesive in a shoe manufacturing process. It is about a method.

Conventionally, a solvent type UV (ultraviolet) primer was prepared using a chloroprene rubber (CR, chlorinated rubber) or a chlorinated polyolefin (CPO, chlorine content of about 25%). Solvent-type UV (ultraviolet) primers are excellent in heat resistance, cold resistance and flexibility, have good workability, and have excellent adhesion to EVA (ethylene vinyl acetate copolymer) foam of various hardness. However, these solvent type UV (ultraviolet) primers have excellent adhesion and workability, but contain various organic solvents such as toluene, methylethylketone, cyclohexane, methylcyclopetane, etc. There is a problem that causes environmental pollution. In addition, emission regulations of organic solvents and VOC's (volatile organic compounds) in coatings such as paints and adhesives have recently been tightened.

The present invention is to provide an emulsion-type aqueous UV (ultraviolet) curable adhesive primer emulsion and a method for producing the same that can cope with environmental problems by using water instead of an organic solvent. In another aspect, the present invention is to provide an adhesive primer emulsion for shoe manufacturing that is stable even after a long period of time and good UV (ultraviolet) curing effect. The present inventors have completed the present invention in view of being able to emulsify the polyurethane and dissolve the chlorinated polyolefin in the photocurable monomer by introducing ionic groups into the polyurethane to make it hydrophilic.

According to the present invention, i) isocyanate end groups formed by reacting in a solvent a molecular weight of 500 to 8000 polyol having a molar ratio of 1 to 3, a dimethylol propionic acid having a molar ratio of 1.5 to 4.5 and a isocyanate mixture of 3.5 to 10.5 at a molar ratio in the presence of a catalyst 0.5 to 5 weight ratio of polyurethane prepolymer formed by cooling the isocyanate type prepolymer which has, and neutralizing it by adding 50-100% of tertiary amine of the carboxyl equivalent; ii) 2 to 8 weight ratio of acrylates; iii) 0.3 to 3 weight ratio of chlorinated polyolefin (CPO) iv) 0.35 to 4 weight ratio of surfactant; And v) a polyurethane-based UV (ultraviolet) curing adhesive primer emulsion obtained by adding a residual amount of vi) with stirring while mixing 0.15 to 1.5 weight ratio of photoinitiators sufficiently. Such emulsions can be diluted or used according to concentration. 70 to 97 weight ratio of water is added to prepare the final primer. The polyol is a diol having an alcohol group in the sock end of the molecular weight of 500 to 8000 produced by the condensation reaction of excess glycol and diacid or dicarbonate.

Also by the present invention

1) i) an isocyanate type having an isocyanate terminal group by reacting in a solvent a molecular weight of 500 to 8000 polyol having a molar ratio of 1 to 3, a dimethylol propionic acid of 1.5 to 4.5 at a molar ratio and a 3.5 to 10.5 isocyanate mixture in the presence of a catalyst Obtaining a polymer,

   ii) cooling the isocyanate type prepolymer and neutralizing by adding 50 to 100% of a tertiary amine equivalent to a carboxyl group;

   iii) adding a acrylate of 1.5 to 4.5 in a molar ratio to produce a polyurethane prepolymer consisting of removing residual isocyanates; and

2) 0.5 to 5 weight ratio of the polyurethane prepolymer produced in step 1), a mixture of 2 to 8 weight ratio of acrylate and 0.3 to 3 weight ratio of chlorinated polyolefin (CPO), 0.35 to 4 weight ratio of surfactant, and photoinitiator 0.15 There is provided a method for producing a polyurethane-based UV (ultraviolet) curing adhesive primer emulsion comprising an emulsification step in which a residual amount of water is added while stirring after sufficiently mixing the ˜1.5 weight ratio. 70 to 97 weight ratio of water is added to prepare the final primer. Removing the residual isocyanate of step iii) may be performed together in the emulsification step 2).

The polyol preferably has a molecular weight of 2000 to 4000. For example, polyethyl adipate diol, polybutyl adipate diol, polyethyl adipate diol, poly neopentyl adipate diol, poly 1,6-hexyl adipate diol , Polycaprolactone diol, polycarbonate diol or mixtures thereof.

As an isocyanate compound, it is TDI (toluene isocyanate), IPDI (isophorone diisocyanate), HDI (hexamethylene isocyanate), or MDI (4, 4- methylene bis (phenyl isocyanate), for example.

As an acrylate compound, for example, isobornyl acrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate), 2-hydroxyethyl acrylate, methacrylic acid, acrylic acid, methyl methacrylate, methylacryl Ethylene glycol dimethacrylate and triethylene glycol dimethacrylate.

As a surfactant compound, For example, polyoxyethylene nonyl phenyl ether, polyoxyethylene lauryl ether, polyoxyethylene octyl phenyl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene lauryl amine, Polyoxyethylene stearyl amine, dodecylbenzenesulfonic acid sodium salt, dioctylsulfosuccinate sodium salt, ammonium alkylaryl ether sulfate or mixtures thereof.

The chlorine content of chlorinated polyolefins (CPO) is preferably 20 to 50%.

Photoinitiators are, for example, benzophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetonephenone, 1-hydroxy cyclohexylphenyl ketone, benzoin ether, benzyldimethyl ketal, thioxanthone or mixtures thereof.

Hereinafter, the present invention will be described in detail with reference to Examples. However, these examples are illustrative of the present invention and the scope of the present invention should not be construed as being limited by these examples.

Example 1.

   Prepolymer Preparation:

80 g (0.02 mol) of polyester polyol of 1,4-butanediol / adipic acid, 4 g (0.03 mol) of DMPA (dimethylol propionic acid), 15.5 g (0.07 mol) of IPDI (isophorone diisocyanate), 1 -4 g of methyl-2-pyrrolidone and 0.03 g of dibutyl tin dilaurate are added as a catalyst, and nitrogen is refluxed to inhibit the polymerization inhibition due to oxygen as much as possible.

After 3 hours of reaction at 80 ℃, 0.504g (0.0056mol) of 1,4-BD was added, and after 3 hours of reaction, it was cooled to 50 ℃ and neutralized by adding 2.87g (0.03mol) of TEA (triethylamine). The isocyanate is reacted by adding 3.72 g (0.029 mol) of 2-HEMA (2-hydroethylethylmethacrylate).

    Aqueous UV (ultraviolet) primer emulsion preparation:

In the 500 ml beaker after completion of the reaction, 1.82 g of the polyurethane prepolymer prepared above, 1.36 g of chlorinated polyolefin (CPO) containing 25% of chlorine, 3.41 g (0.0164 mol) of isobornyl acrylate, and 1.36 g of isobornyl methacrylate. (0.00613 mol), 2-hydroxyethyl methacrylate 0.8058 g (0.0062 mol), 0.6198 g (0.0 0313 mol) ethylene glycol dimethacrylate, 0.6198 g (0.00216 mol) triethylene glycol dimethacrylate, as surfactant 0.8250 g of polyoxyethylene nonyl phenol ether, 0.3 g of polyoxyethylene lauryl ether, 0.3750 g of sodium dodecylbenzenesulfonate, 0.3409 g of benzophenone as a photoinitiator, Irgacure-184 (brand name; Shiva specialty chemical company, 1-hydroxy) Cyclohexyl phenyl ketone) 0.3409g was added, and after sufficiently stirring, 190g of water was slowly added to emulsify.

Example 2.

In Example 1, the polyol was used by replacing 80 g (0.02 mol) of 1,6-hexanediol) / adipic acid polyester polyol and the rest was prepared in the same manner.

Example 3.

In Example 1 polyol was used by replacing 80 g (0.02 mol) of caprolactone diol and the rest was prepared in the same manner.

Examples 4 and 5

Examples 4 and 5 were prepared in the same manner as in Example 1 except for the surfactant and used surfactants are summarized in Table 1.

Comparative example

The oil-based UV (ultraviolet) primer was measured for the initial adhesive strength, the late adhesive strength of each of Examples 1 to 5, Comparative Examples, and the results are shown in Table 2 below.

Preparation of Adhesion Specimen

Shoe polyurethane-based emulsion UV (ultraviolet ray) primer was brushed three times with a brush on an EVA foam having a size of 25 × 100 mm and dried at 70 ° C. for 5 minutes.

After drying, it was irradiated with UV (ultraviolet) of 0.5J / cm 2 for 15 seconds, and applied with an aqueous polyurethane adhesive, dried at 70 ° C. for 7 minutes, and then coated with an aqueous polyurethane adhesive, and then bonded with the rubber and the adhesive surface dried at 70 ° C. for 7 minutes. It crimped | bonded and adhered by the load of about 5 kg * f. At this time, five test specimens were used for the same test.

Initial adhesion

The prepared adhesive specimen was left at room temperature for 30 minutes, and then peeled at a tensile rate of 100 ± 10 mm / min using a universal tensile tester (Instron's model name 1011) to measure adhesive strength.

Late adhesion

The prepared adhesive specimens were left at room temperature for 24 hours and then peeled at a tensile rate of 100 ± 10 mm / min using a universal tensile tester (Instron model name 1011) to measure the adhesive strength.

Table 1

(Unit: kg · f / cm) division Examples 1, 2, 3 Example 4 Example 5 1 (g) 2 (g) 3 (g) 1 (g) 2 (g) 3 (g) 1 (g) 2 (g) 3 (g) 0.8250 0.3000 0.3750 2 (g) 3 (g) 1 (g) 2 (g) 3 (g) 1 (g)

① Polyoxyethylene nonyl phenyl ether

② Polyoxythylene lauryl ether

③ Dodecylbenzenesulfonic acid, sodium salt

Table 2

(Unit: kg · f / cm) Example Comparative example One 2 3 4 5 Initial adhesion 3.0 (CF) 2.8 (CF) 2.5 (CF) 2.5 (CF) 2.1 (CF) 3.6 (AB) Late adhesion 3.8 (AB) 3.9 (AB) 3.8 (AB) 3.7 (AB) 3.7 (AB) 4.5 (AB) CF (cohesive failure): Adhesive layer break, AB (adherent break): Substance breakage Comparative example: U-5STF, Hwaseung T & C

When the polyurethane-based aqueous UV (ultraviolet) primer emulsion of the present invention is used as a shoe UV (ultraviolet) primer, the initial adhesion, the late adhesion, the hydrolysis adhesion is good and does not require an organic solvent, a large amount of VOC's oily UV (ultraviolet) It can be seen that compared to the primer can be reduced.

Claims (5)

i) isocyanate type having isocyanate end groups formed by reacting in a solvent a molecular weight of 500 to 8000 polyol having a molar ratio of 1 to 3, a dimethylol propionic acid of 1.5 to 4.5 at a molar ratio and an isocyanate mixture of 3.5 to 10.5 at a molar ratio in the presence of a catalyst 0.5-5 weight ratio of polyurethane prepolymers formed by cooling a polymer and neutralizing by adding 50-100% of tertiary amine of the carboxyl equivalent; ii) 2 to 8 weight ratio of acrylates; iii) 0.3 to 3 weight ratio of chlorinated polyolefin (CPO) iv) 0.35 to 4 weight ratio of surfactant; And v) a polyurethane-based UV (ultraviolet) curing adhesive primer emulsion obtained by sufficiently adding 0.15 to 1.5 weight ratio of the photoinitiator and stirring with vi) remaining water. The method of claim 1, wherein the polyol has a molecular weight of 2000 to 4000, polyethyl adipate diol, polybutyl adipate diol, polyethyl adipate diol, poly neopentyl adipate diol, poly 1,6-hexyl adipate diol, An adhesive primer emulsion for polyurethane-based UV (ultraviolet) curing selected from the group consisting of polycaprolactone diol, polycarbonate diol and mixtures thereof. The said isocyanate compound of Claim 1 or 2 is TDI (toluene isocyanate), IPDI (isophorone diisocyanate), HDI (hexamethylene isocyanate), MDI (4, 4- methylene bis (phenyl isocyanate)), The acrylate compound is selected from the group consisting of mixtures thereof, and isobornyl acrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, methacrylic acid, methyl methacrylate. , Ethylene glycol dimethacrylate, triethylene glycol dimethacrylate, and mixtures thereof, wherein the surfactant compound is polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene octylphenyl ether , Polyoxydetylene cetyl ether, polyoxyethylene styryl ether, polyoxyethylene lauryl Of chlorinated polyolefin (CPO) selected from the group consisting of min, polyoxyethylene stearyl amine, dodecylbenzenesulfonate sodium salt, dioctylsulfosuccinate sodium salt, ammoniumalkylarylethersulfate and mixtures thereof The chlorine content is preferably 20 to 50% and the photoinitiator is a benzophenone and / or 1-hydroxy cyclohexylphenyl ketone polyurethane-based UV (ultraviolet) curing adhesive primer emulsion. 1) i) an isocyanate type having an isocyanate end group by reacting in a solvent a molecular weight of 500 to 8000 polyol having a molar ratio of 1 to 3, a dimethylol propionic acid of 1.5 to 4.5 at a molar ratio and a 3.5 to 10.5 isocyanate mixture in the presence of a catalyst Obtaining a polymer,    ii) cooling the isocyanate type prepolymer and neutralizing by adding 50 to 100% of a tertiary amine equivalent to a carboxyl group;   iii) adding a acrylate of 1.5 to 4.5 in a molar ratio to produce a polyurethane prepolymer consisting of removing residual isocyanates; and 2) 0.5 to 5 weight ratio of the polyurethane prepolymer produced in step 1), a mixture of 2 to 8 weight ratio of acrylate and 0.3 to 3 weight ratio of chlorinated polyolefin (CPO), acrylate 2 to 8 weight ratio, surfactant 0.35 A method for producing a polyurethane-based UV (ultraviolet) curing adhesive primer emulsion, comprising an emulsification step of adding -4 weight ratio and a photoinitiator 0.15-1.5 weight ratio sufficiently and then adding a residual amount of water while stirring. The polyol according to claim 4, wherein the polyol has a molecular weight of 2000 to 4000, polyethyl adipate diol, polybutyl adipate diol, polyethyl adipate diol, poly neopentyl adipate diol, poly 1,6-hexyl adipate diol, The isocyanate compound is selected from the group consisting of polycaprolactone diol, polycarbonate diol, and mixtures thereof. Methylenebis (phenylisocyanate)) and mixtures thereof, and the acrylate compound is isobornyl acrylate, isobornyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxyethyl acrylate, Methacrylic acid, methyl methacrylate, ethylene glycol dimethacrylate, triethylene glycol dimethacrylate and The surfactant compound is selected from the group consisting of a mixture thereof, and the surfactant compound is polyoxyethylene nonylphenyl ether, polyoxyethylene lauryl ether, polyoxyethylene octylphenyl ether, polyoxydecylenecetyl ether, polyoxyethylene stearyl ether, poly Selected from the group consisting of oxyethylene lauryl amine, polyoxyethylene styryl amine, sodium dodecylbenzenesulfonate, sodium dioctylsulfosuccinate acid salt, ammoniumalkylarylethersulfate and mixtures thereof; chlorinated polyolefin) has a chlorine content of 20 to 50% and the photoinitiator is benzophenone, chloroacetophenone, diethoxyacetophenone, hydroxyacetonephenone, 1-hydroxy cyclohexylphenyl ketone, benzoin ether, benzyldimethyl ketal, thi Polyurethane-based UV (ultraviolet) curing adhesive oxanthone or a mixture thereof The method of Murray emulsion.