KR101870777B1 - Manufacturing method of microcapsule type latent curing agent and microcapsule type latent curing agent using the same - Google Patents

Abstract

The present invention relates to a manufacturing method of a microcapsule-type latent curing agent and a microcapsule-type latent curing agent manufactured by the same and, more specifically, to a manufacturing method of a microcapsule-type latent curing agent and a microcapsule-type latent curing agent manufactured by the same which encloses a core material, an unstable or weakly persistent isocyanate-type curing agent, in a micro-container (polyurethane, polyurea barrier, etc.) having a diameter of a few micrometers or a few hundred micrometers without changing unique chemical properties and then discharge the isocyanate curing agent to the outside by heat (100-200°C) to heat and harden an adhesive in a short time to improve adhesion properties. The adhesion properties can be improved and energy can be reduced. Also, a clean and safe work environment is possible, which is suitable for urbanization of a shoe assembly process requiring a lot of personnel and energy.

Description

TECHNICAL FIELD [0001] The present invention relates to a method for producing a microcapsule type latent curing agent and a microcapsule type latent curing agent prepared by the method. BACKGROUND ART < RTI ID = 0.0 >

The present invention relates to a microcapsule type microcapsule type microcapsule type microcapsule type microcapsule type microcapsule type microcapsule type microcapsule type microcapsule type microcapsule type microcapsule type microcapsule type microcapsule type microcapsule type A latent curing agent, and a microcapsulated latent curing agent prepared by the method.

The shoe configuration can be largely divided into an upper and a sole, and a sole is divided into parts such as an outsole, a midsole, and an insole, They are manufactured through each manufacturing process and then assembled by an adhesive.

On the other hand, the adhesive is the most important material in the shoe manufacturing process, and it is used for adhesion of fabric, sole, part logo, toe cap, back counter, etc., There is a problem in that it is difficult to work with toxic substances or odors in the coating process by using an organic solvent as a solvent, and it is difficult to work by discharging pollutants in the city center.

Since the shoe material is a typical non-polar material, it is very difficult to bond. Therefore, various preprocessing processes, primer and adhesive are processed. Before applying the adhesive to the shoe sole composed of sole, midsole and upper, Cleaning is a process to remove contaminants such as mold release agents on the surface of each component. UV (ultraviolet) process changes the surface of the material by chemical method. It is an indispensable process for the development of adhesion force used to strengthen the bonding force.

In order to solve this problem, Patent Document 1 has developed a hot-melt type adhesive which exists in a solid state at room temperature and is melted by heat, and by applying this adhesive to a non-polar material, there is no risk of using a solvent, And to simplify the process.

However, the conventional techniques as described above have a problem that the adhesive property to an actual non-polar material is very low.

The applicant of the present invention has completed the present invention by producing a microcapsule type latent curing agent capable of releasing an isocyanate core material to the outside to heat and cure the adhesive in a short time to improve the adhesive property.

Patent Document 1: Korean Patent Laid-Open Publication No. 10-2011-0104732 entitled "Hot Melt Adhesive Composition"

Disclosure of Invention Technical Problem [8] Accordingly, the present invention has been made to solve the above problems, and it is an object of the present invention to provide a core material which is an unstable or weakly stable isocyanate type curing agent and which can be used as a microcapsule having a diameter of several tens of micrometers to several hundreds of micrometers (polyurethane, ), And the isocyanate core material is released to the outside due to heat (100 to 200 ° C) to heat and cure the adhesive in a short time, thereby improving the adhesive property. It is possible to obtain an energy saving effect as well as an improvement in adhesion properties, and a clean, safe and safe working environment is possible, thereby making it very suitable for the urbanization of a shoe assembly process with a lot of manpower and energy input.

The present invention relates to a method for producing an emulsion, comprising: (S100) mixing an emulsifier and deionized water to prepare an emulsion solution; Separately preparing a prepolymer / core solution (S200); A step (S300) of charging and stirring the prepolymer / core solution into the emulsified solution; Injecting curing materials (S400); And a cleaning, filtration and drying step (S500). The method for producing a microcapsule type latent curing agent and the microcapsule type latent curing agent prepared by the method are a solution to the problem .

In step S100, it is preferable that 2.5 to 15 parts by weight of an emulsifier are mixed with 100 parts by weight of distilled water at room temperature.

In step S200, 30 to 48 parts by weight of an isocyanate-prepolymer is mixed with 100 parts by weight of core materials at 60 to 70 ° C.

In step S300, the prepolymer / core solution is poured into the emulsified solution under a nitrogen atmosphere, and the mixture is stirred at a speed of 100 to 1000 rpm for 40 to 50 minutes while heating to 30 to 40 ° C.

In addition, in step S400, 106 to 227 parts by weight of the curing agent is added to 100 parts by weight of the isocyanate-prepolymer, and the temperature is elevated to 65 to 75 占 폚.

The step S500 is preferably performed by rinsing with distilled water, vacuum filtration, drying at room temperature for one day, and further vacuum desiccation.

The isocyanate-prepolymer is prepared by stirring an isocyanate and a solvent at 75 to 85 ° C, adding 18 to 42 parts by weight of a diol to 100 parts by weight of the isocyanate, reacting the mixture in a nitrogen atmosphere, And distilling off the solvent to remove the solvent.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a microcapsule type latent curing agent capable of improving adhesiveness by heating and curing the adhesive in a short time by releasing the isocyanate core material to the outside, It is possible to provide a clean and safe safe working environment, which makes it very suitable for the urbanization of a shoe assembly process with a lot of manpower and energy input.

1 is a process diagram showing a process for producing a microcapsule type latent curing agent according to the present invention
2 is a micrograph of a microcapsulated latent curing agent according to the present invention

In order to achieve the above-mentioned effects, the present invention relates to a process for producing a microcapsule-type latent curing agent and a microcapsule-type latent curing agent prepared by the method, and only the parts necessary for understanding the technical structure of the present invention are explained It should be noted that the description of other portions will be omitted so as not to obscure the gist of the present invention.

Hereinafter, a method for preparing a microcapsule type latent curing agent according to the present invention and a microcapsule type latent curing agent prepared by the method will be described in detail.

The present invention relates to a method for preparing a prepolymer / core solution, comprising the steps of: preparing an emulsified solution by mixing an emulsifier and deionized water (S100), separately preparing a prepolymer / core solution (S200) A step S300 of charging and stirring the prepolymer / core solution into the emulsified solution, a step S400 of applying curing materials, and a step of cleaning, filtering and drying S500.

In step S100, 2.5 to 15 parts by weight of an emulsifier is mixed with 100 parts by weight of distilled water at room temperature (25 DEG C) to prepare an emulsified solution by mixing emulsifier and deionized water.

Gum arabic may be used as the emulsifying agent. If the amount of the emulsifying agent is less than 2.5 parts by weight, the emulsion concentration may be too low to form capsules. When the amount of the emulsifying agent is more than 15 parts by weight, There is a fear that the core material may not penetrate.

In step S200, 30 to 48 parts by weight of an isocyanate-prepolymer is mixed with 100 parts by weight of core materials at a temperature of 60 to 70 DEG C, separately preparing a prepolymer / core solution.

Here, the core material may be a diisocyanate such as isophorone diisocyanate, meta-tetramethylxylylene diisocyanate, or toluene-2,4-diisocyanate. Triisocyanates such as isophorone triisocyanate, hexamethylene triisocyanate, diphenylmethane triisocyanate, and triphenylmethane triisocyanate can be used as the polyisocyanate.

The isocyanate-prepolymer is prepared by stirring an isocyanate and a solvent at 75 to 85 ° C, and then adding 100 parts by weight of the isocyanate to the isocyanate-prepolymer To 18 to 42 parts by weight of a diol, and reacting the mixture in a nitrogen atmosphere. The reaction product is distilled under reduced pressure at 60 to 70 ° C to remove the solvent.

Here, the isocyanate may be an aromatic isocyanate, such as toluene-2,4-diisocyanate, methylene diphenyl diisocyanate, 1,5-naphthalene diisocyanate (1,5 (4,6-xylylene diisocyanate), or isophorone diisocyanate as an aliphatic isocyanate, 4,4'-methylene bis (cyclohexyl isocyanate) (4,4'-diisocyanate) Methylenebis (cyclohexyl isocyanate), hexamethylene diisocyanate, meta-tetramethylxylylene diisocyanate, para-tetramethylxylylene diisocyanate and the like can be used .

In addition, the solvent may be methyl ethyl ketone or cyclohexanone.

On the other hand, the diol may be 1,4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol or 1,12-dodecanediol can be used. When the content is less than 18 parts by weight, the molecular weight is low and the prepolymer is formed If the amount is more than 42 parts by weight, the content of the pre-isocyanate group may be lowered and the formation of capsules may be difficult.

On the other hand, when the content of the isocyanate-prepolymer is less than 30 parts by weight, the core material may be crosslinked with the curing material. When the content of the isocyanate-prepolymer exceeds 48 parts by weight, the wall of the capsule may become hard.

In step S300, the prepolymer / core solution is poured into the emulsified solution under a nitrogen atmosphere, and the mixture is stirred at a rate of 100 to 1000 rpm for 30 to 40 minutes while being heated to 30 to 40 DEG C, .

In step S400, curing materials are charged. When the content of the isocyanate-prepolymer is 100 parts by weight, 106 to 227 parts by weight of the curing material is added and the temperature is raised to 65 to 75 占 폚.

The curing agent may be selected from the group consisting of diols, diamines, triamines, tetraamines, and pentamines, each of which has 4 to 10 carbon atoms. Examples of the curing agent include 1,4-butanediol (1, 4-butanediol, 1,6-hexanediol, 1,8-octanediol, 1,10-decanediol or 1,12-Dodecanediol, Glycerol, Ethylenediamine, Diethylenetriamine, Triethylenetetramine or Tetraethylenepentamine, and the like. If the content is less than 106 parts by weight, the capsule may not be formed due to not participating in the crosslinking. If the content exceeds 227 parts by weight, the wall of the capsule may become hard.

The step S500 may include rinsing with distilled water, vacuum filtration, drying at room temperature (25 DEG C) for one day, and further vacuum desiccation in the step of washing, filtering and drying The washing, vacuum filtration and vacuum drying are well known in the art, and various detailed washing, vacuum filtration and vacuum drying apparatuses can be used, which are not described in detail.

On the other hand, if the manufacturing conditions (temperature, time, etc.) for each step are out of the above ranges, microcapsules may not be produced properly.

Hereinafter, the present invention will be described in more detail based on the following examples, but the present invention is not limited by the examples.

1. Preparation of microcapsulated latent curing agent

(Production Example 1)

Preparing an emulsified solution (S100) by mixing 2.5 parts by weight of an emulsifying agent, an Arabic rubber solution, at room temperature (15 to 25 占 폚) with 100 parts by weight of distilled water. 100 parts by weight of isoprene diisocyanate as an isocyanate- The prepolymer / core solution was prepared (S200), and the prepolymer / core solution was poured into the emulsion solution under a nitrogen atmosphere and the mixture was stirred at a speed of 100 rpm for 45 minutes while heating to 30 DEG C (S300) 106 parts by weight of 1,4-butanediol as a starting material was added and the mixture was heated to 65 DEG C (S400), washed with distilled water, vacuum filtered, dried at room temperature (25 DEG C) for 1 day, A capsule-type latent curing agent was prepared.

At this time, the isocyanate-prepolymer was prepared by stirring toluene-2,4-diisocyanate, isocyanate, and methyl ethyl ketone as a solvent at 75 DEG C, and then adding 18 parts by weight of diol 1,8-octanediol to 100 parts by weight of the isocyanate And the reaction was carried out in a nitrogen atmosphere, and the reaction product was distilled under reduced pressure at 60 캜 to remove the solvent.

(Production Example 2)

An emulsified solution (S100) was prepared by mixing 15 parts by weight of an Arabic rubber liquid, which is an emulsifier, at room temperature (15 to 25 DEG C) with respect to 100 parts by weight of distilled water, and 100 parts by weight of meta-tetramethylsilylene diisocyanate, A prepolymer / core solution was prepared (S200) by mixing 48 parts by weight of an isocyanate-prepolymer at 70 DEG C, and the prepolymer / core solution was poured into the emulsion solution under a nitrogen atmosphere and stirred at a speed of 1000 rpm for 45 minutes Then, 227 parts by weight of 1,6-hexanediol as a curing agent was added and the mixture was heated to 75 ° C (S400), washed with distilled water, vacuum filtered, dried at room temperature (25 ° C) for 1 day, Followed by vacuum drying to prepare a microcapsule type latent curing agent.

The isocyanate-prepolymer was prepared by stirring isoprene diisocyanate, which is an isocyanate, and cyclohexanone, which is a solvent, at 85 ° C., and then 42 parts by weight of 1,10-decanediol diol was added to 100 parts by weight of the isocyanate, And the reaction product was distilled under reduced pressure at 70 캜 to remove the solvent.

2. Manufacture of adhesives

(Example 1)

10 parts by weight of nickel particles were dispersed and mixed with 100 parts by weight of the polyurethane adhesive, and then 5 parts by weight of the microcapsulated latent curing agent according to Production Example 1 was mixed to prepare an induction heating adhesive.

(Example 2)

10 parts by weight of nickel particles were dispersed and mixed with 100 parts by weight of the EVA adhesive, and then 5 parts by weight of the microcapsulated latent curing agent according to Production Example 1 were mixed to prepare an induction heating adhesive.

(Example 3)

10 parts by weight of nickel particles were dispersed and mixed with 100 parts by weight of the polyurethane adhesive, and then 5 parts by weight of the microcapsulated latent curing agent according to Production Example 2 was mixed to prepare an induction heating adhesive.

(Example 4)

10 parts by weight of nickel particles were dispersed and mixed with 100 parts by weight of the EVA adhesive, and then 5 parts by weight of the microcapsulated latent curing agent according to Production Example 2 was mixed to prepare an induction heating adhesive.

(Comparative Example 1)

The microcapsule type latent curing agent was not added in the same manner as in Example 1.

(Comparative Example 2)

A microcapsule type latent curing agent was not added in the same manner as in Example 4.

3. Adhesive strength test

(1) Adhesion condition

The adhesive according to the examples and the comparative examples were applied to the adherend or inserted between the specimens to be adhered in a sheet form and then placed in the induction coil and an appropriate magnetic field was applied from the induction heating device to raise the temperature of the adhesive, Next, adhere the adhered material. In this experiment, the induction coil is a circular multi - winding coil with an output voltage of 5 KW and a frequency of 456 Hz. The temperature reaches 100 to 200 ° C. When the temperature is less than 100 ° C, the outer wall of the microcapsule does not melt. When the temperature exceeds 200 ° C, the adherend is deformed.

(2) Adhesion process

Crosslinked rubber (butadiene rubber, styrene-butadiene rubber, ethylene-propylene rubber) and midsole (ethylene vinyl acetate foam) were used as the bonding specimen and the bonding strength was measured in accordance with KSM 3725 (test method for peeling strength of adhesive). The crosslinked rubber of 20 × 100 × 4 mm was washed with distilled water for 5 minutes using an ultrasonic washing machine, and then coated with a rubber surface treatment agent (LOCTITE BONDACE 007) and dried at 60 ° C. for 10 minutes. Next, the 20 × 120 × 11 mm midsole was washed with distilled water for 5 minutes using an ultrasonic washing machine, then coated with a UV curing surface treatment agent (LOCTITE BONDACE P 7-2), dried at 60 ° C. for 10 minutes, Fusion systems cop.) At a speed of 15 m / min. Then, the adhesive (sheet form) according to the above Examples and Comparative Examples was put between the prepared specimens, heated, and then adhered using a pressing roller. After the bonding, the peel strength was measured at a peeling speed of 200 mm / min using a universal tensile tester (UTM, Zwick, Zwick-1435) after 24 hours at room temperature. As shown in Table 1.

Evaluation items Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 State adhesive force
(kgf / cm) 4.4 ~ 4.6 6.2 to 6.4 5.2 ~ 5.4 5.0 to 5.2 3.8 to 4.2 3.4 to 3.6 Adhesion state
(Ward) Midsole
Fracture Midsole
Fracture Midsole
Fracture Midsole
Fracture No change No change

As can be seen from Table 1, the microcapsule type latent curing agent according to the present invention and the microcapsule type latent curing agent prepared by this method break the outer wall of the microcapsule by heat, It is found that the curing performance is higher than that of the conventional induction heating adhesive and the adhesive property is more excellent.

As described above, the process for preparing a microcapsule-type latent curing agent according to the present invention and the microcapsule-type latent curing agent prepared by this process are explained through the above-mentioned preferred embodiments and their excellence is confirmed, It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined in the appended claims.

S100: Step of preparing emulsified solution by mixing emulsifier and deionized water
S200: Separately, the step of preparing the prepolymer / core solution
S300: Step of charging and stirring the prepolymer / core solution into the emulsion solution
S400: Step of injecting curing materials
S500: Cleaning, filtration and drying steps

Claims (8)

A method for producing a microcapsulated latent curing agent,
Mixing the emulsifier and deionized water to prepare an emulsified solution (S100);
Separately, preparing a prepolymer / core solution (S200);
A step (S300) of charging and stirring the prepolymer / core solution into the emulsified solution;
Injecting curing materials (S400); And
Washing, filtering and drying (S500)
In step S100, 2.5 to 15 parts by weight of an emulsifier is mixed with 100 parts by weight of distilled water at room temperature.
In step S200, 30 to 48 parts by weight of an isocyanate-prepolymer is mixed with 100 parts by weight of core materials at 60 to 70 DEG C,
In step S300, the prepolymer / core solution is poured into the emulsified solution under a nitrogen atmosphere, and the mixture is stirred at a speed of 100 to 1000 rpm for 40 to 50 minutes while heating to 30 to 40 DEG C,
In step S400, 106 to 227 parts by weight of a curing material is added to 100 parts by weight of the isocyanate-prepolymer, and the temperature is raised to 65 to 75 DEG C,
The step S500 is performed by rinsing with distilled water, vacuum filtration, drying at room temperature for one day, and further vacuum desiccation,
The isocyanate-prepolymer is prepared by stirring an isocyanate and a solvent at 75 to 85 ° C, adding 18 to 42 parts by weight of diol to 100 parts by weight of the isocyanate, reacting the mixture in a nitrogen atmosphere, distilling off the reaction at 60 to 70 ° C And removing the solvent. The method for producing a microcapsule-type latent curing agent according to claim 1,
delete delete delete delete delete delete A microcapsule-type latent curing agent, which is produced by the manufacturing method according to claim 1.

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