KR102615004B1 - One Component Semi-nonflammable Adhesive and a method for preparing the same - Google Patents

Abstract

This application relates to a one-component semi-non-flammable adhesive and a continuous manufacturing method thereof. According to the present invention, not only does it conveniently replace the multi-step process of manufacturing a urethane adhesive and then adding and mixing various flame retardant and non-flammable additives, but also prevents contact with air. It is effective in providing a method for avoiding and continuous manufacturing.

Description

One-component semi-nonflammable adhesive and its manufacturing method {One Component Semi-nonflammable Adhesive and a method for preparing the same}

The present invention relates to a one-component semi-non-combustible adhesive and a method of manufacturing the same. More specifically, it satisfies the 'semi-non-combustible material' grade (flame retardant grade 2) notified by the Ministry of Land, Infrastructure and Transport, and is used for fire doors, heat-insulating fire doors, flooring, building panels, etc. It relates to a one-component semi-non-combustible adhesive that satisfies all of the semi-non-combustibility, workability, product stability, and storage stability required for manufacturing non-combustible or non-combustible building materials and can be easily and continuously produced at low cost and its manufacturing method.

Urethane adhesives have excellent interfacial adhesion, flexibility, strength, and impact resistance, and are superior in constructability and productivity compared to other adhesives such as epoxy and acrylic.

In addition, it is advantageous for bonding structures with complex shapes and exhibits excellent adhesion to various resins such as paper, plywood, steel plate, and synthetic resin.

Accordingly, urethane adhesives are used in various fields as architectural adhesives, including various doors and building panels.

Urethane adhesives come in one-component and two-component types. The two-component type is inconvenient in that the base material and hardener must be mixed before use, so the one-component type is mainly used in the field.

One-component urethane adhesive is a prepolymer with viscosity and an isocyanate group at the end. When used as an adhesive, moisture from the outside acts as a catalyst, causing urethane reaction and foaming to complete curing, that is, adhesion.

The foaming properties of one-component urethane adhesive are especially useful when manufacturing doors, fire doors, and heat-insulating fire doors using honeycomb structures. For example, although the contact area between the internal honeycomb structure and the steel plate is not large, the foaming of the adhesive allows the structure to be firmly joined.

In addition, in the manufacture of heat-insulating fire doors using glass wool as an interior material, the one-component urethane adhesive achieves adhesion by penetrating into the glass wool tissue due to its self-foaming properties when bonding the coarse-surfaced glass wool to the steel plate shell, providing excellent adhesive performance. indicates. This is also true in the manufacturing of building boards that bond urethane boards and steel plates.

Meanwhile, adhesives used in the manufacture of building materials that require fire resistance, such as fire doors, heat-insulating fire doors, semi-non-combustible flooring, and semi-non-combustible urethane boards for construction, are either non-flammable (flame retardant grade 1) or semi-non-flammable (flame retardant grade 2) according to the standards of the Ministry of Land, Infrastructure and Transport. ) must meet the grade.

Among these, products sold in the market as non-combustible are often actually semi-non-combustible. Non-combustible means that it does not combust by flame like metal or ceramics and does not generate flame or gas like a general fire.

Most commercially available non-flammable adhesives are made by adding a small amount of organic compounds or organic adhesives to a solution of an ionic inorganic compound such as water glass. Products claiming to be non-flammable adhesives require relatively high temperatures and long periods of time for drying, and this is because they are used as a dispersion medium for non-flammable adhesives. This is because water is usually used.

When water evaporates from non-flammable adhesives, a very hard inorganic solid remains, and this solid can exhibit constant adhesion as long as it remains dry. However, due to the mechanism in which water evaporates and then dissolves through moisture reabsorption, deformation and peeling of the structure easily occur in the case of fire doors and building boards, etc., so in most cases, they cannot be used in the manufacture of buildings that require a long lifespan.

The inorganic components that make up the non-combustible adhesive are only physically dried at temperatures below 100°C, which is the process temperature applied to the adhesion process using general organic adhesives when manufacturing fire doors or building structures, but the chemical structure of the non-combustible composition or inorganic additive is not modified. I don't lose. For example, cement is a chemical change in inorganic materials that reacts with water and hardens even at temperatures lower than room temperature (curing stage), but it requires a long time to solidify and its adhesion is also unsatisfactory, so it cannot be applied to the manufacture of fire doors. Hardening of most inorganic materials requires solidification above hundreds of degrees Celsius, as is commonly seen in ceramics manufacturing.

Semi-non-flammable adhesives are a mixture of organic and inorganic flame retardants and commercially available organic adhesives, and most adhesives combine the non-flammable or semi-non-flammable characteristics of organic flame retardants or inorganic flame retardants with the adhesive characteristics of organic components. In general, organic flame retardants contain large amounts of halogen elements such as bromine and chlorine, phosphorus, nitrogen, and other elements. Nevertheless, organic flame retardants have limitations in demonstrating quasi-non-flammable performance. Therefore, in order to manufacture an adhesive with semi-non-flammable properties, it is necessary to add an inorganic flame retardant in addition to an organic flame retardant.

According to Korean Patent Publication No. 10-2019-0059733, a related prior art, discloses a technology for producing a semi-non-flammable urethane adhesive by adding a mixture of organic and inorganic flame retardants to a previously prepared one-component urethane adhesive. However, it is cumbersome to manufacture as it consists of two steps: the mixing process of organic and inorganic flame retardants, and the subsequent mixing process of the flame retardant mixture and adhesive, and the mixing process or subsequent foaming of the final semi-non-combustible adhesive product due to contact with moisture during transportation of raw materials and work. There is a high risk that a hardening reaction will occur. To prevent this, the entire mixing and reaction process must be carried out in a sealed state, but it is not easy to maintain complete sealing from the reactor or mixer to the final canned product.

In order to solve the above problems, this application seeks to provide a one-step process for manufacturing a semi-non-flammable one-component urethane adhesive through a continuous reaction from a sealed reactor or mixer to the packaging container of the final product.

In detail, polyol, flame retardant and solvent are added to one of the two mixing tanks equipped with a stirrer and stirred, diisocyanate is added to the other tank, and a certain amount is sent from each of the two tanks to the mixing head in a short period of time at high speed. After mixing, the process of filling and sealing the mixture into a packaging can is continuously performed to produce a one-component semi-non-flammable adhesive.

According to the present invention, the organic-inorganic mixture is mixed in a sealed state to prevent the inflow of moisture, and continuous manufacturing is possible from mixing raw materials to product packaging, resulting in stable and high productivity, and a one-component semi-non-combustible moisture-curing type. Urethane adhesive can be manufactured.

The present invention is to solve the above problems,

A one-component semi-non-flammable adhesive is provided, which has an NCO index of 1.1 to 2.0 in the urethane bond and has semi-non-flammable performance.

The urethane bond may be obtained by mixing a mixture of organic-inorganic flame retardant system polyol:diisocyanate at a weight ratio of 5 to 7:1 (organic-inorganic flame retardant system polyol:diisocyanate) at an average speed of 200 g per second.

The organic-inorganic flame retardant system polyol is 30 to 50% by weight of a polyol selected from PEG and PPG and having a molecular weight in the range of 1000 to 5000 g/mol; 15 to 25% by weight of an inorganic flame retardant selected from aluminum hydroxide, magnesium hydroxide and zinc borate and having an average particle size of 10㎛ or less; 10 to 15% by weight of an organic flame retardant selected from one or more of Tris(chloroisopropyl)phosphate (TCPP), Triethylphosphate (TEP), Trichloroethylphosphate (TCEP) and ammonium phosphate; Dispersant 0.1-0.5% by weight; Catalyst 0.01-1.0% by weight; And it may be provided from 3 to 10% by weight of solvent.

The dispersant is one or more selected from ethoxylated aliphatic alcohol, polyethylene oxide carboxylic ester, polyethylene glycol ester, fatty acid sorbitol ester, fatty acid glycol ester, phosphoric ester of polyethoxylated alkyl phenol, and sulfated fatty acid ester. You can.

The catalyst may be one or more types selected from dibutyltin dilaurate (DBTDL) and dimethylethanolamine (DMEA).

The solvent may be one or more selected from MEK, MIBK, and DMC (dimethyl carbonate).

The diisocyanate may be one or more types selected from MDI, PMDI, and TDI, and may have an average molecular weight of 380 g/mol and an average number of NCOs per molecule of 2.7.

The mixing ratio of the system polyol and diisocyanate is such that the NCO index of the urethane bond is 1.1 to 2.0, and the one-component semi-non-flammable adhesive may be a moisture-curing urethane adhesive.

In addition, the present invention,

30 to 50% by weight of a polyol selected from PEG and PPG and having a molecular weight in the range of 1000 to 5000 g/mol in one of the two mixing tanks equipped with a stirrer; 15 to 25% by weight of an inorganic flame retardant selected from aluminum hydroxide, magnesium hydroxide and zinc borate and having an average particle size of 10㎛ or less; 10 to 15% by weight of an organic flame retardant selected from one or more of TCPP, TCEP, TEP and ammonium phosphate; Dispersant 0.1-0.5% by weight; And adding 3 to 10% by weight of solvent and stirring to prepare an organic-inorganic flame retardant system polyol, and adding diisocyanate to the remaining tank;

Performing high-speed mixing in a short time while transferring the organic-inorganic flame retardant system polyol and diisocyanate from the tanks to a mixing head so that the NCO index of the urethane bond is 1.1 to 2.0; and

A method for manufacturing a one-component semi-non-flammable adhesive is provided, characterized in that the step of filling and sealing the high-speed mixed mixture into a packaging can containing 0.01 to 1.0% by weight of catalyst is carried out continuously without contact with moisture.

In addition, the present invention

A substrate selected from paper, plywood, steel plate, and synthetic resin film; and

Contains a foamed elastic film,

The foamed elastic film is obtained by applying the above-described one-component urethane adhesive onto the substrate and then curing it at room temperature (25°C).

The one-component urethane adhesive provides an adhesive article comprising a one-component urethane adhesive, wherein the one-component urethane adhesive is a milky white suspension having a viscosity (25° C.) of 1500 to 1600 cps.

According to the present invention, instead of manufacturing a semi-non-flammable adhesive by adding a separate flame retardant to a pre-prepared urethane adhesive, a simple process of mixing system polyol and diisocyanate to which an organic-inorganic flame retardant is added at high speed, discharging and placing it in a container is carried out with moisture and One-component semi-non-flammable adhesive can be manufactured safely and continuously while avoiding contact with the product.

Figure 1 shows a schematic diagram of sealed continuous production of a one-component semi-non-combustible adhesive according to the present invention.
Figure 2 is a test report showing the application of the one-component semi-non-flammable adhesive according to the present invention to a glass door.

Hereinafter, the present invention will be described in detail.

According to one embodiment of the present invention, it is possible to provide a one-component semi-non-flammable adhesive having an NCO index of 1.1 to 2.0 in the urethane bond and semi-non-flammable performance.

The urethane bond may be obtained by mixing a mixture of organic-inorganic flame retardant system polyol:diisocyanate at a weight ratio of 5 to 7:1 (organic-inorganic flame retardant system polyol:diisocyanate) at an average speed of 200 g per second.

The organic-inorganic flame retardant system polyol is 30 to 50% by weight of a polyol selected from PEG and PPG and having a molecular weight in the range of 1000 to 5000 g/mol; 15 to 25% by weight of an inorganic flame retardant selected from aluminum hydroxide, magnesium hydroxide and zinc borate and having an average particle size of 10㎛ or less; 10 to 15% by weight of an organic flame retardant selected from one or more of TCPP, TCEP, TEP and ammonium phosphate; Dispersant 0.1-0.5% by weight; Catalyst 0.01-1.0% by weight; And it may be provided from 3 to 10% by weight of solvent.

The dispersant is one or more selected from ethoxylated aliphatic alcohol, polyethylene oxide carboxylic ester, polyethylene glycol ester, fatty acid sorbitol ester, fatty acid glycol ester, phosphoric ester of polyethoxylated alkyl phenol, and sulfated fatty acid ester. You can.

The catalyst may be one or more types selected from dibutyltin dilaurate (DBTDL) and dimethylethanolamine (DMEA).

The solvent may be one or more selected from MEK, MIBK, and DMC (dimethyl carbonate).

The diisocyanate may be one or more types selected from MDI, PMDI, and TDI, and may have an average molecular weight of 380 g/mol and an average number of NCOs per molecule of 2.7.

The mixing ratio of the system polyol and diisocyanate is such that the NCO index of the urethane bond is 1.1 to 2.0, and the one-component semi-non-flammable adhesive may be a moisture-curing urethane adhesive.

According to another embodiment of the present invention, in one of the two mixing tanks equipped with a stirrer, 30 to 50% by weight of a polyol selected from PEG and PPG and having a molecular weight in the range of 1000 to 5000 g/mol; 15 to 25% by weight of an inorganic flame retardant selected from aluminum hydroxide, magnesium hydroxide and zinc borate and having an average particle size of 10㎛ or less; 10 to 15% by weight of an organic flame retardant selected from one or more of TCPP, TCEP, TEP and ammonium phosphate; Dispersant 0.1-0.5% by weight; Catalyst 0.01-1.0% by weight; And adding 3 to 10% by weight of solvent and stirring to prepare an organic-inorganic flame retardant system polyol, and adding diisocyanate to the remaining tank; Performing high-speed mixing in a short time while transferring the organic-inorganic flame retardant system polyol and diisocyanate from the tanks to a mixing head so that the NCO index of the urethane bond is 1.1 to 2.0; and filling and sealing the high-speed mixed mixture into a packaging can. A method for manufacturing a one-component semi-non-flammable adhesive can be provided, characterized in that the steps are carried out continuously without contact with moisture.

According to another embodiment of the present invention, a substrate selected from paper, plywood, steel plate, and synthetic resin film; and a foamed elastic film, wherein the foamed elastic film is obtained by applying the above-described one-component urethane adhesive to the substrate and then curing it at room temperature (25°C). The one-component urethane adhesive has a viscosity (25°C) of 1500. to 1600 cps. It may be a milky white suspension.

Hereinafter, the present invention will be examined in more detail with reference to the drawings.

Figure 1 below is a schematic diagram of the closed continuous production of a one-component semi-non-combustible adhesive according to the present invention.

According to Figure 1 below, a certain unit amount from two tanks containing the organic-inorganic flame retardant system polyol and diisocyanate is transferred to the mixing head, mixed at high speed, and then discharged directly into the packaging container to fill it.

Here, the organic-inorganic flame retardant system polyol may be composed of polyol, inorganic flame retardant, organic flame retardant, dispersant, urethane reaction catalyst, and solvent.

The organic-inorganic flame retardant system polyol is, for example, 30 to 50% by weight of polyol, 15 to 25% by weight of inorganic flame retardant, 10 to 15% by weight of organic flame retardant, 0.1 to 0.5% by weight of dispersant, 0.01 to 1.0% by weight of catalyst, and solvent. It consists of 3 to 10% by weight, and the equivalent ratio of system polyol and diisocyanate may be OH: NCO = 1.0:1.1 to 1.0:1.3.

Finally, the polyol and isocyanate in the mixture filled in the container gradually undergo a urethane reaction to form polyurethane. At this time, the equivalent weight of isocyanate is relatively higher than the OH group of polyol, so an isocyanate group is present at the end of the urethane polymer chain.

The isocyanate group at the end of the urethane chain absorbs moisture or moisture when the adhesive is exposed to the outside, causing a curing reaction and simultaneous foaming, enabling various types of interfacial adhesion.

The head mixing and discharging method of the system polyol and isocyanate is a method mainly used to manufacture intermittent urethane panels.

In this case, a certain amount of system polyol, which is a mixture of polyol, curing catalyst, foaming agent, flame retardant, and other additives, and diisocyanate (mainly MDI) are transferred from two containers to the mixing head and mixed at high speed for a few seconds and then mixed under strong pressure. By discharging and foaming, the inside of the panel guide is filled with foamed urethane between presses. The polyol used at this time is a polyol containing three or more OH groups to induce a crosslinking reaction.

The polyol, which is the main component of the organic-inorganic flame retardant system polyol in the present invention, uses PEG or PPG with two OH groups, and no foaming agent is used.

Therefore, after mixing at high speed for a short period of time in the mixing head, polyol and diisocyanate have a two-dimensional chain structure rather than a three-dimensional structure through a urethane reaction. As a viscous liquid, it has adhesive properties and hardens only after contact with moisture outside the container. A slight foaming occurs and a firm bond is created between the adherends.

Polyol may be, for example, polyethylene glycol (PEG), polypropylene glycol (PPG), or a mixture thereof.

For example, the average molecular weight of the polyol is preferably 1,000 to 5,000 g/mol. If the molecular weight is too large, it is solid at room temperature and is not easy to handle, and the viscosity of the adhesive may be too high. If the molecular weight is too low, the adhesive may lack adhesiveness. Otherwise, the intensity may decrease.

As a specific example, PEG 2,000 or PEG 3,000 can be used. Here, when PEG 3,000 is used compared to PEG 2,000, longer polymer chains are obtained, resulting in an adhesive with relatively high viscosity. PPG may be used instead of PEG, or PEG or PPG of various molecular weights may be used, or mixtures thereof may be used. However, a molecular weight that is too low can reduce the viscosity and adhesion of the adhesive, while a molecular weight that is too high can cause the viscosity to be too high and reduce the quality of the product. Therefore, the molecular weight of PEG or PPG is preferably 1,000 to 4,000, preferably 2,000 to 3,000.

The inorganic flame retardant may be one or more selected from aluminum hydroxide, magnesium hydroxide, and zinc borate. Zinc borate is known to have a smoke suppression effect in addition to a flame retardant effect, but it has the disadvantage of being expensive.

Since the inorganic flame retardant is an insoluble powder, the smaller the particle size, the better. However, as the cost tends to increase as the particle size decreases, it is appropriate to use one with an average particle size of 10 ㎛ or less for the purpose of the present invention.

Organic flame retardants can be used as a variety of flame retardants used to manufacture architectural urethane boards.

As a specific example, liquid flame retardants such as TCPP, TCEP, and TEP or solid flame retardants such as ammonium phosphate and melamine cynurate may be used. At this time, the more solid flame retardants there are compared to liquid flame retardants, the better the semi-non-flammable properties are, which lowers the heating value of the adhesive and reduces the emission of harmful gases.

Meanwhile, fire doors, heat-insulating fire doors, and architectural panels that require semi-non-combustible adhesives should not easily collapse in the event of a fire, but Styrofoam or general adhesives catch fire easily in the event of a fire, generate a large amount of smoke, and can easily melt and flow away due to heat. You can.

Adhesives used in the manufacture of building materials should not flow down easily, and therefore, it is desirable that the ingredients of the adhesive form solid char or leave an incombustible mineral in the event of a fire, so it is good for the flame retardant to contain an inorganic flame retardant. However, if the content of the inorganic flame retardant is excessive, the viscosity of the organic-inorganic flame retardant system polyol increases, making it difficult to manufacture, or the adhesion of the final one-component adhesive may decrease. Therefore, the content of the inorganic flame retardant is preferably less than 30% by weight.

Inorganic flame retardants are simply dispersed rather than dissolved inside the adhesive, and their specific gravity is higher than that of organic materials. Therefore, as time passes, the inorganic flame retardant settles to the bottom, and caking may occur. This phase separation not only reduces the quality of the adhesive, but can also cause serious problems in distribution and storage of the product.

Therefore, it is important to maintain product quality for a long time by preventing precipitation of inorganic components and minimizing phase separation, and for this purpose, the use of a dispersant is necessary.

Dispersants include anionic, cationic, and nonionic dispersants. Since the organic-inorganic flame retardant system polyol of the present invention is a neutral mixture, nonionic dispersants with excellent compatibility are preferred.

Examples include Ethoxylated aliphatic alcohol, Polyethylene oxide Carboxylic ester, Polyethylene glycol ester, Fatty acid sorbitol ester, Fatty acid glycol ester, Phosphoric ester of polyethoxylated alkyl phenol, Sulfated fatty acid ester, etc.

In the present invention, the production process is completed by efficiently mixing the organic-inorganic flame retardant system polyol and diisocyanate, then discharging them into a container and sealing it. Specifically, the adhesive product is finally completed as the urethane reaction proceeds between the polyol and the isocyanate in the container to form polyurethane. At this time, the container is stored at room temperature and a urethane reaction catalyst is added to complete the reaction without external heating.

The urethane reaction catalyst may be dimethylethanolamine (DMEA), dibutyltindilaurate (DBTDL), or an amine-based catalyst. A variety of amine-based catalysts can be used, but DMEA is preferred as a commonly used urethane catalyst, and its amount is preferably less than 1.0% by weight. It is recommended that the urethane reaction in the container proceed slowly over a period of about a day, because excessive use of a catalyst speeds up the reaction and generates additional reaction heat, which may cause internal pressure to be applied to the container, which may cause damage or bursting.

Solvent or solvent is necessary to control the final viscosity of the adhesive. The solvent is not limited as long as it is compatible with the adhesive and is not reactive. For example, ketones such as MEK and MIBK or dimethyl carbonate (DMC) can be used. .

In particular, DMC, which is classified as an eco-friendly catalyst and has recently been recommended for use, is preferable. The solvent content can be adjusted depending on the purpose of the adhesive, but if it exceeds 10%, the viscosity becomes too low, which is not desirable.

According to another embodiment of the present invention, the system polyol and diisocyanate stored in a separate stirring tank are mixed by injecting a set amount per unit time into a mixing head, and then the mixture is placed in a packaging container (e.g., a 20L can) and sealed, Through the aging process, one-component semi-non-flammable urethane adhesive can be manufactured continuously while avoiding contact with moisture.

Here, the organic-inorganic flame retardant system polyol composition ratio is 30 to 50% by weight of polyol, 15 to 25% by weight of inorganic flame retardant, 10 to 15% by weight of organic flame retardant, 0.1 to 0.5% by weight of dispersant, 0.01 to 1.0% by weight of catalyst, and 3 to 3% of solvent. It consists of 10% by weight, and the diisocyanate may be one of MDI, TDI, or a mixture thereof. In particular, it is preferable that the catalyst is not added to the mixing step, but is added to the packaging container in the subsequent sealing step.

In addition, the mixing ratio of the organic-inorganic flame retardant system polyol and diisocyanate is, for example, the ratio of the OH equivalent of the polyol to the NCO equivalent of the isocyanate is 1:1.1 or more, specifically 1:1.1 to 2.0, 1:1.1 to 1.5, 1:1.1 to 1.3. , or it may be a weight ratio of 1:1.1 to 1.2.

Hereinafter, this invention will be described in more detail through examples of the invention. However, this invention is not limited by the examples and comparative examples.

Example 1: System polyol preparation example 1

PEG2000 25% by weight, PEG3000 25% by weight, aluminum hydroxide (average particle size 8 ㎛) 25% by weight, TCPP 18% by weight, DMC 6.7% by weight, Phosphoric ester of polyethoxylated alkyl phenol 0.2% by weight, DBTDL 0.1% by weight; It was placed in an installed sealed mixer and mixed evenly.

Example 2: System polyol preparation example 2

In Example 1, the same process as Example 1 was repeated except that PPG2000 was used instead of PEG2000.

Example 3: Preparation Example 1 of one-component semi-non-flammable adhesive

PMDI (average molecular weight 380, average number of NCOs per molecule 2.7) was added to a separate mixer equipped with a stirrer, and then system polyol (Example 1): PMDI was added to the mixing head connected to the two mixers in a ratio of 6:1 by weight at a pressure of 7 kgf. It was injected, mixed at high speed, and then injected into a 20L can.

At this time, the discharge speed was an average of 200 g per second.

The mixture in the can was left at room temperature for more than 24 hours to obtain the final adhesive.

The obtained adhesive was a milky white suspension with a viscosity of 1500 cps at 25°C.

Example 4: Preparation example 2 of one-component semi-non-flammable adhesive

The same process as Example 3 was repeated except that system polyol (Example 2) was used instead of system polyol (Example 1).

The obtained adhesive was a milky white suspension with a viscosity of 1600 cps at 25°C.

Test Example 1: Elastic foam film manufacturing test 1

When the one-component semi-non-flammable adhesive obtained in Example 3 was applied to paper and left indoors at 25 degrees, it was confirmed that it foamed and cured into a slightly elastic film within 60 minutes.

Test Example 2: Elastic foam film manufacturing test 2

When the one-component semi-non-flammable adhesive obtained in Example 4 was applied to paper and left indoors at 25 degrees, it was confirmed that it foamed and cured into a film with some elasticity within 60 minutes.

Test Example 3: Storage Stability Test 1

As a result of visual observation after leaving the one-component semi-incombustible adhesive obtained in Example 3 at room temperature for 4 weeks, no phenomenon of phase separation due to inorganic particles settling to the bottom of the container was found.

After 3 months, it was visually confirmed that some inorganic particles had settled, but it was confirmed that it returned to a uniform suspension with slight agitation.

Test Example 4: Storage Stability Test 2

As a result of visual observation after leaving the one-component semi-incombustible adhesive obtained in Example 4 at room temperature for 4 weeks, no phenomenon of phase separation due to inorganic particles settling to the bottom of the container was found.

After 3 months, it was visually confirmed that some inorganic particles had settled, but it was confirmed that it returned to a uniform suspension with slight agitation.

Test Example 5: Semi-non-flammable performance test of semi-non-flammable adhesive

The semi-non-flammable performance of the semi-non-flammable adhesive prepared in Example 3 was tested according to the KS F ISO 5660-1 and KS F 2271 test methods. The test environment was conducted at a temperature of (20 ± 3) ℃ and humidity (50 ± 15) % RH. The test result was 'suitable for semi-non-combustible materials' and details are shown in Table 1 below.

As shown in Table 1 above, in the case of the three types of test specimens according to the present invention, it was confirmed that the total amount of heat released and the time exceeding 200 kW/m2 met the standards.

Furthermore, it can be seen that the observation results of cracks, holes, and melting penetrating the test specimen and the gas hazard, which can be an important criterion for semi-non-combustible applications, are also appropriate.

Test Example 6: Fire door performance test using semi-non-combustible adhesive

A performance test was conducted on a fire door using the semi-non-combustible adhesive prepared in Example 3. A fire door performance test was requested from the Hongcheon-based Construction Fire and Energy Research Institute, and the fire resistance of fire doors was tested in accordance with the Ministry of Land, Infrastructure and Transport Notification No. 2016-193 "Standards for Automatic Fire Shutters and Fire Doors" for three types of fire resistance performance, smoke blocking performance, and door sets. The test method was KS F 2268-1: 2014, the fire door gap test method was KS F 2846:2013, and the door set was tested according to KS F-3109:2016.

Specific test results can be found in Figure 2 on the glass door test report.

As shown in Figure 2, all items of fire resistance test (non-insulation), insulation test (air leakage at 25 Pa), and door set (50N opening/closing force, 100,000 opening/closing repeatability, torsional strength, vertical load strength, impact resistance) It was confirmed that the performance conditions announced by the Ministry of Land, Infrastructure and Transport were satisfied.

Claims (10)

delete delete delete delete delete delete delete delete Providing a one-step process for manufacturing a semi-non-combustible one-component urethane adhesive through a continuous reaction from a sealed reactor or mixer to a packaging container for the final product;
30 to 50% by weight of a polyol selected from PEG and PPG and having a molecular weight in the range of 1000 to 5000 g/mol in one of the two mixing tanks equipped with a stirrer; 15 to 25% by weight of an inorganic flame retardant selected from aluminum hydroxide, magnesium hydroxide and zinc borate and having an average particle size of 10㎛ or less; 10 to 15% by weight of an organic flame retardant selected from one or more of TCPP, TCEP, TEP and ammonium phosphate; Dispersant 0.1-0.5% by weight; And adding 3 to 10% by weight of solvent and stirring to prepare an organic-inorganic flame retardant system polyol, and adding diisocyanate to the remaining tank;
Performing high-speed mixing in a short time while transferring the organic-inorganic flame retardant system polyol and diisocyanate from the tanks to the mixing head so that the NCO index of the urethane bond is 1.1 to 2.0; and
A method for manufacturing a one-component semi-non-flammable adhesive, characterized in that the step of filling and sealing the high-speed mixed mixture into a packaging can containing 0.01 to 1.0% by weight of catalyst is carried out continuously without contact with moisture.
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