KR20090016809A - Process for preparing flame retardant one component inorganic adhesive and one component inorganic adhesive prepared thereby - Google Patents

Abstract

A one-part inorganic adhesive is provided to ensure excellent flame retardancy and to prevent the generation of a volatile organic compound due to the organic solvent by using soluble materials and inorganic materials as a main material. A method for manufacturing a one-part inorganic adhesive comprises a step for mixing sodium silicate liquid 40-98 parts by weight and water soluble polymer emulsion 0-50 parts by weight; a step for mixing a material for phase stability 0.1-50 parts by weight and viscosity modifier 0.1-50 parts by weight; and a step for defoaming the mixture.

Description

TECHNICAL FOR PREPARING FLAME RETARDANT ONE COMPONENT INORGANIC ADHESIVE AND ONE COMPONENT INORGANIC ADHESIVE PREPARED THEREBY}

The present invention relates to a method for preparing a one-component inorganic adhesive having flame retardancy, and to a one-component inorganic adhesive prepared by the same. More particularly, by adding a water-soluble polymer emulsion, a substance for phase stability, and a viscosity modifier to liquid sodium silicate. The present invention relates to an environmentally friendly inorganic adhesive and a method for producing the same, which exhibit excellent flame retardancy and are particularly excellent in storage stability.

Until now, most adhesives have been prepared in the form of using a volatile organic compound as a solvent or formaldehyde, isocyanate and the like as a curing agent. However, these volatile organic compounds and curing agents such as formaldehyde and isocyanate have been pointed out as a problem because they can have a fatal adverse effect on the human body.

In order to solve this problem, an emulsion-type water-soluble polymer adhesive that uses water as a solvent instead of a volatile organic compound and does not use a curing agent has been developed. However, it also has no flame retardancy and emits a large amount of various poisonous gases as it is burned in a fire. Caused it.

In general, sodium silicate is called sodium metasillica, sesqui-sillicate, ortho-sillicate, etc., depending on the ratio of Na ₂ O to SiO ₂ . More than one type of sodium silicate is commercially available. In particular, liquid sodium silicate, called water glass, is a transparent solution showing viscous alkalinity. The liquid sodium silicate defined by the Korean Industrial Standard (KSM1415) is divided into several species according to its molar ratio and specific gravity.

Type 1 2 types 3 types 4 types Specific gravity (20 ℃) 1.690 or higher 1.590 or more 1.380 or more 1.260 or more Water insoluble content (%) 0.2 or less 0.2 or less 0.2 or less 0.2 or less Sodium oxide (Na ₂ O) (%) 17-18 14-15 9-10 6 to 7 Silicon Dioxide (SiO ₂ ) (%) 36-38 34-36 28-30 23-25 Iron oxide (III) (Fe ₂ O ₃ ) (%) 0.05 or less 0.05 or less 0.03 or less 0.03 or less

This liquid sodium silicate has inherent flame retardancy and adhesive strength, and is used as an adhesive of various materials. The liquid sodium silicate is widely used because of its simple manufacturing process, simple equipment, and low production cost than other adhesives. In particular, unlike the organic adhesives before, during and after the manufacturing process has the advantage that does not cause pollution has attracted the spotlight in terms of environmental friendliness.

However, when sodium silicate is used alone as an adhesive, it has a weakness in water resistance, such as a decrease in adhesion strength when exposed to moisture or moisture in the air. It is easy to bend when bent (면) has a characteristic that represents a big problem in terms of flexibility.

In connection with the above problems, Japanese Patent Laid-Open No. 61-252395 and Japanese Patent Laid-Open No. 5-32931 produce an intensifier or coating agent by mixing a tacky organic compound such as water-soluble polyvinyl alcohol with sodium silicate. The technique is introduced, and Korean Laid-Open Patent Publication No. 1999-0070515 and Laid-Open Patent Publication No. 1999-0070516 disclose a technique of mixing ethylene vinyl acetate, acrylic resin, and the like with sodium silicate, but the above technique. The adhesive produced by the present invention has a problem in that its storage stability is significantly lowered, causing problems in the distribution process and degrading its value as a product.

Accordingly, the present inventors have made great efforts to solve the above problems, and thus, the present inventors have invented a one-part inorganic adhesive having a markedly improved storage stability.

Accordingly, the present invention is to solve the above problems, and mixed liquid sodium silicate with a certain amount of an aqueous polymer emulsion, a material for phase stability, a viscosity modifier in an appropriate ratio, and if necessary, volatile through heat treatment at an appropriate temperature Solving the problems of human and environmental hazards due to the use of organic compounds, formaldehyde, isocyanate and other hardening agents, it can express excellent flame retardancy, and in particular, an eco-friendly flame retardant adhesive with excellent storage stability and a one-component type by the manufacturing method It is an object to provide an inorganic adhesive.

In order to achieve the above object, according to the present invention, in the method for preparing a one-component inorganic adhesive having flame retardancy, stirring by mixing 40 to 98 parts by weight of liquid sodium silicate and 0 to 50 parts by weight of a water-soluble polymer emulsion, phase stability There is provided a method for producing a one-component inorganic adhesive comprising the steps of mixing and stirring 0.1 to 50 parts by weight of a material for degassing the mixture.

At this time, when using less than 40 parts by weight of liquid sodium silicate, there is a problem that the flame retardancy and adhesive strength is lowered, when using more than 98 parts by weight has a disadvantage that can not overcome the problem when using liquid sodium silicate alone. If the water-soluble polymer emulsion is used in excess of 50 parts by weight can not represent the proper viscosity of the finished product, there is a problem that the price competitiveness of the product is lowered, and if it contains less than 0.1 parts by weight of material for phase stability affects the phase stability If not included, if included in more than 50 parts by weight rather adversely affects the phase stability and there is a problem that can cure the adhesive.

In addition, according to the present invention in order to achieve the above object, the production of a one-pack inorganic inorganic adhesive further comprising the step of mixing and stirring additionally 0.1 to 50 parts by weight of a viscosity modifier to the mixture in order to adjust the viscosity and improve the feeling of use of the adhesive A method is provided.

In this case, when the viscosity modifier is contained in less than 0.1 parts by weight, it does not actually exhibit a viscosity control ability, if it exceeds 50 parts by weight can lose the function as an adhesive due to excessive viscosity rise. Therefore, the viscosity modifier may be arbitrarily adjusted according to the nature of the product.

In addition, according to the present invention, in order to achieve the above object, when calcium carbonate is used as the viscosity modifier, the step of heating to 60 ℃ to 80 ℃ to maintain for 5 to 30 minutes and then cooling to 20 ℃ to 30 ℃ There is further provided a method for producing a one-part inorganic adhesive.

At this time, the method and the order of each component of the adhesive are mixed and stirred and heat treated are not limited as described above. For example, after putting the liquid sodium silicate into the reactor, the material and viscosity modifier for phase stability are first mixed and then mixed and stirred while putting it into the reactor, or the viscosity modifier is first mixed with the liquid sodium silicate and stirred. After the heat treatment, the aqueous polymer emulsion may be prepared by further mixing and stirring.

In addition, according to the present invention in order to achieve the above object, there is provided a one-component inorganic adhesive, flame retardant and greatly improved storage stability produced by the above production method.

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

As described above, sodium silicate exists in various forms according to the molar ratio of Na ₂ O and SiO ₂ constituting the molecule, but the liquid sodium silicate used in the present invention may be any of those specified in the Korean Industrial Standard (KSM1415). It is preferable to mix and use sodium silicate. In addition, when calcium silicate and lithium silicate are used in combination with the above sodium silicate, a better flame retardant effect can be expected.

The aqueous polymer emulsion used with the above sodium silicate may be an emulsion such as polyvinyl alcohol, polyvinylacetate, ethylene vinyl acetate, acryl, and the like, and is not limited to the kind of emulsion mentioned.

In addition, as the material for phase stability used with the sodium silicate described above, baking soda, calcium chloride, kaolin, sodium silicate, magnesium silicate, potassium chloride, magnesium chloride, bentonite, silica, gypsum, zeolite, potassium cement, etc. may be used. Can be.

In addition, calcium carbonate, talc, aluminum oxide, alumina, loess, glass powder and other fillers may be used as viscosity modifiers used for viscosity control and a feeling of use of the product, and in this case, less reactive fillers for viscosity and phase stability It is preferable to use.

Moreover, when calcium carbonate is used as a viscosity modifier in this invention, satisfactory stability is obtained also by heating to 60 degreeC-80 degreeC, and holding for 5 to 30 minutes. Therefore, in this case, it is possible to achieve the purpose of improving the stability only by adding a small amount of the material for the phase stability.

As described above, the present invention is excellent in flame retardancy, using water-soluble materials and inorganic materials as the main raw materials, there is no generation of volatile organic compounds due to organic solvents in use, does not generate VOC compounds even after use, especially storage stability is greatly It is a useful invention to provide an adhesive that is improved and a method of making the same.

Hereinafter, the present invention will be described in more detail with reference to the following Examples, Comparative Examples, and Experimental Examples, but the scope of the present invention is not limited to the following examples.

<Example 1>

22 parts by weight of two kinds of sodium silicate and 40 parts by weight of sodium silicate are mixed in a high-viscosity vacuum mixer (KSM1415) and mixed well, 35 parts by weight of calcium carbonate, 1.5 parts by weight of silica, 0.5 parts by weight of calcium chloride powder and silica Mix 1 part by weight of sodium fluoride first and stir slowly under vacuum (more than 700mmHg) with a high viscosity vacuum mixer. At this time, the paddle mixer and the high speed dissolver mixer are operated simultaneously so that they are mixed sufficiently uniformly at the beginning. Finally, after completely stirring, the dissolver mixer was stopped and the paddle mixer was operated to maintain a degree of vacuum of at least 740 mmHg and completely degassed to prepare an adhesive.

<Example 2>

78 parts by weight of two kinds of sodium silicate specified in Korean Industrial Standard (KSM1415) were put into a high viscosity vacuum mixer, and 20 parts by weight of talc, 1 part by weight of calcium chloride powder and 1 part by weight of sodium silicate were mixed first under vacuum with a high viscosity vacuum mixer (700 mm). Hg)) was prepared in the same manner as in Example 1 except that the mixture was slowly added and stirred to prepare an adhesive.

<Example 3>

22 parts by weight of two kinds of sodium silicate and 40 parts by weight of sodium silicate are mixed in a high-viscosity vacuum mixer (KSM1415), and thoroughly mixed. 20 parts by weight of calcium carbonate, 15 parts by weight of talc, 1.5 parts by weight of silica and 0.5 weight of potassium chloride. An adhesive was prepared in the same manner as in Example 1 except that 1 part by weight of parts and 1 parts by weight of magnesium silicate were mixed and slowly added under a high viscosity vacuum mixer under vacuum (700 mmHg or more) and stirred.

 <Example 4>

88 parts by weight of one type of sodium silicate specified in Korean Industrial Standard (KSM1415) was added to a high-viscosity vacuum mixer, and 2 parts by weight of calcium carbonate was added thereto. The mixture was stirred well to be thoroughly mixed and then heated to maintain the temperature of the contents at 80 ° C. for 15 minutes. After cooling to 10 ℃ by adding 10 parts by weight of the acrylic emulsion, the mixture was sufficiently stirred, the dissolver mixer was stopped, and the vacuum was maintained at 740 mmHg or more while only the paddle mixer was operated, thereby preparing an adhesive.

Example 5

5 parts by weight of one kind of sodium silicate, 20 parts by weight of two kinds of sodium silicate, and 35 parts by weight of three kinds of sodium silicate are put into a high viscosity vacuum mixer (KSM1415), and then 2 parts by weight of calcium carbonate is added and thoroughly stirred to mix. After heating, the temperature of the contents is maintained at 80 ° C. for 15 minutes, and then cooled to 30 ° C., followed by the addition of ethylene vinyl acetate emulsion, followed by sufficient stirring. The remaining 28 parts by weight of calcium carbonate is added to the mixture, and the dissolver mixer is stopped. The adhesive was prepared by completely degassing while maintaining the vacuum degree of 740 mmHg or more while operating only the paddle mixer.

<Example 6>

78 parts by weight of one kind of sodium silicate specified in the Korean Industrial Standards (KSM1415) was added to a high viscosity vacuum mixer, 2 parts by weight of calcium carbonate was added thereto, and the mixture was sufficiently stirred to warm it, and the temperature of the contents was maintained at 80 ° C. for 15 minutes. After cooling to 30 ° C, 10 parts by weight of polyvinylacetate emulsion is added to the mixture and stirred sufficiently. 10 parts by weight of zeolite is added to the mixture, followed by sufficient stirring. The dissolver mixer is stopped, the paddle mixer is operated, and the vacuum is maintained at 740 mmHg or more. To prepare an adhesive.

Comparative Example 1

78 parts by weight of two kinds of sodium silicate specified in the Korean Industrial Standard (KSM1415) were added to a high viscosity vacuum mixer, and 20 parts by weight of ethylene vinyl acetate emulsion was added. The mixture was sufficiently stirred, the dissolver mixer was stopped, and the paddle mixer was operated. The adhesive was prepared by degassing completely while maintaining the pressure.

Comparative Example 2

78 parts by weight of one kind of sodium silicate specified in Korean Industrial Standard (KSM1415) was added to a high viscosity vacuum mixer, and 2 parts by weight of talc and 10 parts by weight of zeolite were added thereto, followed by stirring. The dissolver mixer was stopped and the paddle mixer was operated. The adhesive was prepared by defoaming completely while maintaining at or above Hg.

Product usability and stability performance were tested with the adhesives prepared in the above examples and comparative examples.

Experimental Example 1 Product Usability Test

Viscosity, initial adhesion, and adhesion changes under warm humidification conditions were tested with regard to product usability.

The viscosity of the adhesive prepared in Examples 1 to 6 and Comparative Examples 1 and 2 was measured using a Brookfield Viscometer (BROOKFIELD RV T-5) at 20 ° C.

Initial adhesion was tested by attaching 50 × 50 × 10 pieces of MDF wood to the cement walls and ceilings using their respective adhesives and then observing whether they fell off.

The change in adhesion at warming conditions was tested by observing the state after one week under 80 ° C., and the change in adhesion at humidification condition was tested by observing the state after 24 hours under 80% relative humidity.

The test obtained the same result as Table 1 below.

Viscosity (cps) Initial Adhesion Change in adhesion Wall panel zenith Gaon Humidification Example 1 18,000 ○ ○ Good Good Example 2 9,000 ○ × Good Good Example 3 20,000 ○ ○ Good Good Example 4 12,000 ○ × Good Somewhat defective Example 5 20,000 ○ ○ Good Good Example 6 15,000 ○ ○ Good Somewhat defective Comparative Example 1 3,000 × × - - Comparative Example 2 18,000 ○ × Good Bad

The initial adhesive strength was obtained as the viscosity is higher, the adhesion was somewhat poor in the Example mainly using one type of sodium silicate under high humidity conditions. The adhesives of Examples 1 to 6 exhibited slightly different usability depending on their composition, composition ratio, and heat treatment conditions, but were suitable for use as adhesives. In Comparative Examples 1 and 2, the initial adhesive strength was good, but the adhesive force change was poor under the warm humidification condition.

Experimental Example 2 Stability Test

In order to test the viscosity stability and phase stability of the adhesive prepared in Examples 1 to 6 and Comparative Examples 1 and 2, various temperature conditions, 4 ℃, room temperature (R / T), 45 ℃, 24 hours a day 12 It was observed for 4 weeks under repeated (freezing cycle) conditions at 12 hours of freezing time. Each temperature sample was left at room temperature for at least 24 hours to observe viscosity and phase stability. The results are shown in Tables 2 and 3 below.

division term Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2     Viscosity Stability  4 ℃ 1 week Good Good Good Good Good Good Good Good 2 weeks Good Good Good Good Good Good Unchanged Unchanged 3 weeks Good Good Good Good Good Good Bad Bad 4 Weeks Good Good Good Good Good Good Bad Bad  R / T 1 week Good Good Good Good Good Good Good Good 2 weeks Good Good Good Good Good Good Unchanged Unchanged 3 weeks Good Good Good Good Good Good Bad Bad 4 Weeks Good Good Good Good Good Good Bad Bad  45 ℃ 1 week Good Good Good Good Good Good Good Unchanged 2 weeks Good Good Good Good Good Good Bad Bad 3 weeks Unchanged Good Good Unchanged Unchanged Unchanged Bad Bad 4 Weeks Unchanged Good Good Unchanged Unchanged Unchanged Bad Bad Refrigeration cycle 1 week Good Good Good Good Good Good Unchanged Bad 2 weeks Good Good Good Good Good Good Bad Bad 3 weeks Good Good Good Good Good Good Bad Bad 4 Weeks Good Good Good Good Good Good Bad Bad

Viscosity stability evaluation is 'good' if it is within the range of -20% to + 20% of the viscosity immediately after preparation, 'unchanged' if it is outside the range of -20% to + 20% of the viscosity immediately after preparation, and -50 of the viscosity immediately after preparation. If it is outside the range of% to + 50%, it was evaluated as 'bad'.

division term Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Comparative Example 1 Comparative Example 2     Stability  4 ℃ 1 week ○ ○ ○ ○ ○ ○ ○ ○ 2 weeks ○ ○ ○ ○ ○ ○ △ △ 3 weeks ○ ○ ○ ○ ○ ○ × × 4 Weeks ○ ○ ○ ○ ○ ○ × ×  R / T 1 week ○ ○ ○ ○ ○ ○ ○ ○ 2 weeks ○ ○ ○ ○ ○ ○ △ △ 3 weeks ○ ○ ○ ○ ○ ○ × × 4 Weeks ○ ○ ○ ○ ○ ○ × ×  45 ℃ 1 week ○ ○ ○ ○ ○ ○ ○ ○ 2 weeks ○ ○ ○ ○ ○ ○ △ △ 3 weeks △ ○ ○ △ △ △ × × 4 Weeks △ ○ ○ △ △ △ × ×  Refrigeration cycle 1 week ○ ○ ○ ○ ○ ○ ○ ○ 2 weeks ○ ○ ○ ○ ○ ○ △ × 3 weeks ○ ○ ○ ○ ○ ○ × × 4 Weeks ○ ○ ○ ○ ○ ○ × ×

The phase stability evaluation was evaluated as '○' when maintaining a stable phase, '△' when some transparent liquid layer was found on the surface, and '×' when complete phase separation.

Experimental results showed that the use of a less reactive filler (Viller) as a viscosity control agent is very advantageous for viscosity and phase stability, and when there is an appropriate amount of calcium carbonate in the embodiment without the added material for phase stability Satisfactory viscosity and phase stability were obtained by heat treatment at 80 ° C. for about 15 minutes.

1 is a block diagram schematically showing an example of a manufacturing process of a one-component inorganic adhesive according to the present invention.

Claims (12)

In the manufacturing method of a one-component inorganic adhesive having flame retardancy, 40 to 98 parts by weight of liquid sodium silicate and 0 to 50 parts by weight of a water-soluble polymer emulsion are mixed and stirred; Additionally mixing 0.1 to 50 parts by weight of the material for phase stability and 0.1 to 50 parts by weight of the viscosity modifier; And Method for producing a one-component inorganic adhesive comprising the step of defoaming the mixture. The method of claim 1, wherein the liquid sodium silicate is a mixed liquid of a plurality of liquid sodium silicates. The method of claim 1, wherein the water-soluble polymer emulsion is one or more selected from the group consisting of polyvinyl alcohol, polyvinylacetate, ethylene vinyl acetate, and an acrylic emulsion. The method of claim 1, wherein the material for phase stability is selected from the group consisting of baking soda, calcium chloride, kaolin, sodium silicate, magnesium silicate, potassium chloride, magnesium chloride, bentonite, silica, gypsum, zeolite, and potassium cement. A method for producing a one-component inorganic adhesive, characterized in that more than one. The method of claim 1, wherein the viscosity modifier is one or more selected from the group consisting of calcium carbonate, talc, aluminum oxide, alumina, loess, and glass powder. According to claim 1 or 5, when calcium carbonate is used as the viscosity modifier further comprises the step of heating to 60 ℃ to 80 ℃ to hold for 5 minutes to 30 minutes and then cooled to 20 ℃ to 30 ℃ Method of producing a one-component inorganic adhesive. In the one-component inorganic adhesive having flame retardancy, One-part inorganic adhesive prepared by mixing 40 to 98 parts by weight of liquid sodium silicate, 0 to 50 parts by weight of a water-soluble polymer emulsion, 0.1 to 50 parts by weight of a material for phase stability, and 0.1 to 50 parts by weight of a viscosity modifier. 8. The one-component inorganic adhesive according to claim 7, wherein the liquid sodium silicate is a mixed liquid of various liquid sodium silicates. 8. The one-component inorganic adhesive according to claim 7, wherein the water-soluble polymer emulsion is at least one selected from the group consisting of polyvinyl alcohol, polyvinylacetate, ethylene vinyl acetate, and acrylic emulsion. The method of claim 7, wherein the material for phase stability is selected from the group consisting of baking soda, calcium chloride, kaolin, sodium silicate, magnesium silicate, potassium chloride, magnesium chloride, bentonite, silica, gypsum, zeolite, and potassium cement. One-component inorganic adhesive, characterized in that more than one. The one-component inorganic adhesive according to claim 7, wherein the viscosity modifier is at least one selected from the group consisting of calcium carbonate, talc, aluminum oxide, alumina, loess, and glass powder. According to claim 7 or 11, when calcium carbonate is used as the viscosity modifier is prepared by heating to 60 ℃ to 80 ℃ to hold for 5 to 30 minutes and then cooled to 20 ℃ to 30 ℃ One component inorganic adhesive.

Images