KR20170076641A - Silicone emulsion for waterproofing, waterproof board and method for preparing the same - Google Patents

Abstract

The present invention relates to a waterproof silicone emulsion, and a waterproof board manufactured using the waterproof silicone emulsion, and more particularly, to a waterproof silicone emulsion containing a silicone oil and an emulsifier, and an emulsion, a hemihydrate gypsum and a catalyst The present invention relates to a waterproof board including a cured product of a water-based gypsum slurry and having a low density, exhibiting a low total water absorption rate at the same time, and greatly reducing a raw material cost, and a manufacturing method thereof.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a waterproof silicone emulsion, a waterproof board, and a method of manufacturing the waterproof board.

The present invention relates to a waterproof silicone emulsion, and a waterproof board manufactured using the waterproof silicone emulsion, and more particularly, to a waterproof silicone emulsion containing a silicone oil and an emulsifier, and an emulsion, a hemihydrate gypsum and a catalyst The present invention relates to a waterproof board including a cured product of a water-based gypsum slurry and having a low density, exhibiting a low total water absorption rate at the same time, and greatly reducing a raw material cost, and a manufacturing method thereof.

The gypsum board, which is a non-combustible and light-weight material with excellent car sound, is widely used as a building interior material due to its low price. The raw material of general gypsum board for construction is semi-gypsum, which is obtained by firing natural high-grade or desulfurized lime stone and removing crystal water. Half-gypsum is converted into an algebraic structure with a crystal structure, which is heated when reacted with water. During this process, the well-developed crystal structure of the needle-shaped bed increases the strength of the gypsum board itself and produces a gypsum board wrapped with a covering material by closely engaging with the gypsum board fiber.

In order to improve the productivity, various additives are also put in order to produce a gypsum board having various functions. For example, the foaming agent is an essential additive for forming gypsum board pores to lighten the gypsum board. As the foaming agent, a surfactant which mainly provides pores in the gypsum board is used. As another example, the water reducing agent reduces the amount of water used so that the sludge generated by the reaction of the water with the hemihydrate gypsum has a proper fluidity to process the gypsum board form.

The gypsum board is a material that is weak to moisture, but it can also be used on the wall of a shower room by giving it a waterproof function. As a waterproofing agent, silicone, asphalt or paraffin wax is generally used. However, asphalt has an advantage in that it is inexpensive, but it has a disadvantage in that it can only produce a black solid color. In case of paraffin wax, it is made water-soluble by using emulsifier and added to the gypsum board manufacturing process. Since paraffin wax covers the surface of gypsum and exhibits waterproof effect, it needs to use a lot of paraffin. Quot;

Further, in the case of paraffin wax dispersed in an aqueous solution, it is mixed and dispersed in the slurry during the process of producing the gypsum slurry. The dispersed paraffin wax is pushed to the gypsum surface as the semi-gypsum slurry grows into an asteroid solid. As the paraffin wax is dispersed evenly on the surface of the gypsum, the water repellency effect increases. However, since the paraffin wax does not form a strong bond with the gypsum surface, as the process water in the center of the board moves to the surface during drying of the gypsum board, It is difficult to spread them evenly on the surface of the gypsum. Therefore, a relatively large amount of paraffin wax is required to impart an effective waterproofing function. If there is a thermal change in the gypsum board in the future, the paraffin wax moves to one side or is eluted by the organic material, And provides a cause of a high defect rate.

When a silicone compound is used as a waterproofing agent, the hydrogene functional group of the silicone oil is hydrolyzed into a hydroxyl functional group during the production of the gypsum slurry, and this functional group is hydrolyzed by reacting with the hydroxyl functional group, Is fixed to the solid body. Through this process, the silicone oil is chemically bonded to the surface of the gypsum so as to cover the surface of the gypsum, and the water-repellent methyl group is positioned perpendicular to the surface of the gypsum, thereby exhibiting an effective water-repellent function on the surface of the gypsum. However, the silicone oil has a strong defoaming property and thus has a problem of removing bubbles generated in the gypsum core by using a foaming agent.

There is a patent (for example, US Patent Application Publication No. 2006/0162839 A1) disclosing a chemical stabilization method for enhancing the stability of a foam by adding an organic stabilizer to a surfactant, It is suitable for the purpose of avoiding vesicular action or suppressing the defoaming by hydrocarbons of paraffin waxes. However, it is difficult to apply the silicone-based waterproofing agent because of its large defoaming property. In recent years, a physical solution (for example, European Patent EP 1 637 302 A1) such as a facility improvement has been disclosed, but the above problems can not be solved.

It is an object of the present invention to provide a silicone emulsion which can provide excellent waterproof performance even with a small amount of silicone oil, and can greatly reduce raw material costs, a waterproof board manufactured using the silicone emulsion, and a method of manufacturing the same.

The waterproof silicone emulsion of the present invention includes a silicone oil and an emulsifier.

The waterproof board provided according to a specific aspect of the present invention includes a cured product of a water-based gypsum slurry including a semi-gypsum, a silicone oil, an emulsifier and a catalyst.

A waterproof board manufacturing method provided according to another specific aspect of the present invention includes forming an aqueous gypsum slurry containing a semi-gypsum, a silicone oil, an emulsifier and a catalyst, and curing the slurry.

When the silicone emulsion according to the present invention is used in the production of a waterproof product, it is possible to suppress the defoaming property of the silicone oil so that the final product can maintain a low density, while the size of the bubble is equal to that of the paraffin wax, A low total absorption rate (for example, 6% or less) can be exhibited even with the amount of oil used, and the raw material cost can be greatly reduced.

1 is an optical microscope photograph of a gypsum board section produced using methylhydrogenpolysiloxane (MHP), which is a silicone oil, as a waterproofing agent and styrene-maleic acid (SMA) copolymer as an emulsifier, according to the present invention.
2 is an optical microscope photograph of a section of a gypsum board prepared by using methylhydrogenpolysiloxane (MHP) as a waterproofing agent and without using an emulsifier.
3 is an optical microscope photograph of a section of a gypsum board produced using paraffin wax as a waterproofing agent and without using an emulsifier.

Hereinafter, the present invention will be described in detail.

The waterproof silicone emulsion of the present invention includes a silicone oil and an emulsifier.

The silicone oil may be a linear or cyclic, at least partially hydrogen-modified polysiloxane, which is used for imparting a water-proofing function. Such polysiloxanes can be polymerized in a basic environment to form highly crosslinked siloxane polymers, which polymers exhibit high water resistance. More specifically, the polysiloxane may include a structure represented by the following formula.

In the above formulas, R ₁ is independently hydrogen or a non-hydrogen substituent (e.g., alkyl, cycloalkyl, aryl, or heteroaryl substituted with unsubstituted or halogen), provided that at least one of the plurality of R ₁ is more specifically 10 % Or more (e.g., 10 to 100%) is hydrogen; R ₂ is a non-hydrogen substituent as described above; n is an integer from 1 to 200;

In the above, for example, the number of carbon atoms of alkyl may be 1 to 4, the number of carbon atoms of cycloalkyl may be 5 to 10, the number of carbon atoms of aryl may be 6 to 12, and the total number of ring atoms of heteroaryl may be 5 to 12 And may also have at least one heteroatom selected from N, O and S. The halogen may be fluorine, chlorine, bromine or iodine.

More specifically, the polysiloxane may comprise a structure represented by the following formula.

In the above structural formulas, x and y are mole fractions of the structural units to which they respectively indicate x + y = 1, x is 0.1 to 1, and y is 0 to 0.9.

According to a preferred embodiment of the present invention, silicone oil containing methylhydrogenpolysiloxane (MHP) is used as the silicone oil, and may be 0.1 to 60 parts by weight based on 100 parts by weight of the silicone emulsion.

The emulsifier may be a copolymer of a lipophilic monomer and a hydrophilic monomer, which is used for enhancing the dispersibility of the aqueous solution of the silicone oil to suppress the bubble formation thereof. For example, the lipophilic monomer may be aromatic or aryl benzene or aryl naphthalene having 1 to 3 benzene rings, and typically benzene, toluene or naphthalene may be used, and more preferably, Styrene is used. The hydrophilic monomer may be at least one selected from the group consisting of a polymerizable monomer containing at least one hydroxyl group (-OH) (e.g., an alcohol, a glycol, etc.), a halo-styrene, a maleic acid or an anhydride thereof, Methacrylic monomers or derivatives thereof. In addition, salt forms (e.g., Na salt, K salt, ammonium salt, etc.), hydrolyzed form, sulfonated form, and partially or fully esterified form of the copolymer of the oleophilic monomer and the hydrophilic monomer can also be used as the emulsifier have.

More specifically, the copolymer of the oleophilic monomer and the hydrophilic monomer may be a copolymer of styrene and allyl alcohol, a copolymer of styrene and ethylene glycol, a copolymer of styrene and chlorostyrene, a copolymer of styrene and acrylonitrile, (SMA copolymer) with maleic acid or an anhydride thereof, a copolymer of styrene and maleic acid or an anhydride thereof finished with cumene, a hydrolyzed form of a copolymer of styrene and maleic acid or an anhydride thereof , A sulfonated form of a copolymer of styrene and maleic acid or an anhydride thereof, an esterified form of a copolymer of styrene and maleic acid or an anhydride thereof, a copolymer of styrene and acrylic acid, a copolymer of styrene and methacrylic acid, And their salt forms. Commercially available products such as copolymers of styrene and maleic acid or its anhydrides include SMA1000, SMA2000, SMA3000, SMA4000, SMA17352 and the like manufactured by Clay Vally.

In the copolymer of the lipophilic monomer and the hydrophilic monomer, the molar ratio of the lipophilic monomer: hydrophilic monomer may be, for example, from 1: 1 to 8: 1, and more specifically from 1: 1 to 4: 1. In order to convert the copolymer of the lipophilic monomer and the hydrophilic monomer into an aqueous solution, the copolymer may be dissolved into a salt form using a basic solution such as NaOH, KOH, or aqueous ammonia. At this time, if the pH of the aqueous solution is too high, it may affect the reactivity of the hydrogen atoms in the silicone oil, so that the pH of the aqueous solution of the copolymer is preferably maintained between 9 and 12.

The copolymer of the lipophilic monomer and the hydrophilic monomer physically bonds with the silicone oil polymer to form micelles, thereby allowing the lipophilic silicone oil to be uniformly dispersed in the water. As a result, For example, gypsum) so as to exhibit a high waterproof performance even with a small amount of silicon used. In addition, it is possible to produce lightweight waterproof products by suppressing the defoaming of the silicone oil so that a large size bubble is appropriately formed inside the product.

The content of the emulsifier in the silicone emulsion of the present invention may be, for example, 0.002 to 10 parts by weight, more specifically 0.3 to 5 parts by weight, based on 100 parts by weight of the silicone oil. If the content of the emulsifier in the silicone emulsion is less than the above range, the emulsion may not be able to be produced because it does not reach the critical micelle concentration (CMC). On the contrary, if the emulsifier content is too high, There may be a problem of speeding up.

The silicone emulsion of the present invention may further comprise a foaming agent for the purpose of improving the density and bubble of the product to which it is applied. The foaming agent may be a surfactant for foaming, more specifically, an anionic surfactant (for example, an anionic surfactant containing a sulfate group), an amphoteric surfactant (for example, betaine), an alkylpoly Glucosides, alkyl alcohols (e.g., C8 to C20 alkyl alcohols), and the like may be used alone or in combination, but the present invention is not limited thereto.

When the foaming agent is contained in the silicone emulsion of the present invention, the content thereof may be, for example, 2 to 60 parts by weight, more specifically 5 to 40 parts by weight, based on 100 parts by weight of the silicone oil. If the amount of the foaming agent in the silicone emulsion is less than the above-mentioned range, there may be a problem that the density of the bubbles disappears due to the defoaming property of the silicone oil. On the contrary, if the foaming agent content is too high, the viscosity of the slurry of the product to which the silicone emulsion is applied increases, There may be a problem that mixing is not done well in the mixer.

The silicone emulsion according to the present invention can provide excellent waterproof performance even with a small amount of silicone oil and contributes to weight reduction of the product to which it is applied and can be applied to various waterproof products. For example, the silicone emulsion can be applied to waterproof boards, It is not.

Accordingly, a waterproof board provided in accordance with a specific aspect of the present invention includes a cured product of a water-based gypsum slurry comprising a semi-gypsum, a silicone oil, an emulsifier, and a catalyst. The cured product of the gypsum slurry can be used as the core of the board.

The semi-gypsum gypsum is obtained by calcining a natural alumite or desulfurization alumite to remove a part of the crystal water.

In the waterproof board of the present invention, the gypsum content in the gypsum slurry may be, for example, 40 to 80% by weight, more specifically 50 to 70% by weight, based on 100% by weight of the slurry. In addition, the water content in the gypsum slurry of the present invention may be, for example, 20 to 60 wt%, more specifically 30 to 50 wt%, based on 100 wt% of the slurry.

The silicone emulsion contained in the waterproof board of the present invention is as described above, and the silicone emulsion includes a silicone oil and an emulsifier. Also, the gypsum slurry may further contain a foaming agent as described above.

In the waterproof board of the present invention, the content of the silicone emulsion in the gypsum slurry may be 0.0002 to 4 parts by weight, more specifically 0.001 to 1.5 parts by weight, based on 100 parts by weight of the gypsum slurry. If the content of the silicone emulsion in the gypsum slurry is less than the above range, there may be a problem that the desired waterproof property is not exhibited. On the contrary, if it is too much, the amount of the gypsum used is increased due to the bubble- There is a problem that the viscosity is increased and the inside of the mixer is hardened.

The catalyst reacts with active hydrogen present in the silicone oil to form a siloxane polymer on the product surface, and a basic catalyst can be used. For example, as the catalyst, limestone, lime, cement, MgO, CaO, CaMgO, dolomite (dolomite), etc. may be used singly or in combination. More specifically, light MgO, light CaMgO, But are not limited thereto.

In the waterproof board of the present invention, the catalyst content in the gypsum slurry may be, for example, 0.2 to 1.5 parts by weight, and more specifically 0.3 to 1.0 parts by weight, based on 100 parts by weight of the gypsum. If the catalyst content in the gypsum slurry is less than the above range, the silicone oil may not be polymerized to exhibit sufficient water resistance. On the contrary, if the catalyst content is too large, the pH of the whole sludge may increase and the strength may be weak.

According to another specific aspect of the present invention, there is provided a method of manufacturing a waterproof board, which comprises forming an aqueous gypsum slurry containing a semi-gypsum, a silicone oil, an emulsifier and a catalyst, and curing the slurry.

According to one embodiment of the present invention, the waterproof board of the present invention comprises a step of mixing an aqueous emulsion containing a silicone oil and an emulsifier with a mixture of a catalyst and a semi-gypsum to form an aqueous gypsum slurry, and And molding and curing the gypsum slurry.

Generally, for the production of a lightweight gypsum board having pores, pre-foam is prepared by injecting high-pressure air into an aqueous solution containing an anionic surfactant, mixed with semi-gypsum and metered process water, Processing. In the case of a light gypsum board, a proper combination of large pores and small pores is required because large pores are mainly formed at the center of the gypsum board and small pores are mainly located at the upper and lower surfaces of the gypsum board, Hardness and drying conditions. Therefore, it is important to maintain adequately large bubbles.

In the case of silicon, it exhibits excellent waterproof performance even in a small amount compared with paraffin wax, but on the other hand acts as a defoaming agent to break the air bubbles in the gypsum sludge and increase the density of the gypsum. When the blowing agent is added in an excess amount to compensate for the reduction of the bubbles caused by the silicon, the size of the bubbles becomes small and the viscosity of the sludge increases. In addition, when the basic catalyst is used, the reaction rate is too fast, so cracks (cracking) may occur in the gypsum product due to the rapid generation of hydrogen molecules as reaction byproducts.

In the present invention, by using a silicone oil as a waterproofing agent, an excellent waterproof performance can be obtained even by using a small amount of water. By using emulsifiers in combination, it is possible to suppress the defoaming property of the silicone oil, Thereby preventing cracking.

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

[ Example ]

A silicone emulsion was first prepared to prepare gypsum specimens. The silicone emulsion was prepared by passing water, methylhydrogenpolysiloxane (MHP), and emulsifier through a high pressure homogenizer at 450 bar. When an emulsifier was used, emulsions were prepared while varying the composition as shown in Table 1 in order to characterize the silicone emulsion. SMA used in emulsions 2 to 7 was a copolymer of styrene and maleic acid, and a copolymer in which styrene was copolymerized in a molar ratio of 1 to 4 with respect to 1 mole of maleic acid was used. The styrene acrylic acid and methacrylic acid polymers used in the emulsions 8 to 9 each had a polymer copolymerized with styrene and a hydrophilic group at a molar ratio of 1: 1.

Example  One

A gypsum specimen is prepared from the prepared emulsion and the density is observed. 0.5 part by weight of a water-reducing agent (Poly-naphthalene sulfonate), 0.6 parts by weight of light-weight dolomite as a catalyst and 49 parts by weight of water as the emulsion prepared in the contents shown in Table 1 were added to 100 parts by weight of a semi-gypsum, To this was added a pre-foam (a mixture of 0.05 part by weight of a foaming agent (GPA-01 from Stepane) and 21 parts by weight of water, which was previously foamed at 2500 rpm for 1 minute in a high-speed stirrer) was poured and mixed to prepare a gypsum slurry And then hardened to prepare a gypsum specimen. At this time, in Comparative Example 1-1, a gypsum specimen was prepared by using the MHP emulsion not containing an emulsifier as described above. The densities of the prepared gypsum specimens were measured and are shown in Table 2.

Example 2

The same experiment as in Example 1 was carried out for the emulsion 3 and the emulsion 4 in which the amount of the emulsifier was adjusted in the emulsion 2, and the results are shown in Table 3.

Example 3

The total absorbency of the gypsum specimens of Examples 1-1 and 1-3 was measured. Total absorbency was obtained by measuring gypsum specimens according to KS F 3504 standard, measuring weight gain (%) against 100% of original weight after immersing plaster specimens in water at 20 ° C for 2 hours. As Comparative Example 3-1, a gypsum specimen prepared without using an emulsifier and MHP was used. In Comparative Example 3-2, paraffin wax (Paraffin Wax) was used instead of MHP as a waterproofing agent in an amount of 100 parts by weight And 2.5 parts by weight per 100 parts by weight of the gypsum. The measurement results are shown in Table 4.

Example 4

The emulsions 5 to 7 in which the ratio of the hydrophilic group and the hydrophilic group of the emulsifier in emulsion 2 were adjusted were tested in the same manner as in Example 1. The results are shown in Table 5.

Example 5

The emulsions 8 to 9, in which the hydrophilic groups were changed in the emulsion 2, were subjected to the same tests as in Example 1, and the results are shown in Table 6.

Example 6

The same test as in Example 1 was carried out on the emulsion 10 in which the emulsifier was mixed and used. The results are shown in Table 7.

Example 7

The MHP emulsion was prepared in the same manner as in the emulsion 2 of Example 1 except that the hydrogen content of the silicone oil was changed. Each of the prepared emulsions was used to prepare a gypsum specimen in the same manner as in Example 1, Respectively. In Comparative Example 7-1, a gypsum specimen prepared by using paraffin wax as a waterproofing agent in an amount of 3.5 parts by weight per 100 parts by weight of a semi-gypsum used amount was used. The measurement results are shown in Table 8.

- Example 7-1: Hydrogen in MHP: methyl content = 100%: 0%

- Example 7-2: Hydrogen in MHP: methyl content = 50%: 50%

- Example 7-3: Hydrogen in MHP: methyl content = 10%: 90%

Example 8

A gypsum specimen was prepared in the same manner as in Example 1-1, and the foaming agent shown in Table 9 was further used. The densities of the prepared gypsum specimens were measured and are shown in Table 9.

Example 9

The MHP emulsion was prepared in the same manner as Emulsion 2 except that the emulsifier was changed as described below. Each of the prepared emulsions was used to prepare gypsum specimens in the same manner as in Example 1. The densities of the gypsum specimens thus prepared were measured and shown in Table 10 .

* - Example 9-1: Use of cumene-finished SMA copolymer

Example 9-2: Use of partially esterified SMA copolymer

Example 9-3: Use of Sulfonated SMA Copolymer

Claims (9)

Methylhydrogenpolysiloxane, a copolymer of styrene and maleic acid, and water,
A copolymer of styrene and maleic acid in an amount of 0.3 to 5 parts by weight based on 100 parts by weight of the methylhydrogenpolysiloxane,
Wherein the copolymer of styrene and maleic acid is a water-soluble silicone emulsion having a pH of 9 to 12 in the form of an aqueous solution.
The waterproof silicone emulsion according to claim 1, further comprising a foaming agent.
The waterproof silicone emulsion according to claim 1, wherein the foaming agent is selected from anionic surfactants, amphoteric surfactants, alkyl polyglucosides, alkyl alcohols and combinations thereof.
A waterproof board comprising a cured product of an aqueous gypsum slurry comprising 0.0002 to 4 parts by weight of a silicone emulsion and 0.2 to 1.5 parts by weight of a catalyst based on 100 parts by weight of a gypsum gypsum,
Wherein the silicone emulsion comprises methylhydrogen colsiloxane, a copolymer of styrene and maleic acid, and water,
Wherein the copolymer of styrene and maleic acid is contained in an amount of 0.3 to 5 parts by weight based on 100 parts by weight of the methylhydrogenpolysiloxane,
Wherein the copolymer of styrene and maleic acid has a pH of 9 to 12 in the form of an aqueous solution.
5. The waterproofing board of claim 4, wherein the catalyst is a basic catalyst.
5. The waterproofing board of claim 4, wherein the water based gypsum slurry further comprises foaming agent.
7. A waterproofing board according to claim 6, wherein the foaming agent is selected from anionic surfactants, amphoteric surfactants, alkyl polyglucosides, alkyl alcohols and combinations thereof.
A method for manufacturing a waterproof board comprising forming an aqueous gypsum slurry comprising 0.0002 to 4 parts by weight of a silicone emulsion and 0.2 to 1.5 parts by weight of a catalyst based on 100 parts by weight of a gypsum gypsum,
Wherein the silicone emulsion comprises methylhydrogen colsiloxane, a copolymer of styrene and maleic acid, and water,
Wherein the copolymer of styrene and maleic acid is contained in an amount of 0.3 to 5 parts by weight based on 100 parts by weight of the methylhydrogenpolysiloxane,
Wherein the copolymer of styrene and maleic acid has a pH of 9 to 12 in the form of an aqueous solution.
9. The method of claim 8, further comprising the steps of: mixing a mixture of an aqueous emulsion comprising a silicone oil and an emulsifier with a catalyst and a semi- gypsum slurry to form an aqueous gypsum slurry; and molding and curing the gypsum slurry Gt;

Images