KR101515922B1 - Composition for improving water repellency - Google Patents

Abstract

The present invention provides a composition for improving water repellency and waterproofing property of a substrate including water-dispersible poly(urethane-acrylic) resins with fluorine group and carbodiimide group.

Description

[Composition for improving water repellency]

The present invention relates to a composition capable of improving water repellency or water resistance of a substrate.

Since various construction structures are repeatedly exposed to external environment such as moisture, ultraviolet rays, chemical substances for a long period of time, application of a water repellent agent and a waterproofing agent is required to improve durability. Examples of the compound used as a water repellent agent and a water repellent agent include a silicone system that imparts water repellency to the surface of the structure without filling the pores of the structure, a non-silicone system that exhibits performance by filling the pores of the structure, . Existing water repellent and water repellent agents often lose their function in a short period of time due to continuous repeated attack of external factors, and they are often not free to use because they discharge a large amount of environmental pollutants or have a high unit price.

Korean Patent Publication No. 10-2004-0002327 (2004.01.07.) Korean Patent Laid-Open No. 10-2012-0003316 (Jan. 10, 2012)

An aspect of the present invention is to provide a composition and a method for producing the same that are excellent in improving water repellency and waterproofness of a substrate.

One aspect of the present invention provides a composition for improving water repellency or water resistance of a substrate comprising a water-dispersed poly (urethane-acrylic) resin having fluoro groups and carbodiimide groups.

Another aspect of the present invention relates to a process for producing a polyol which comprises reacting 2 to 8 parts by weight of dimethylol propionic acid and 20 to 60 parts by weight of a diisocyanate compound with respect to 100 parts by weight of a polyol, A prepolymer producing step of producing a prepolymer; A fluorine group bonding step of adding 5 to 15 parts by weight of perfluoroalkylalcohol to 100 parts by weight of the prepared prepolymer to bond a fluorine group to the NCO group at one end of the prepolymer; A carbodiimide group bonding step of adding 0.001 to 0.5 part by weight of a catalyst to 100 parts by weight of the prepolymer to bond the carbodiimide group to the other end of the prepolymer; Preparing a prepolymer by neutralizing a carboxyl group derived from dimethylol propionic acid by adding an amine neutralizing agent to a prepolymer having fluorine groups and carbodiimide groups bonded to both ends thereof to a pH of 7 to 10; A water-dispersed polyurethane production step of adding 150 to 350 parts by weight of water to the polyurethane produced; Dispersible poly (urethane-acrylic) resin (10 to 35 parts by weight), which is obtained by grafting acrylate to polyurethane by adding at least one of alkyl methacrylate, alkyl acrylate and styrene to 100 parts by weight of water-dispersed polyurethane The present invention also provides a method for producing a composition for improving the water repellency or water resistance of a substrate comprising a production step.

The composition according to the present invention is excellent in water repellency, water resistance, breathability, weather resistance, acid resistance, chemical resistance, ultraviolet ray resistance, heat resistance and weather resistance by including an aqueous dispersion poly (urethane- acrylic) resin having a fluoro group and a carbodiimide group. Adhesion and reinforcing effect of corrosion inhibition. In addition, it is environmentally friendly because it does not contain an organic solvent and can be used regardless of the pore size of the substrate, so that the need for repeated use is low, which is economical.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is an illustration of a method of making a water-dispersed poly (urethane-acrylic) resin having fluoro groups and carbodiimide groups.

As used herein, the term " water repellent " refers to a property of causing a substrate to repel water without impregnation, and "water repellency" refers to a property that prevents water from penetrating or penetrating the substrate.

In the present specification, the term "substrate" means a base material such as a structure. A substrate such as concrete, stone, wood, plastic or gypsum is used in a structure and is continuously exposed to the external environment, so that excellent water repellency and waterproofness are required.

One aspect of the present invention provides a composition for improving water repellency or water resistance of a substrate comprising a water-dispersed poly (urethane-acrylic) resin having fluoro groups and carbodiimide groups.

In one aspect of the invention, the substrate comprises a construction substrate, and specifically includes concrete, stone, wood, plastic or gypsum, and more specifically concrete.

In another aspect of the present invention, the water-dispersed poly (urethane-acrylic) resin may have a fluorine group at one end and a carbodiimide group at the other end. As described above, the water-dispersed poly (urethane-acrylic) resin according to one aspect of the present invention has a carbodiimide group that is hydrophilic at one end thereof, thereby sufficiently forming a chemical cross-linking structure with the substrate. Therefore, the mechanical properties such as water resistance, abrasion resistance, Excellent adhesion strength. It is also easy to reinforce physical and chemical properties after curing because it can be cured at room temperature. At the same time, the water-dispersible poly (urethane-acrylic) resin according to one aspect of the present invention has a hydrophobic, specifically superfluous fluorine group at the other end thereof, and effectively blocks moisture permeating from the outside, thereby exhibiting excellent water repellency and waterproof property . That is, the water-dispersible poly (urethane-acrylic) resin having a hydrophobic fluorine group at one end and a carbodiimide group at the other end both exhibits hydrophobicity and hydrophilicity, thereby giving a solid structure resulting from excellent mechanical properties, So that it can not easily fall into the water and the water permeation of the outside is fundamentally blocked, so that it can have excellent water repellency and waterproofness.

The water-dispersed poly (urethane-acrylic) resin according to one aspect of the present invention is excellent in permeability, water resistance, weather resistance, acid resistance and chemical resistance by acrylate grafting.

The composition according to one aspect of the invention has a particle size of 40 to 100 nm, specifically 50 to 90 nm, more specifically 60 to 80 nm. Therefore, the composition according to one aspect of the present invention can be used regardless of the pore size of the substrate, so that it is highly utilized and can penetrate into the substrate to form a waterproof layer and can form a separate barrier layer on the surface of the substrate, And water resistance.

Urethane compounds, which have been used as waterproofing compositions in the past, contain a large amount of an organic solvent having a low flash point such as methyl ethyl ketone, ethyl acetate, butyl acetate, and toluene, which not only increases the risk of fire but also increases volatile organic compounds (VOC) Releases, lowers the health and productivity of workers, and has a high possibility of air and water pollution. Since the water-dispersible poly (urethane-acrylic) resin according to one aspect of the present invention exhibits water-dispersibility, the organic solvent can be replaced by water, thereby showing no disadvantages of the existing composition for improving water resistance due to the content of the organic solvent and being environmentally friendly.

The composition for improving water repellency or water resistance of a substrate according to an aspect of the present invention includes a composition for coating that is coated on a substrate to improve the water repellency or water resistance of the substrate.

The composition according to one aspect of the present invention may further comprise at least one of a crosslinking agent, a dispersing agent and a pigment. Compositions comprising a water-dispersed poly (urethane-acrylic) resin according to one aspect of the present invention may include various additives within the scope of not changing the technical characteristics of the present invention. For example, an antistatic agent selected from a conductive polymer, a quaternary ammonium salt, an inorganic salt, a metal particle and a (meth) acrylate modified quaternary ammonium salt, and may contain an antioxidant, a UV absorbent, a light stabilizer, , A leveling agent, a surfactant, a lubricant, and the like, but the present invention is not limited thereto.

The composition comprising the water-dispersed poly (urethane-acrylic) resin having a fluorine group and a carbodiimide group according to one aspect of the present invention is environmentally friendly in terms of the durability of various structures such as a single house, an apartment, a school, And can be freely used to enhance the waterproofness of the water tank of the water purification plant and the water supply and drainage related facilities which are always in contact with the water and the release of harmful substances is not allowed and frequent water exposure, neutralization and chemical erosion are concerned, It is possible to prevent the deterioration of difficult underground structures and factories and to prevent the salinity of coastal and port structures in which salt penetration is a concern and to increase the surface hardness of the structures such as roads and runways that are concerned with friction or wear It can increase the water resistance of bridge piers, tunnel lining and various slabs. It can also be used to improve water repellency, water repellency, and waterproofing of existing structures that suffer from damage such as neutralization, salting, whitening, freezing and thawing, and chemical erosion.

One aspect of the present invention provides water-dispersed poly (urethane-acrylic) resins having fluoro groups and carbodiimide groups. In another aspect of the present invention, the water-dispersed poly (urethane-acrylic) resin may have a fluorine group at one end and a carbodiimide group at the other end. In this case, both the hydrophobicity and the hydrophilicity are high, And at the same time, moisture penetration from the outside to the substrate can be prevented, and excellent water repellency and waterproofness can be imparted.

One aspect of the present invention relates to a process for producing a polyol which comprises reacting 2 to 8 parts by weight of dimethylol propionic acid and 20 to 60 parts by weight of a diisocyanate compound with respect to 100 parts by weight of a polyol, A prepolymer producing step of producing a prepolymer; A fluorine group bonding step of adding 5 to 15 parts by weight of perfluoroalkylalcohol to 100 parts by weight of the prepared prepolymer to bond a fluorine group to the NCO group at one end of the prepolymer; A carbodiimide group bonding step of adding 0.001 to 0.5 part by weight of a catalyst to 100 parts by weight of the prepared prepolymer to bond a carbodiimide group to the other end of the prepolymer; Preparing a prepolymer by neutralizing a carboxyl group derived from dimethylol propionic acid by adding an amine neutralizing agent to a prepolymer having fluorine groups and carbodiimide groups bonded to both ends thereof to a pH of 7 to 10; A water-dispersed polyurethane production step of adding 150 to 350 parts by weight of water to the polyurethane produced; Dispersible poly (urethane-acrylic) resin (10 to 35 parts by weight), which is obtained by grafting acrylate to polyurethane by adding at least one of alkyl methacrylate, alkyl acrylate and styrene to 100 parts by weight of water-dispersed polyurethane The present invention also provides a method for producing a composition for improving the water repellency or water resistance of a substrate comprising a production step.

In the prepolymer preparation step of the process according to one aspect of the present invention, the polyol has from ₁ to ₂₀ carbon atoms, in particular from ₃ to ₁₈ carbon atoms, more particularly from ₅ to ₁₅ carbon atoms, and from 2 to 10, Includes compounds having 3 to 7 hydroxyl groups (-OH). In another aspect of the invention, the polyol comprises a polycarbonate diol. In another aspect of the present invention, the polyol includes a polyol having a number average molecular weight of 200 to 2,000, specifically 500 to 2,000.

In one aspect of the present invention, the prepolymer comprises a polymer having a relatively low degree of polymerization, and specifically includes a polyurethane.

In the method according to one aspect of the present invention, the isocyanate-based compound in the prepolymer preparation step contains at least one of isophorone diisocyanate and methylene diphenyl diisocyanate.

In the step of preparing the prepolymer of the method according to one aspect of the present invention, 2 to 8 parts by weight, specifically 5 to 8 parts by weight, of dimethylol propionic acid and 20 to 60 parts by weight, specifically 30 to 50 parts by weight, A diisocyanate compound can be reacted.

 In the step of preparing the prepolymer of the method according to one aspect of the present invention, 0.001 to 0.1 part by weight of the tin catalyst may be further reacted with respect to 100 parts by weight of the polyol. In another aspect of the present invention, the tin catalyst comprises dibutyltin dilaurate (DBTL).

In one aspect of the present invention, a prepolymer prepared by reacting a polyol, an isocyanate compound, and dimethylol propionic acid comprises a NCO terminated prepolymer.

In one aspect of the present invention, the prepolymer is prepared by reacting the polyol, dimethylol propionic acid and the diisocyanate compound at 60-100 ° C for 3-6 hours. In another aspect of the present invention, the prepolymer is prepared by reacting an isocyanate with a polyol to prepare a urethane prepolymer, and reacting the prepared urethane prepolymer with dimethylol propionic acid to prepare a prepolymer. . In another aspect of the present invention, the prepolymer obtained by reacting dimethylol propionic acid and introducing an anionic group is stable in water. The method according to one aspect of the present invention uses a self-emulsifying method in which an ionic group is introduced into a urethane to increase the water dispersibility of the hydrophobic urethane and then self-emulsification is performed. Therefore, an emulsifier is not used, Excellent physical properties.

In the fluorine group bonding step of the method according to one aspect of the present invention, 5 to 15 parts by weight of perfluoroalkylalcohol is added to the prepolymer in an amount of 100 parts by weight of the prepolymer, and the mixture is reacted for 3 to 8 hours to bond the fluorine group to the terminal NCO group . And perfluoroalkylalcohol are less than 5 parts by weight, sufficient water repellency is not exhibited. When the amount is more than 15 parts by weight, the unbonded monomers may impair the stability of the prepolymer and the efficiency is low in terms of production cost.

In the method according to one aspect of the present invention, the carbodiimide group bonding step is carried out by reacting the carbodiimide group with 0.001 to 0.5 part by weight of at least one of phospholene oxide and amine as a catalyst for 3-9 hours . When the amount of the at least one catalyst selected from the group consisting of phosphorane oxide and amine is less than 0.001 part by weight, the formation of carbodiimide groups is difficult to obtain sufficiently. If the amount is more than 0.5 part by weight, It is uneconomical in terms of unit price.

In another aspect of the invention, the amine comprises C = N = C.

In the polyurethane preparation step of the process according to one aspect of the present invention, the amine neutralizing agent comprises NR ₃ and R is a C ₁ to C ₁₀ hydrocarbon, such as methyl, ethyl, propyl, butyl, pentyl or phenyl, .

When the amount of water added to the polyurethane is less than 150 parts by weight, sufficient water dispersion is not achieved. When the amount of water added to the polyurethane is less than 350 parts by weight, the water content and water repellency It is difficult to be effectively expressed.

In the step of preparing the water-dispersed poly (urethane-acrylic) resin of the method according to an aspect of the present invention, 10 to 35 parts by weight, specifically 15 to 30 parts by weight, of alkyl methacrylate, alkyl Acrylate and styrene may be added. When alkyl methacrylate, alkyl acrylate and styrene are used in an amount of less than 10 parts by weight, sufficient copolymerization can not be carried out, resulting in a resin having a low mechanical strength such as water resistance, chemical resistance, thermal stability and tensile strength, If the amount is more than 35 parts by weight, the viscosity increases and the fluidity remarkably decreases, so that it is not easy to use. In one aspect of the invention, the alkyl comprises a C ₁ to C ₆ hydrocarbon group. Specifically, the alkyl methacrylate includes methyl methacrylate, the alkyl acrylate includes butylacrylate, and the styrene includes a styrene monomer.

The step of preparing the water-dispersed poly (urethane-acrylic) resin of the process according to one aspect of the present invention comprises reacting alkyl methacrylate, alkyl acrylate and styrene in an amount of from 7 to 9: 1 to 3: 0.1 to 1.5, 1 to 2: 0.1 to 1. When used in such a ratio, the technical characteristics to be exhibited by the present invention can be exerted well, and the cost effectiveness can be enhanced.

In the step of producing the water-dispersed poly (urethane-acrylic) resin of the method according to one aspect of the present invention, 0.1 to 3 parts by weight, particularly 0.5 to 2 parts by weight, based on the water-dispersed polyurethane, of a water- It can be done more easily. In another aspect of the present invention, the peroxide initiator comprises potassium persulfate, sodium persulfate or lithium persulfate.

The method according to one aspect of the present invention may further comprise the step of adding at least one of a crosslinking agent, a dispersing agent and a pigment to the composition.

The method according to one aspect of the present invention may include the step of applying various additives within a range that does not change the technical characteristics of the present invention. For example, it may include a step of adding an antistatic agent selected from a conductive polymer, a quaternary ammonium salt, an inorganic salt, metal particles and a (meth) acrylate-modified quaternary ammonium salt, and may further comprise an antioxidant, a UV absorber, a light stabilizer, A leveling agent, a surfactant, a lubricant, and the like in a usual range, but the present invention is not limited thereto.

The method according to an aspect of the present invention may further include the step of curing the composition by adding a phosphorus-containing curing agent to the composition. The composition cured with the phosphorus-containing curing agent is characterized by excellent mechanical strength such as corrosion resistance, thermal stability, tensile strength and the like.

The method for manufacturing a composition for improving the water repellency or water resistance of a substrate according to an aspect of the present invention is a method for producing a composition comprising a water-dispersed poly (urethane-acrylic) resin having a fluorine group and a carbodiimide group according to another aspect of the present invention .

Hereinafter, the constitution and effects of the present invention will be described in more detail with reference to Examples, Comparative Examples and Experimental Examples. However, these examples, comparative examples, and experimental examples are provided for illustrative purposes only in order to facilitate understanding of the present invention, and the scope and scope of the present invention are not limited thereto.

EXAMPLES AND COMPARATIVE EXAMPLES Preparation of water-dispersed poly (urethane-acrylic) resins having fluorine groups and carbodiimide groups

30 g of a polycarbonate diol (DOW chemical, C1000) having a molecular weight of 1,000 as a polyol, 13 g of isophorone diisocyanate, 0.005 g of di-n-butyltin dilaurate (DBTL) as a polyol was placed in a 500 mL four necked reactor connected to a thermometer, a condenser, , 2 g of dimethylol propionic acid (DMPA) dissolved in 6 g of NMP (N-methyl pyrrolidone) was added, and the mixture was stirred at 75 ° C for 3 hours to prepare a prepolymer. 5 parts by weight of perfluoroalkylethanol (PFAE, MW 500) was added to 100 parts by weight of the prepared prepolymer and stirred at 75 ° C for 5 hours to introduce a fluorine group into one end of the prepolymer. Then, 0.05 part by weight of 3-methyl-1-phenyl-2-phospholene-1-oxide as a phosphorane oxide catalyst was added thereto, Followed by stirring for a time period to introduce a carbodiimide group into the other side terminal of the prepolymer. After the reaction, the temperature is lowered to 50 ° C and triethylamine (TEA) is slowly added to neutralize the reaction mixture. After the neutralization, 200 parts by weight of distilled water was slowly added to the reaction vessel, and an aqueous dispersion solution was prepared while stirring at a high speed. 2 g of ethylenediamine (EDA) is diluted by adding 8 g of ultrapure water to a water dispersion solution, followed by stirring for 1 hour to prepare a water-dispersed polyurethane composition. 80% of methyl methacrylate in water dispersion reaction solution. 15 parts by weight of a monomer containing 15% of butyl acrylate and 5% of styrene monomer and 0.5 parts by weight of potash persulfate as an initiator were added dropwise to water at 80 캜 for 3 hours while stirring to form an aqueous dispersion poly (urethane-acrylic) resin To prepare Example 1.

Using substantially the same procedure as above except that perfluoroalkylethanol, 3-methyl-1-phenyl-2-phosphorene-1-oxide catalyst and methyl methacrylate 80% by weight as shown in Table 1 below. Examples 2 to 4 and Comparative Examples 1 to 4 were prepared using monomers containing 15% of butyl acrylate and 5% of styrene monomer.

Composition (parts by weight) Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 And fluoroalkylethanol 5 7 10 15 0 One 3 4 3-methyl-1-phenyl-2-phosphorene-1-oxide 0.05 0.1 0.3 0.5 0 0.01 0.03 0.04 Methyl methacrylate 80%. 15% of butyl acrylate, 5% of styrene monomer 15 20 25 35 15 20 25 35

[Experimental Example] Property evaluation method

Each of the indicators was evaluated using the methods shown in Table 2 below for Examples 1 to 4 and Comparative Examples 1 to 4, and the results are shown in Table 3.

Indicators Experimental Method One Water resistance (day) Constitution bath (40 ± 1%) 2 Contact angle (water, °) ASTM D 5946 3 Tensile Strength (MPa) KS F 2423 (ASTM D-638) 4 Bond strength (MPa) KS F 4715 5 Organic solvent content (g / m ² ) TA-Luft 6 Water absorption coefficient KS F 2609

Indicators Example 1 Example 2 Example 3 Example 4 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 One Water resistance (days) 8 9 10 10 2 3 4 4 2 Contact angle (water, °) 103 106 109 115 55 59 60 68 3 Tensile Strength (MPa) 2.3 2.3 2.4 2.5 1.3 1.3 1.5 1.6 4 Bond strength (MPa) 1.8 1.9 2.0 2.0 0.8 0.9 1.0 1.0 5 Organic solvent content (g / m ² ) 15 15 15 15 15 15 15 15 6 Water absorption coefficient 0.03 0.01 0.002 0.001 0.21 0.20 0.16 0.13

As shown in Table 3, Examples 1 to 4, which are water-dispersed polyurethane compositions prepared using 5 to 15 parts by weight of perfluoroalkylethanol and 0.01 to 0.5 parts by weight of phosphorane oxide, show that perfluoroalkylethanol and Compared with Comparative Examples 1 to 4 using phosphorane oxide, the water resistance, the contact angle, the water absorption coefficient, and the mechanical strength were excellent both in tensile strength and adhesion strength.

Claims (13)

delete delete delete delete delete A prepolymer for producing a prepolymer having an NCO group at the terminal by reacting 2 to 8 parts by weight of dimethylol propionic acid and 20 to 60 parts by weight of a diisocyanate compound with respect to 100 parts by weight of polyol Manufacturing steps;
A fluorine group bonding step of adding 5 to 15 parts by weight of perfluoroalkylalcohol to 100 parts by weight of the prepared prepolymer to bond a fluorine group to the NCO group at one end of the prepolymer;
A carbodiimide group bonding step of adding 0.001 to 0.5 part by weight of a catalyst to 100 parts by weight of the prepared prepolymer to bond a carbodiimide group to the other end of the prepolymer;
Adding an amine neutralizing agent to a prepolymer having fluorine groups and carbodiimide groups bonded to both ends thereof to a pH of 7 to 10 to neutralize the carboxyl group derived from dimethylolpropionic acid to prepare a prepolymer;
A water-dispersed polyurethane production step of adding 150 to 350 parts by weight of water to the polyurethane produced;
Dispersible poly (urethane-acrylic) resin (10 to 35 parts by weight), which is obtained by grafting acrylate to polyurethane by adding at least one of alkyl methacrylate, alkyl acrylate and styrene to 100 parts by weight of water-dispersed polyurethane A manufacturing method of a composition for improving water repellency or water resistance of a substrate comprising a manufacturing step.
The method according to claim 6,
Wherein the polyol in the prepolymer production step comprises a polyol having a number average molecular weight of 200 to 2,000.
The method according to claim 6,
Wherein the isocyanate compound in the preparation step of the prepolymer comprises at least one of isophorone diisocyanate and methylene diphenyl diisocyanate.
The method according to claim 6,
Wherein the prepolymer is prepared by further reacting 0.001 to 0.1 part by weight of a tin catalyst.
The method according to claim 6,
Wherein the catalyst in the carbodiimide group bonding step comprises at least one of phospholene oxide and amine.
The method according to claim 6,
Wherein the step of preparing the water-dispersed poly (urethane-acrylic) resin is performed by using alkyl methacrylate, alkyl acrylate and styrene at a ratio of 7 to 9: 1 to 3: 0.1 to 1.5.
The method according to claim 6,
Wherein the substrate comprises concrete.
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