KR100595530B1 - Acrylic resin composition, waterproofing material including same, and method for manufacturing same - Google Patents

Abstract

The present invention comprises 68 to 77% by weight of one or more alkyl (meth) acrylate monomers; 14 to 16% by weight of styrene monomer; 7 to 10% by weight of acrylonitrile monomers; Provided is a resin composition comprising a copolymer resin emulsion of 1-3 wt% of an unsaturated monomer comprising an acid group and 1-3 wt% of an unsaturated monomer comprising a hydroxyl group, emulsion-polymerized, a waterproofing material including the same, and a method of manufacturing the same.

The resin composition according to the present invention is capable of effective self-crosslinking in a specific monomer composition without a separate crosslinkable monomer or a crosslinking agent, thereby forming a uniform coating film, and having excellent physical properties such as water permeability, adhesion strength, and tensile strength. In addition, the waterproofing material including the resin composition is excellent in waterproof effect and corrosion resistance.

Description

Acrylic resin composition, waterproofing material including same and manufacturing method thereof {Acrylic resin composition, water proofing agent containing the same and manufacturing method

The present invention relates to an acrylic resin composition for forming a coating film by magnetic crosslinking, a waterproofing material including the composition, and a method of manufacturing the same, and more specifically, self-crosslinking is possible and cured at room temperature without a separate curing agent or crosslinking agent to impart water resistance. The present invention relates to an acrylic resin composition capable of forming a coating film having excellent properties, adhesion strength, tensile strength, and the like, a waterproof material provided with the composition, and a method of manufacturing the same.

Due to the development of building technology and civil engineering technology, various kinds of waterproofing techniques and technologies such as sheet waterproofing, concrete waterproofing, coating waterproofing, asphalt waterproofing, metal sheet waterproofing and improved asphalt sheet waterproofing have been developed. However, according to the construction method, there are problems of each feature and specification. These problems include differences in effects after construction, labor costs during reconstruction, ease of construction, aging and deterioration due to ultraviolet rays, absorbency and water repellency problems, and adhesion problems with adhesives. Convenience and economics are becoming a problem in the building repair industry and the waterproof industry.

Conventional general waterproofing material is a two-component waterproofing material, which is disclosed in many prior art such as, for example, Korean Patent Publication No. 2005-0000816. The two-component waterproof material is a mixture of the first liquid of the copolymer emulsion and the second liquid containing cement and the like, and shows good physical properties when properly constructed. However, it requires a lot of time because the compounding is required, the compounding ratio is very important, in practice, this is not strictly observed, the theoretical properties are not well implemented and the coating has been pointed out as a problem.

As an alternative to this, a urethane-based and acrylic-based waterproofing material is generally used as a one-component waterproofing material that is used as it is without mixing. However, since urethane-based waterproofing materials use a large amount of amines and isocyanates as hardeners, they are deteriorated by direct sunlight and the like, resulting in damage to the coating film or rapid cracking, resulting in fine cracks in the coating film, thereby reducing the waterproofing effect. There is a problem that is easy to be damaged by the impact. Regarding such a urethane-based waterproofing material, Japanese Patent Laid-Open No. 1993-17553 can be referred to.

In addition, in the case of acryl series, as a kind of thermosetting resin, self-cross linking is possible by heat and the like, but a separate curing agent is not used, but a crosslinkable monomer or crosslinker is additionally used to promote crosslinking. In this regard, Japanese Patent Publication No. 2004-210845, US Patent Registration No. 5,869,589, and Korean Patent Publication No. 2004-0009140 can be referred to.

Although the crosslinkable monomer or crosslinking agent has an effect of making crosslinking easier, there is a problem of unbalanced coating film formation or gelation in the resin manufacturing process, which adversely affects the physical properties of the copolymer.

Therefore, there is a need for a resin composition capable of crosslinking without separately adding the crosslinkable monomer or crosslinking agent and a waterproofing material including the same.

The technical problem to be achieved by the present invention is to provide an acrylic resin composition which forms a coating film by self-crosslinking without including a crosslinkable monomer or a crosslinking agent.

Another object of the present invention is to provide a waterproof material comprising the acrylic resin composition.

Another technical problem to be achieved by the present invention is to provide a method for producing the acrylic resin emulsion.

The present invention to achieve the above technical problem,

68-77 wt% of at least one alkyl (meth) acrylate monomer;

14 to 16% by weight of styrene monomer;

7 to 10% by weight of acrylonitrile monomers;

1-3 wt% of an unsaturated monomer comprising an acid group; And

1 to 3% by weight of the unsaturated monomer containing a hydroxyl group provides a resin composition comprising an emulsion polymerized copolymer resin emulsion.

According to an embodiment of the present invention, the at least one alkyl (meth) acrylate monomer is n-butyl acrylate, ethyl acrylate, 2-ethyl hexyl acrylate, methyl methacrylate, styrene-based monomers are styrene, acrylic As for a ronitrile-type monomer, it is preferable that the unsaturated monomer containing an acrylonitrile and an acidic group is acrylic acid, and the unsaturated monomer containing a hydroxyl group is 2-hydroxy ethyl methacrylate.

According to one embodiment of the present invention, it is preferable to further include 10 to 70 parts by weight of the emulsion-polymerized ethylene vinyl acetate copolymer emulsion based on 100 parts by weight of the copolymer resin emulsion.

The present invention provides a waterproof material comprising the resin composition in order to achieve the above technical problem.

The present invention to achieve the above other technical problem,

68 to 77% by weight of one or more alkyl (meth) acrylate monomers, 14 to 16% by weight of styrene monomers, 7 to 10% by weight of acrylonitrile monomers, 1 to 3% by weight of unsaturated monomers including acid groups and hydroxyl groups Preparing a monomer dispersion by mixing 1 to 3% by weight of an unsaturated monomer;

Emulsifying and polymerizing 3 to 10% by weight of the monomer dispersion at a temperature of 80 to 90 ℃ to prepare a seed dispersion in which the copolymer seed (dised) is dispersed: And

It provides a method for producing a resin composition comprising the step of additionally adding the remaining monomer dispersion to the seed dispersion by emulsion polymerization at a temperature of 80 to 90 ℃ to prepare a copolymer resin emulsion.

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

Unlike conventional self crosslinkable resin compositions additionally include a crosslinkable monomer or a crosslinking agent to promote crosslinking, the resin composition according to the present invention enables effective self crosslinking in a specific monomer composition without a separate crosslinkable monomer or a crosslinking agent. While forming a uniform coating film, it has excellent physical properties such as water resistance, adhesion strength, and tensile strength. In addition, the waterproofing material including the resin composition is excellent in waterproof effect and corrosion resistance.

The resin composition of the present invention is emulsified by one or more alkyl (meth) acrylate monomers, styrene-based monomers, acrylonitrile and acrylamide, at least one monomer selected from the group consisting of unsaturated monomers including acid groups and unsaturated monomers including hydroxyl groups. Polymerized copolymer resin emulsions.

The at least one alkyl (meth) acrylate monomer is an unsaturated monomer containing neither an acid group nor a hydroxyl group. As for carbon number of alkyl (meth) acrylate, 1-18 are preferable, Specifically, methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, n-butyl (meth) acrylate, iso- Butyl (meth) acrylate, t-butyl (meth) acrylate, hexyl (meth) acrylate, 2-ethyl hexyl (meth) acrylate, octyl (meth) acrylate, nonyl (meth) acrylate, decyl (meth ) Acrylate, dodecyl (meth) acrylate, stearyl (meth) acrylate, mixtures of one or more thereof, and the like.

The styrene monomers include styrene, α-methyl styrene, α-ethyl styrene, mixtures of one or more thereof, and the acrylonitrile monomers include acrylonitrile, methylacrylonitrile, mixtures of one or more thereof, and the like. do.

The acid group-containing unsaturated monomer is an ethylenically unsaturated compound having at least one acid group in a molecule, and the acid group is selected from, for example, a carboxyl group, a sulfonic acid group and a phosphoric acid group.

Specific examples of the carboxyl group-containing unsaturated monomers among the acid group-containing polymerizable monomers include, but are not limited to, acrylic acid, methacrylic acid, ethacrylic acid, propyl acrylic acid, isopropyl acrylic acid, itaconic acid, maleic anhydride and fumaric acid. Specific examples of the sulfonic acid group-containing unsaturated monomers include, but are not limited to, p-vinyl benzene sulfonic acid, p-acrylamide propane sulfonic acid, t-butyl acrylamide sulfonic acid and the like. Specific examples of the phosphoric acid group-containing unsaturated monomers include, but are not limited to, phosphoric acid mono esters of 2-hydroxy ethyl acrylate, phosphoric acid mono esters of 2-hydroxy propyl methacrylate, mixtures of one or more thereof, and the like.

The acid group-containing unsaturated monomer improves overall stability such as storage stability, mechanical stability, and stability against freezing of the copolymer resin emulsion obtained by emulsion polymerization, and acts as a catalyst for promoting crosslinking reaction in forming a coating film. It is preferable to use the monomer containing a carboxylic acid group from the viewpoint of the stability improvement of the said monomer, or the acceleration | stimulation of a crosslinking reaction. It is preferable that the monomer containing a carboxylic acid group occupies at least 50 weight% or more among the said acidic radical containing unsaturated monomers.

Specific examples of the hydroxyl group-containing polymerizable monomer include, but are not limited to, 2-hydroxy ethyl (meth) acrylate, 2-hydroxy propyl (meth) acrylate, 2-hydroxy butyl (meth) acrylate, allyl alcohol and It includes at least one selected from the group consisting of ε-caprolactone modified acrylic monomers.

The hydroxyl group-containing unsaturated monomers impart hydrophilicity based on hydroxyl groups by copolymerization, and increase the workability and stability against freezing, and impart reactivity to the crosslinking reaction when the resin emulsion obtained is used as a waterproofing material.

More specifically, the resin composition of the present invention is 68 to 77% by weight of at least one alkyl (meth) acrylate monomer, 14 to 16% by weight of styrene monomer, 7 to 10% by weight of acrylonitrile monomer, unsaturated monomer containing an acid group 1-3 weight% and 1-3 weight% of unsaturated monomer containing a hydroxyl group contain the emulsion-polymerized copolymer resin emulsion.

In the composition, the alkyl (meth) acrylate has a problem that the coating film is excessively retarded when it exceeds 77% by weight and the coating film is easily cured when it is less than 68% by weight.

The acid group-containing unsaturated monomer has a problem in that the water resistance and alkali resistance of the coating film are lowered when it exceeds 3% by weight, and when the acid group-containing unsaturated monomer is less than 1% by weight, the adhesion of the coating film is decreased.

When the hydroxyl group-containing unsaturated monomer is more than 3% by weight has little effect on the physical properties, when the hydroxyl group-containing unsaturated monomer is less than 1% by weight there is a problem in that the surface of the coating film occurs. Such cracking eventually leads to cracking of the coating film, which degrades the waterproofing performance.

If the styrene-based monomer is more than 16% by weight, there is a problem that the coating film is excessively cured, and if the styrene monomer is less than 14% by weight, the corrosion resistance of the coating film is poor.

If the acrylonitrile-based monomer is more than 10% by weight, there is a disadvantage that a uniform coating film is difficult to be obtained, and when the acrylonitrile monomer is less than 7% by weight, the adhesion to the substrate to be constructed is inferior.

In the case of the resin composition that satisfies the range of the composition, effective self-crosslinking is possible without the addition of a separate crosslinkable monomer or crosslinking agent, and thus, in the case of the barrier member including the resin composition, a coating film having excellent physical properties such as water permeability is uniformly formed. Can be.

In the above resin composition, when the composition of the alkyl (meth) acrylate monomer 68 to 77% by weight is shown in more detail, 30 to 35% by weight of n-butyl acrylate, 9 to 10% by weight of ethyl acrylate, 2-ethyl hexyl acrylate 16-18 weight% and 13-15 weight% of methyl methacrylate are preferable.

The resin composition comprising the specific composition of the alkyl (meth) acrylate monomer is preferably 30 to 35% by weight of n-butyl acrylate, 9 to 10% by weight of ethyl acrylate, 16 to 18% by weight of 2-ethyl hexyl acrylate. %, 13-15 wt% methyl methacrylate, 7-10 wt% acrylonitrile, 14-16 wt% styrene, 1-2 wt% acrylic acid and 1-2 wt% 2-hydroxy ethyl methacrylate And

Most preferably 32% by weight of n-butyl acrylate, 9.5% by weight of ethyl acrylate, 17% by weight of 2-ethyl hexyl acrylate, 14% by weight of methyl methacrylate, 9% by weight of acrylonitrile, 15% by weight of styrene, 1.5% by weight acrylic acid and 2% by weight 2-hydroxy ethyl methacrylate.

The specific composition of the alkyl (meth) acrylate in the resin composition is determined according to the conditions of use at normal room temperature, but the composition can be changed if the conditions used are different.

On the other hand, it is preferable to further comprise 10 to 70 parts by weight of the emulsion-polymerized ethylene vinyl acetate copolymer emulsion based on 100 parts by weight of the copolymer resin emulsion. In particular, it is preferable to further include 10 to 70 parts by weight of an ethylene vinyl acetate copolymer emulsion based on 100 parts by weight (50% by weight of solid content) of the acrylic copolymer resin emulsion. As described above, in the case of additionally including a copolymer emulsion such as ethylene vinyl acetate, the resin composition has an advantage of improving adhesion strength. However, if the additional content is less than 10 parts by weight, the effect on the adhesion strength is insignificant, and if it exceeds 70 parts by weight, there is no significant effect on the increase in adhesion strength. As for the glass transition temperature (Tg) of the said ethylene vinyl acetate copolymer, -15-17 degreeC is preferable. If the glass transition temperature is less than -15 ° C, there is a problem that the coating film formation is too late, and if the glass transition temperature exceeds 17 ° C, the construction is not easy in winter.

The waterproofing material including the resin composition according to the present invention may be prepared by adding various additives in addition to the resin composition. Examples of such additives include emulsifiers, cryoprotectants, preservatives, inorganic dyes, fillers, plasticizers, thickeners, dispersants, antifoaming agents, and the like. In addition to the waterproofing material, it is possible to use the resin composition in all other fields such as paint, which requires the formation of a waterproof and stretchable coating film.

Inorganic fillers may be used to increase the strength, such as carbonate, silicate, sulfate, and more specifically, calcium carbonate, magnesium carbonate, silicon dioxide, calcium sulfate, magnesium sulfate, barium sulfate, and the like.

Emulsifiers are selected from compounds which form micelles which have a hydrophobic hydrocarbon group having at least 6 carbon atoms and a hydrophilic portion of carboxylate, sulfonate or sulfate salt in the molecule, which is essential for emulsion polymerization and for stable dispersion of monomers and copolymers. Anionic or nonionic emulsifiers are used. Among these, anionic emulsifiers include alkali metal salts or ammonium salts of alkyl phenols or higher alcohols sulfuric acid; Alkali metal salts or ammonium salts of alkyl or allyl sulfonates; Sulfate alkali metal salt or ammonium salt of polyoxyethylene alkyl phenol ether, polyoxyethylene alkyl ether, or polyoxyethylene allyl ether, etc. are mentioned. Moreover, polyoxyethylene alkyl phenyl ether, polyoxyethylene alkyl ether, polyoxyethylene allyl ether, etc. are mentioned as a nonionic emulsifier. In addition, they may have unsaturated double bonds in the molecules of general-purpose anionic and nonionic emulsifiers. That is, various anionic and nonionic emulsifiers such as acryl, methacrylic, propenyl, allyl, allyl ether, and maleic acid may be used.

In addition, alkylating compounds are added to neutralize some or all of the carboxylic acid with respect to the waterproofing material comprising the resin composition obtained in the present invention and to protect the safety of the resin emulsion composition contained in the waterproofing material. As these alkaline compounds, ammonia, various amines, alkali metals and the like can be usually used.

The inorganic pigment is added to give a color to the coating film produced by the construction of the waterproofing material, but is not limited to inorganic pigments such as carbon black, iron oxide, titanium dioxide and the like, and organic pigments are also possible.

Antifoaming agent is used to eliminate the bubble phenomenon that occurs during the construction of the waterproofing material. If bubbles occur, the coating film is generated and the adhesion to the substrate is also lowered, which reduces the performance of the coating film. Defoamers used in the present invention may be modified silicone-based, etc. More specifically, for example, Nopco NXZ, Nopco 8034L Nopco NDW, SNDef 154, etc. of SanNopco, but is not limited to these, mineral oil and metal oil may be used.

Preservatives used in the present invention are not particularly limited, but are 2-hydroxy-amino-ethanol, 1,2-benzisothiazoline and the like.

The cryoprotectant may be used to prevent emulsification when the waterproofing material is frozen at low temperature and then melted. Specific examples thereof are not particularly limited, but examples thereof include ethylene glycol and propylene glycol.

In addition, when the viscosity of the composition is too low, it is difficult to install on an inclined surface, etc., so that a thickener is used to secure proper workability. The thickener used in the present invention is not particularly limited, but alkyl cellulose may be used.

Plasticizers are widely used in polymer polymerization, and in the case of the present invention, in the absence of a plasticizer, when the coating film made of the waterproofing material including the resin composition is too hard, cracks and the like easily occur in external impact. The plasticizer used in the present invention is not particularly limited as long as it is used in the art, and an organic solvent or the like can be used.

The composition of the waterproofing material according to the present invention including the above components is 40 to 55% by weight of the copolymer resin composition (50% by weight of solid content), 23 to 53% by weight of inorganic filler, 0.5 to 10% by weight of an emulsifier, and 0.1 to 0.1% of an antifoaming agent. 2.8 wt%, plasticizer 0.9-6 wt%, inorganic dye 0.2-4.3 wt%, pH adjuster 1.5-13 wt%, cryoprotectant 0.5-10 wt%, preservative 0.1-1.1 wt%, thickener 0.05-5 wt% and It is preferable to include the remaining amount of water.

 When the copolymer resin composition is less than 40% by weight in the waterproofing material composition, there is a problem that the three-dimensional crosslinking density is low and the acid resistance is low, and when it exceeds 55% by weight, gelation proceeds and thus long-term stability is deteriorated. If the content of the inorganic filler is less than 23% by weight, there is a problem that the hardness of the coating film is falling, and when the content of the inorganic filler exceeds 53% by weight, the elasticity of the coating film is lowered, so that a crack occurs easily in external impact. Other components fall within the general scope of use used in the art.

On the other hand, when the ethylene vinyl acetate copolymer emulsion further comprises 10 to 70 parts by weight based on 100 parts by weight of the copolymer resin emulsion, specifically, 100 parts by weight of the copolymer resin composition (50 wt% solids) of ethylene vinyl It is preferable to further include 10 to 70 parts by weight of the acetate copolymer emulsion and 5 to 30 parts by weight of the silicate.

The composition of the waterproof material considering the ratio of parts by weight is added 5 to 25% by weight of an ethylene vinyl acetate copolymer emulsion in addition to 30 to 42% by weight of the copolymer resin composition (50% by weight of solid content), and 1 to 20% by weight of a dispersant. , Inorganic filler 23 to 55% by weight, silicate 2 to 15% by weight, emulsifier 0.5 to 9.4% by weight, antifoaming agent 0.1 to 2.5% by weight, plasticizer 1 to 6.8% by weight, inorganic dye 0.2 to 5% by weight, pH adjuster 1.5 to 12.3 It is preferred to include by weight, antifreeze 0.5 to 9.2% by weight, thickener 0.05 to 4.5% by weight and the remaining amount of water.

The manufacturing method of the copolymer resin emulsion contained in the resin composition of this invention is as follows.

First, ion-exchanged water is first introduced into a monomer tank at room temperature and atmospheric pressure, and a surfactant solution is prepared by completely dispersing the surfactant while stirring at a constant rate. While continuously stirring the surfactant solution, 68 to 77% by weight of one or more alkyl (meth) acrylate monomers, 14 to 16% by weight of styrene monomers, 7 to 10% by weight of acrylonitrile monomers, unsaturated monomers including acid groups 1 to 3% by weight of the unsaturated monomer containing 1 to 3% by weight and hydroxyl groups is added to prepare a monomer dispersion.

Next, ion-exchanged water is first introduced into the reaction tank, and the surfactant is added while stirring slowly at a constant speed to completely disperse the temperature, and the temperature is maintained at 80 to 90 ° C. In the monomer tank, 3 to 10% by weight of the monomer dispersion is aliquoted, added to the reaction tank, and a polymerization initiator is added to cause an emulsion polymerization to prepare a seed dispersion in which a seed polymer is produced.

 Then, the remaining monomer dispersion remaining in the monomer tank is slowly added to the seed dispersion together with the polymerization initiator. After the addition of the monomers, while maintaining the temperature of the reaction tank at 80 to 90 ℃ aging the reactants for a certain time to proceed the emulsion polymerization reaction so that the unreacted monomers remain.

After the temperature of the reaction tank is lowered by 5 to 20 ° C., the polymerization initiator is added again and aged for a predetermined time. The process of adding and aging the polymerization initiator is repeated once more.

After aging for a certain time, a part of the emulsion is taken and the amount of the residual monomer is analyzed by GC, LC, etc. to improve the amount of the residual monomer within the allowable value. In addition, buffers such as ammonia water (25 to 28%), triethanolamine and 2-amino-2-methylpropanol are added to adjust the pH to a range of 5.5 to 10.5 to maintain the stability of the emulsion.

The use of a chain transfer agent for molecular weight control such as mercaptan-based compounds and lower alcohols during emulsion polymerization is preferable in terms of advancing the emulsion polymerization and promoting the formation of a uniform coating film and improving adhesion to the substrate. It can be used selectively depending on the situation.

The emulsion polymerization method for preparing the copolymer resin emulsion is preferably, but not limited to, the above-described methods, and the conventional one-stage continuous monomer dropping method, the multi-stage monomer supply method, the core / shell polymerization method, and the composition of the monomers supplied during the polymerization are continuously Other manufacturing methods used in the art, such as a varying power supply polymerization method, can also be used.

Although the weight average molecular weight of the copolymer resin contained in the copolymer resin emulsion manufactured by the method of this invention is not specifically limited, 50,000-1 million are preferable, More preferably, it is 100,000-800,000.

Next, the manufacturing method of the waterproofing material which concerns on this invention is demonstrated.

Other additives are added to the copolymer resin emulsion prepared as described above. They function to adjust the performance of the waterproofing material so that the properties of the waterproofing material are more suitable for the user or the use environment. Specifically, an inorganic filler, an emulsifier, an antifreezing agent, an antiseptic agent, an inorganic dye, a filler, a plasticizer, a thickener and an antifoaming agent are added while stirring the copolymer resin emulsion at a constant speed at room temperature and normal pressure. In this case, inorganic fillers and thickeners are most preferably added for uniform mixing of the additives. Depending on the amount of the additive or the composition of the copolymer handmade emulsion, the solids content of the copolymer resin emulsion used in the waterproofing material can be adjusted up to 48% by weight to 70% by weight, and the viscosity can also be adjusted to 1000 (centipoise) to 12000 cps. It can be used suitably for the construction conditions.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples, which are intended to explain the present invention to those skilled in the art, but the present invention is not limited thereto.

Synthesis of Copolymer Resin Emulsion

Synthesis Example 1

At room temperature and normal pressure, 700 g of ion-exchanged water was first added to the monomer tank, and 50 g of the surfactant was added thereto while slowly stirring at about 120 rpm to completely disperse it. With continuous stirring of the dispersion, 233 g of acrylonitrile, 850 g of n-butyl acrylate, 245 g of ethyl acrylate, 450 g of 2-ethylhexyl acrylate, 370 g of methyl methacrylate, 396 g of styrene monomer, 40 g of acrylic acid and 2-hydroxy ethyl 48 g of methacrylate was added to prepare a monomer emulsion.

Next, 850 g of ion-exchanged water was first introduced into the reaction tank, and the surfactant was added while slowly stirring at about 80 rpm to completely disperse and maintained at 85 ° C. in temperature.

100 g of the monomers dispersed in the monomer tank was added to the reaction tank, and then allowed to stand for 3 minutes, followed by 50 g of a 10% by weight solution of ammonium bicarbonate. After clarifying again for 4 minutes, 60 g of a 10% by weight solution of persulfate sodium salt was added to initiate the reaction to produce a seed polymer.

After waiting for about 8 minutes, the polymer tank is slowly added with 60 g of the persulfate sodium salt solution to the reaction tank in which the polymer seed is dispersed. Adjust the dosing time so that the total dosing time is about 3 hours. After the addition of the monomer, the reaction was aged for about 60 minutes while maintaining the temperature of the reaction tank at 85 ° C. to proceed with the polymerization so that no unreacted monomer remained.

After the temperature of the reaction tank was lowered to 75 ° C., 40 g of 10 wt% t-butyl hydroperoxide solution was added thereto, and aged for about 30 minutes. The polymerization initiator was added and aged for about 30 minutes.

About 1 g of the copolymer resin emulsion thus obtained was collected and the amount of residual monomer was analyzed by GC to further mature until the amount of residual monomer became 0.2 to 0.15% by weight or less.

In order to increase the stability of the emulsion, etc., the pH of the emulsion was also adjusted to 6.5 to 10.5 by adding a buffer solution (25-10% aqueous ammonia) to maintain the stability of the emulsion.

Synthesis Example 2

A copolymer resin emulsion was prepared in the same manner as in Synthesis Example 1, except that 30 g of acrylic acid and 32 g of 2-hydroxy ethyl methacrylate were used in Synthesis Example 1 and 876 g of n-butyl acrylate was used instead.

Synthesis Example 3

A copolymer resin emulsion was prepared in the same manner as in Synthesis Example 1, except that 50 g of acrylic acid and 64 g of 2-hydroxy ethyl methacrylate were used in Synthesis Example 1 and 824 g of n-butyl acrylate was used instead.

Synthesis Example 4

A copolymer resin emulsion was prepared in the same manner as in Synthesis Example 1, except that 20 g of acrylic acid and 16 g of 2-hydroxy ethyl methacrylate were used in Synthesis Example 1 and 902 g of n-butyl acrylate was used instead.

Synthesis Example 5

A copolymer resin emulsion was prepared in the same manner as in Synthesis Example 1, except that 75 g of acrylic acid and 80 g of 2-hydroxy ethyl methacrylate were used in Synthesis Example 1 and 783 g of n-butyl acrylate was used instead.

Waterproof material manufacturer

Examples 1 to 3

A waterproof material including the copolymer resin composition according to Synthesis Examples 1 to 3 was prepared. Various additives were prepared to the resin composition.

2275 g of the copolymer resin emulsion (50 wt% solids) prepared in Synthesis Examples 1 to 3 was added to a 10 L container, where 60 g of octoxynol 40, 100 g of PEG, 45 g of paraffinic solvent, 26 g of mineral oil defoaming agent, and isothia 13 g of isothiazolin, 1242 g of calcium carbonate, 190 g of titanium dioxide (TiO ₂ ), 135 g of texanol, 200 g of triethanolamine, 140 g of methylcellulosolve, 224 g of ammonium chloride A one-component waterproof was prepared by adding an amount of water to make 5000 g.

Example 4

1562 g of the copolymer resin emulsion (50 wt% solids) prepared according to Synthesis Example 1 was added to a 10 L container, and 500 g of ethylene vinyl acetate copolymer, 250 g of butyl carbitol, and 220 g of silicate were further added. Here, 56 g of octoxynol 40, PEG 88 g, paraffin solvent 40 g, mineral oil defoamer 8 g, isothiazolin 4 g, calcium carbonate 1288 g, titanium dioxide (TiO ₂ ) 218 g, texanol 105g, triethanolamine 110g, methylcellulosolve 150g, ammonium chloride 150g were added, and the remaining amount of water was added to make 5000g to prepare a one-component waterproofing material.

Comparative Examples 1 and 2

One-component waterproofing agents were prepared in the same manner as in Examples 1 to 3, except that the copolymer resin emulsions synthesized in Synthesis Examples 4 and 5 were used, respectively.

Comparative Example 3

A commercial one-component waterproofing agent (Australia, Norcros, trade name superflex I) was used.

Experimental Example: Performance Evaluation of Waterproofing Film

5 g of each of the waterproofing materials prepared according to Examples 1 to 4 and Comparative Examples 1 to 2 and the waterproofing material of Comparative Example 3 were coated on a glass chalet, and dried for 5 days at room temperature for outdoor drying. The film was peeled from the glass chalet and the performance of the peeled film was tested by the KS F 4919-98 method and the results are shown in Table 1 below.

Adhesion Strength (N / cm ² ) Creep resistance Absorption amount (g) Water resistance Tensile Strength (N / cm ² ) Elongation (%) Tear strength (N / cm) Example 1 164 clear 1.0 clear 181 309 82 Example 2 162 clear 0.9 clear 178 315 80 Example 3 167 clear 1.1 clear 185 302 85 Example 4 180 clear 1.0 clear 178 320 70 Comparative Example 1 148 Minute ripples 0.9 clear 155 350 70 Comparative Example 2 170 clear 1.3 Slight leakage 190 300 86 Comparative Example 3 150 Minute ripples 1.2 clear 180 310 80 KS Standard 80 or more No surface cracking on the surface of waterproof layer 2.0 or less Not permeable at water pressure of 30 N / cm ² 100 or more 50 or more 50 or more

As shown in Table 1, when the contents of acetic acid and 2-hydroxy ethyl methacrylate, which are monomers containing an acid group or a hydroxyl group in Examples 1 to 3, are in the range of 1 to 2.5% by weight of the total weight of the monomer in the synthesis example, respectively Without a crosslinkable monomer or a crosslinking agent, the waterproofing material having excellent physical properties such as water permeability, adhesion strength and tensile strength could be produced by self-crosslinking. In addition, in Example 4, even when ethylene vinyl acetate was additionally added to the basic composition of the waterproofing material, good adhesion strength was shown. On the contrary, in Comparative Examples 1 and 2, the content of the monomer containing the acid group or the hydroxyl group was relatively out of the proper composition of the present invention. The waterproofing materials of Examples 1 to 4 passed KS standards in all evaluation items and showed improved physical properties compared to products on the market (Comparative Example 3).

As described above, the resin composition according to the present invention is capable of effective self-crosslinking in a specific monomer composition without a separate crosslinkable monomer or a crosslinking agent to form a uniform coating film, while having water permeability, adhesion strength and tensile strength. great. In addition, the waterproofing material including the resin composition is excellent in waterproof effect and corrosion resistance.

Claims (7)

68-77 wt% of at least one alkyl (meth) acrylate monomer; 14 to 16% by weight of styrene monomer; 7 to 10% by weight of acrylonitrile monomers; 1-3 wt% of an unsaturated monomer comprising an acid group; And 1 to 3% by weight of the unsaturated monomer containing a hydroxyl group comprises a copolymer resin emulsion emulsion polymerized. The method of claim 1, wherein the at least one alkyl (meth) acrylate monomer is n-butyl acrylate, ethyl acrylate, 2-ethyl hexyl acrylate, methyl methacrylate, and the styrene monomer is styrene or acrylonitrile. The unsaturated monomer containing an acrylonitrile and an acidic radical in a monomer is acrylic acid and the unsaturated monomer containing a hydroxyl group are 2-hydroxy ethyl methacrylate, The resin composition characterized by the above-mentioned. The resin composition of claim 1, further comprising 10 to 70 parts by weight of the emulsion-polymerized ethylene vinyl acetate copolymer emulsion based on 100 parts by weight of the copolymer resin emulsion. A waterproofing material comprising the resin composition according to any one of claims 1 to 3. The method according to claim 4, wherein the copolymer resin composition 40 to 55% by weight, inorganic filler 23 to 53% by weight, emulsifier 0.5 to 10% by weight, antifoaming agent 0.1 to 2.8% by weight, plasticizer 0.9 to 6% by weight, inorganic dye 0.2 to Waterproofing material comprising 4.3% by weight, pH adjuster 1.5 to 13% by weight, cryoprotectant 0.5 to 10% by weight, preservative 0.1 to 1.1% by weight, thickener 0.05 to 5% by weight and the remaining amount of water. The method of claim 4, further comprising an ethylene vinyl acetate copolymer emulsion, 30 to 42 wt% of the copolymer resin composition, 5 to 25 wt% of ethylene vinyl acetate copolymer emulsion, 1 to 20 wt% of dispersant, 23 to 55 wt% of inorganic filler, 2 to 15 wt% of silicate, 0.5 to 9.4 wt% of emulsifier %, Antifoam 0.1 to 2.5%, plasticizer 1 to 6.8%, inorganic dye 0.2 to 5%, pH adjuster 1.5 to 12.3%, cryoprotectant 0.5 to 9.2%, thickener 0.05 to 4.5% and the remaining amount Waterproofing material comprising water. 68 to 77% by weight of one or more alkyl (meth) acrylate monomers, 14 to 16% by weight of styrene monomers, 7 to 10% by weight of acrylonitrile monomers, 1 to 3% by weight of unsaturated monomers including acid groups and hydroxyl groups Preparing a monomer dispersion by mixing 1 to 3% by weight of an unsaturated monomer; Emulsifying and polymerizing 3 to 10% by weight of the monomer dispersion at a temperature of 80 to 90 ℃ to prepare a seed dispersion in which the copolymer seed (dised) is dispersed: And Preparing a copolymer resin emulsion by additionally adding the remaining monomer dispersion to the seed dispersion by emulsion polymerization at a temperature of 80 to 90 ° C .; Method for producing a resin composition comprising a.