KR20230114563A - Binder composition for high elongation and high elasticity waterproofing agent - Google Patents

Abstract

The present invention relates to a binder for a waterproofing agent having high elongation and high elasticity, and more particularly, an aqueous ethylenically unsaturated monomer copolymer emulsion resin having a self-crosslinking function at room temperature and a silicone having a hydroxyl group (-OH) at both ends. It relates to a binder composition for a waterproofing agent in which a water-dispersible silicone-modified polyurethane resin using oil is blended.
In the present invention, in order to provide a high elongation and high elasticity binder composition for a waterproofing agent capable of protecting a base material from moisture without breaking, cracking, or tearing of a coating film even when contraction, expansion, or twisting occurs in a building due to temperature or external force, aqueous ethylene Measures such as appropriately blending the unsaturated monomer copolymer emulsion resin and the water-dispersible silicone-modified polyurethane resin to which the silicone oil was applied were applied.

Description

Binder composition for high elongation and high elasticity waterproofing agent {Binder composition for high elongation and high elasticity waterproofing agent}

The present invention relates to a binder for a waterproofing agent having high elongation and high elasticity, and more particularly, an aqueous ethylenically unsaturated monomer copolymer emulsion resin having a self-crosslinking function at room temperature and a silicone having a hydroxyl group (-OH) at both ends. It relates to a binder composition for a waterproofing agent in which a water-dispersible silicone-modified polyurethane resin using oil is blended.

A waterproofing agent is a chemical that is applied to the surface of a substrate to form a moisture permeable barrier to protect the substrate from moisture, and is used in various places such as civil engineering and construction.

The present invention relates to a high elongation and high elasticity waterproofing agent binder composition capable of protecting a substrate from moisture without cracking, cracking, or tearing of a coating film even when a building is contracted, expanded, or twisted by temperature or external force. In order to compensate for the insufficient elongation and elasticity of the unsaturated monomer copolymer emulsion resin, a room temperature self-crosslinking material is added and a silicone-modified aqueous dispersion silicone-modified polyurethane resin is blended with the synthesized resin to provide a waterproofing agent binder composition with supplemented mechanical properties.

Currently, there are various types of buildings, but most buildings other than factories or warehouses are made of building materials such as steel bars, steel frames, and concrete. Concrete is a building material with good strength and durability, but it is easy to penetrate moisture, and if it is continuously exposed to moisture, durability problems arise.

Causes of deterioration in the durability of buildings include stress due to unevenly occurring external forces, stress due to internally generated continuous loads, and stress due to repeated contraction and expansion of building materials due to temperature changes. As it works, cracks or twists occur, and moisture penetrates easily, reducing the durability of concrete, reinforcing bars, and steel structures. Due to these problems, waterproof construction is essential in spaces where rainwater, condensation, and water for living are frequently used, such as rooftops, exterior walls, underground parking lots, bathrooms, and verandas.

The waterproofing agent required for such waterproof construction varies depending on the application area and characteristics. Currently commercially available waterproofing agents include epoxy, urethane, inorganic elastic coating film, cement liquid waterproofing agent, etc. Liquid composition includes a two-component type consisting of a main agent and a hardener, and a one-component type consisting of a moisture curing type and natural drying type.

Epoxy and urethane, which are especially widely used among waterproofing agents, have many solvent types. The solvents used are organic compounds that cause air pollution and are highly volatile, so they are easily inhaled and can cause problems with the respiratory system and skin when exposed for a long time. In addition, in the case of a urethane curing agent, isocyanate and diisocyanate compounds having cyanide ions are the main components, and these compounds generally have strong toxicity, and when exposed for a long time, there is a risk of carcinogenicity and reproductive toxicity. In addition, epoxy or urethane has excellent mechanical properties such as water resistance, chemical resistance, and abrasion resistance in terms of physical properties, but epoxy has poor weather resistance, so whitening, cracking, and gloss loss occur when exposed to ultraviolet rays for a long time. Urethane is also a raw material. As a result, yellowing may occur.

In order to improve this problem, it is required to develop a waterproofing agent binder that considers not only physical properties but also environmental aspects as a water-based binder by blending two or more resins with good compatibility with the waterproofing agent to modify and compensate for the inherent disadvantages of a single resin.

The purpose of the present invention is to provide a high elongation and high elasticity binder composition for a waterproofing agent capable of protecting a base material from moisture without cracking, cracking, or tearing of a coating film even when contraction, expansion, or twisting occurs in a building due to temperature or external force. there is.

To this end, in the present invention, a waterproofing agent binder composition having the desired effect was obtained by properly blending an aqueous ethylenically unsaturated monomer copolymer emulsion resin and a water-dispersible silicone-modified polyurethane resin to which silicone oil was applied.

The liquid binder composition for a waterproofing agent of the present invention for solving the above problems is

A liquid binder composition for a waterproofing agent comprising an aqueous ethylenically unsaturated monomer copolymer emulsion resin, a water-dispersible silicone-modified polyurethane resin, and ion-exchanged water,

The aqueous ethylenically unsaturated monomer copolymerization emulsion resin is a copolymer obtained by copolymerization of at least one hydrophobic ethylenically unsaturated monomer and at least one hydrophilic ethylenically unsaturated monomer in the presence of a surfactant and a water-soluble polymerization initiator. resin, and the aqueous ethylenically unsaturated monomer copolymer emulsion resin is a resin having a self-crosslinking function at room temperature,

The water-dispersible silicone-modified polyurethane resin includes one polyester polyol, one polydimethylsiloxane diol, one ionic group compound, one isocyanate or diisocyanate compound, and a solvent, a neutralizer, a diluting solvent, and a dispersion medium. Characterized in that it is a resin of 33 to 37% by weight.

At this time, the isocyanate or diisocyanate compound is a liquid binder composition for a waterproofing agent, characterized in that dicyclohexylmethane-4,4-diisocyanate.

In addition, the aqueous ethylenically unsaturated monomer copolymer emulsion resin contains 30 to 40 parts by weight of diacetone acrylamide and 6 to 12 parts by weight of adipic acid dihydrazide as a room temperature self-crosslinking agent to have a self-crosslinking function at room temperature Characterized in that it is a resin.

In addition, in the present invention as described above, the blending ratio of the aqueous ethylenically unsaturated monomer copolymer emulsion resin and the water-dispersible silicone-modified polyurethane resin is characterized in that the weight ratio is 8: 1.5 to 2.5.

In addition, the surfactant is a sulfate-based anionic surfactant,

The water-soluble polymerization initiator is characterized in that any one of sodium persulfate, potassium persulfate, and ammonium persulfate.

In addition, the aqueous ethylenically unsaturated monomer copolymer emulsion resin has a molecular weight of 800,000 to 1,000,000 and a viscosity of 900 to 1,200 cps,

The water-dispersible silicone-modified polyurethane resin has a molecular weight of 20,000 to 50,000 and a viscosity of 10 to 100 cps.

If the numerical range is not specified above, it is not a feature of the present invention per se, and it is because those skilled in the art can properly determine the content as needed.

The composition according to the present invention is a water-based binder for a one-component waterproofing agent that emits less VOC than a two-component type that uses an existing organic solvent. It is significantly reduced, and appropriate tensile strength and elasticity can be obtained by blending the water-dispersible silicone-modified polyurethane resin with silicone oil incorporating the poor physical properties of the acrylic emulsion resin itself.

Hereinafter, the present invention will be described with specific examples. However, the following examples are intended to aid understanding of the present invention and are not intended to limit the scope thereof.

Aqueous ethylenically unsaturated copolymer emulsion resin composition

The term “seed” refers to a basic initial particle polymer synthesized from 5 to 10% by weight of an emulsion resin preemulsion to uniformly grow the particle size of emulsion polymerization.

The average particle size of the swollen seed polymer is 130 nm to 180 nm.

The surfactant of the aqueous ethylenically unsaturated monomer copolymer emulsion resin is an anionic surfactant, for example, alkyl sulfate, ether sulfate, phosphate esters, sulfonate, sulfosac sulfosuccinates, mono-ester sulfosuccinates, preferably sulfonates, sulfosuccinates, mono-ester sulfosuccinates.

The polymerization initiator of the aqueous ethylenically unsaturated monomer copolymer emulsion resin is a water-soluble initiator, for example, sodium persulfate, potassium persulfate, ammonium persulfate, tertiary hydroperoxide ( tert-butyl hydroperoxide), 2,2'-azobis-(2-methylpropionamidine)dihydrochloride (2,2'-azobis(2-methylpropionamidine)dihydrochloride, preferably sodium persulfate ), potassium persulfate, and ammonium persulfate.

The aqueous ethylenically unsaturated monomer copolymer emulsion resin is formed by at least one hydrophobic ethylenically unsaturated monomer and at least one hydrophilic ethylenically unsaturated monomer. The hydrophobic or hydrophilic ethylenic monomer is not particularly limited as long as it is hydrophobic or hydrophilic, respectively, and may be appropriately selected from general polymerized monomers.

For example, the ethylenically unsaturated hydrophobic monomer is styrene, butyl acrylate, butyl methacrylate, isobutyl acrylate, methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, 2-ethylhexyl acrylate , 2-ethylhexyl methacrylate, benzyl acrylate, benzyl methacrylate, lauryl acrylate, lauryl methacrylate, stearyl acrylate, stearyl methacrylate, vinyltoluene, ethylene, butadiene, vinyl acetate, Acrylonitrile, acrylamide, 2-hydroxyethyl acrylate, glycidyl methacrylate, preferably methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, butyl acrylate, butyl methacrylate acrylate, 2-ethylhexyl acrylate, 2-ethylhexyl methacrylate, styrene, and acrylonitrile.

Ethylenically unsaturated hydrophilic monomers are, for example, acrylic acid, methacrylic acid, itaconic acid, linoleic acid, aconitic acid, crotonic acid, maleic acid, maleic anhydride, linseed oil, fumaric acid, preferably acrylic acid, methacrylic acid, itaconic acid, Conic acid, maleic acid.

The aqueous ethylenically unsaturated monomer copolymer emulsion resin is a room temperature self-crosslinking monomer, for example, acetoacetoxyethyl methacrylate, diacetone acrylamide-adipic acid dihydrazide ), preferably diacetone acrylamide-adipic acid dihydrazide.

The aqueous ethylenically unsaturated monomer copolymer emulsion resin is a neutralizing agent, for example, ammonium hydroxide, dimethylethanolamine, triethanolamine, diethanolamine, propanolamine, Diethanol-isopropanolamine, sodium hydroxide, potassium carbonate, sodium bicarbonate, potassium bicarbonate, 2-amine-2-methyl-1-propanol (2 -amine-2-methyl-propanol), preferably aqueous ammonia, 2-amine-2-methyl-1-propanol, and diethanol isopropanolamine.

Here, the content of the ethylenic copolymer contained in the aqueous ethylenically unsaturated monomer copolymer emulsion resin may be 40 to 55% by weight based on the total weight of the ethylenically unsaturated monomer copolymer emulsion resin. When the content of the water-soluble ethylenically unsaturated monomer copolymer emulsion resin is less than 40% by weight, the resin cannot sufficiently function as a waterproofing agent binder, and when it exceeds 55% by weight, the dispersibility of other mixtures of the waterproofing agent binder is reduced. can

Water-dispersed silicone-modified polyurethane resin composition

The water-dispersible silicone-modified polyurethane resin is a main polyol, for example, a hydroxyl value (mg KOH / g) of 545 to 585 and a number average molecular weight of 200 polyester polyol (polyethylene glycol)-based polyol, hydroxyl value (mg KOH /g) 356~395, number average molecular weight 300 polyester polyol, hydroxyl value (mg KOH/g) 265~295, number average molecular weight 400 polyester polyol, hydroxyl value (mg KOH/g) 150~170, number average molecular weight 700 polyester polyol, hydroxyl value (mg KOH/g) 145 to 155, number average molecular weight 750 polyester polyol, hydroxyl value (mg KOH/g) 108 to 116, number average molecular weight 1,000 polyester polyol, hydroxyl value (mg KOH /g) 54~58, number average molecular weight 2,000 polyester polyol, hydroxyl value (mg KOH/g) 33~37, number average molecular weight 3,200 polyester polyol, hydroxyl value (mg KOH/g) 26.5~29.5, number average molecular weight 4,000 polyester polyol, preferably hydroxyl value (mg KOH / g) 54 to 58, number average molecular weight 2,000 polyester polyol, hydroxyl value (mg KOH / g) 33 to 37, number average molecular weight 3,200 polyester polyol, hydroxyl value (mg KOH/g) 26.5-29.5, number average molecular weight 4,000 polyester polyol.

The water-dispersed silicone-modified polyurethane resin is an auxiliary polyol, for example,

Hydroxyl value (mg KOH/g) 650~700, number average molecular weight 250 polypropylene glycol polyol, hydroxyl value (mg KOH/g) 540~580, number average molecular weight 300 polypropylene glycol polyol, hydroxyl value (mg KOH/g) 385 to 415, number average molecular weight 400 polypropylene glycol polyol, hydroxyl value (mg KOH/g) 265 to 295, number average molecular weight 600 polypropylene glycol polyol, hydroxyl value (mg KOH/g) 230 to 250, number average molecular weight 700 polypropylene glycol polyol, hydroxyl value (mg KOH/g) 158 to 178, number average molecular weight 1,000 polypropylene glycol polyol, hydroxyl value (mg KOH/g) 110 to 114, number average Molecular weight 1,500 polypropylene glycol-based polyol, hydroxyl value (mg KOH/g) 54-58, number average molecular weight 3,000 polypropylene glycol-based polyol, hydroxyl value (mg KOH/g) 40-44, number average molecular weight 4,000 polypropylene glycol-based Polyol, hydroxyl value (mg KOH / g) 31 ~ 35, number average molecular weight 5,000 polypropylene glycol-based polyol, hydroxyl value (mg KOH / g), number average molecular weight 5,000 polydimethylsiloxane diol (Polydimethylsiloxane diol), preferably It is polydimethylsiloxane diol with a number average molecular weight of 5,000.

An ionic compound may be introduced for the water dispersibility of the water-dispersible silicone-modified polyurethane resin. For example, dimethylolpropionic acid, dimethylolbutanoic acid, dimethylolbutyric acid, dimethylolbutyric acid, dimethylol valeic acid, N-dimethyldiethanolamine, preferably dimethylpropionic acid or dimethylolbutanoic acid.

As the diluted organic solvent for recovery of the water-dispersible silicone-modified polyurethane resin, lower alcohol, propylene glycol, butylene glycol, glycerin, acetone, diethyl ether, hexane, ethyl acetate, butyl acetate, methyl ethyl ketone, preferably acetone , hexane, methyl ethyl ketone.

The isocyanate or diisocyanate of the water-dispersible silicone-modified polyurethane resin is not particularly limited, and may be a polyisocyanate compound having three isocyanate functional groups. For example, p-phenylene diisocyanate, 1,6-hexamethylene diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4 -Diisocyanate (dicyclohexylmethane-4,4-diisocyanate), preferably dicyclohexylmethane-4,4-diisocyanate.

An aqueous product of the water-dispersed silicone-modified polyurethane resin may be neutralized with a neutralizing agent. The neutralizing agent is a neutralizing agent that neutralizes an anionic group, for example, triethanolamine, tributylamine, triethylamine, trimethylamine, N,N-dimethylethanolamine (N ,N-dimethylethanolamine), N,N-dimethylpropanolamine, N,N-dipropylethanolamine, preferably triethylamine or triethanolamine.

Here, the content of the polyol, silicone oil, ionic group compound, and isocyanate or diisocyanate contained in the water-dispersible silicone-modified polyurethane resin may be 33 to 37% by weight based on the total weight of the water-dispersible silicone-modified polyurethane resin. there is. When the content of the water-dispersible silicone-modified polyurethane resin is less than 33% by weight, the resin cannot sufficiently function as a waterproofing auxiliary binder, and when it exceeds 37% by weight, miscibility of the waterproofing agent binder may deteriorate.

Binder composition for high elongation and high elasticity waterproofing agent

The composition of the binder for high elongation and high elasticity waterproofing agent is a blend of the aqueous ethylenically unsaturated copolymer emulsion resin polymeric compound and the water-dispersible silicone-modified polyurethane resin polymeric compound in a specific ratio, and the aqueous ethylenically unsaturated monomer copolymerized emulsion resin is for waterproofing agent It may be 70 to 90% by weight based on the total weight of the binder, and the water-dispersed silicone-modified polyurethane resin may be 10 to 30% by weight based on the total weight of the binder for the waterproofing agent, and in the most preferred case, the mutual ratio is 8 : In the case of a weight ratio of 1.5 to 2.5.

[Synthesis Example]

(1) Preparation of aqueous ethylenically unsaturated monomer copolymer emulsion resin 1

First, a polymerization reactor equipped with an agitator, a condenser, and two injection funnels capable of stirring is prepared, 135 to 150 parts by weight of ion-exchanged water is added to the polymerization reactor, heated to a temperature of 75 to 85 ° C, and one injection funnel capable of stirring 160-170 parts by weight of ion-exchanged water, 55-65 parts by weight of Koremul 707SF (Han Nong Chemical), 340-360 parts by weight of normal butyl acrylate (BASF Korea), 120-130 parts by weight of acrylonitrile (Rhino Chemical), normal butyl A preliminary emulsion was prepared by adding 45 to 55 parts by weight of methacrylate (LGMA) and 2 to 6 parts by weight of acrylic acid (Daelim Corporation). When the temperature of the polymerization reactor is heated to 80 ~ 82 ℃, 5 ~ 10% by weight of the pre-emulsion is introduced into the reactor, 4 ~ 6 parts by weight of ion-exchanged water and 0.5 ~ 1.0 parts by weight of ammonium persulfate (Changdae Chemical) are introduced into the reactor to Polymerized for minutes to generate seeds. Thereafter, a mixed solution of 45 to 55 parts by weight of ion-exchanged water and 1.0 to 1.5 parts by weight of ammonium persulfate (Changdae Chemical) was uniformly added to the remaining pre-emulsion at 80 ° C. for 240 minutes. Thereafter, a mixed solution of 4 to 6 parts by weight of ion-exchanged water and 0.5 to 1.0 parts by weight of ammonium persulfate (Changdae Chemical) was introduced into the injection funnel for 30 minutes to post-treat residual monomers. After that, the temperature of the reactor is cooled to 40 ° C., and 5 to 15 parts by weight of ion-exchanged water and 2 to 3 parts by weight of 28% by weight of ammonia aqueous solution (Gene Chemical) are added, and the reaction is terminated. , An aqueous ethylenically unsaturated monomer copolymer emulsion resin composition having a Brookfield viscosity of 1,100 ± 300 poise and a pH of 8 to 9 at 25 ° C was obtained.

(2) Preparation of aqueous ethylenically unsaturated monomer copolymer emulsion resin 2

First, a polymerization reactor equipped with an agitator, a condenser, and two injection funnels capable of agitation is prepared, 145 to 155 parts by weight of ion exchange water is added to the polymerization reactor, heated to a temperature of 75 to 85 ° C, and one injection funnel capable of stirring 160-170 parts by weight of ion-exchanged water, 55-65 parts by weight of Koremul 707SF (Han Nong Chemical), 10-20 parts by weight of diacetone acrylamide (KJ Chemicals), 350-360 parts by weight of normal butyl acrylate (BASF Korea), A preliminary emulsion was prepared by adding 118 to 128 parts by weight of acrylonitrile (Rhino Chemical), 43 to 53 parts by weight of normal butyl methacrylate (LGMMA), and 2 to 6 parts by weight of acrylic acid (Daelim Corporation). When the temperature of the polymerization reactor is heated to 80 ~ 82 ℃, 5 ~ 10% by weight of the pre-emulsion is introduced into the reactor, 4 ~ 6 parts by weight of ion exchange, and 0.5 ~ 1.0 parts by weight of ammonium persulfate (Changdae Chemical) are introduced into the reactor to 30 Polymerized for minutes to generate seeds. Thereafter, a mixed solution of 45 to 55 parts by weight of ion-exchanged water and 1.0 to 1.5 parts by weight of ammonium persulfate (Changdae Chemical) was uniformly added to the remaining pre-emulsion at 80 ° C. for 240 minutes. Thereafter, a mixed solution of 4 to 6 parts by weight of ion-exchanged water and 0.5 to 1.0 parts by weight of ammonium persulfate (Changdae Chemical) was introduced into the injection funnel for 30 minutes to post-treat residual monomers. Thereafter, the reactor temperature is cooled to 40 ° C., and 2 to 8 parts by weight of ion exchange water, 6 to 12 parts by weight of adipic acid dihydrazide (KJ Chemicals), and 28% by weight of ammonia aqueous solution (Zin Chemical) are mixed with 2 to 3 parts by weight. After adding parts by weight, the reaction was terminated to obtain an aqueous ethylenically unsaturated monomer copolymer emulsion resin composition having a non-volatile content of 53 to 57% by weight, a Brookfield viscosity of 900 ± 300 poise at 25 ° C, and a pH of 8 to 9.

(3) Preparation of aqueous ethylenically unsaturated monomer copolymer emulsion resin 3

First, a polymerization reactor equipped with an agitator, a condenser, and two injection funnels capable of stirring is prepared, 145 to 155 parts by weight of ion exchange water is added to the polymerization reactor, heated to a temperature of 75 to 85 ° C, and one injection funnel capable of stirring 160-170 parts by weight of ion-exchanged water, 55-65 parts by weight of Koremul 707SF (Han Nong Chemical), 30-40 parts by weight of diacetone acrylamide (KJ Chemicals), 340-350 parts by weight of normal butyl acrylate (BASF Korea), A preliminary emulsion was prepared by adding 118 to 128 parts by weight of acrylonitrile (Nino Chemical), 43 to 53 parts by weight of normal butyl methacrylate (BASF Korea), and 2 to 6 parts by weight of acrylic acid (LGMMA). When the temperature of the polymerization reactor is heated to 80 ~ 82 ℃, 5 ~ 10% by weight of the pre-emulsion is introduced into the reactor, 4 ~ 6 parts by weight of ion-exchanged water, and 0.5 ~ 1.0 parts by weight of ammonium persulfate (Changdae Chemical) are introduced into the reactor to 30 Polymerized for minutes to generate seeds. Thereafter, a mixed solution of 45 to 55 parts by weight of ion-exchanged water and 1.0 to 1.5 parts by weight of ammonium persulfate (Changdae Chemical) was uniformly added with the rest of the pre-emulsion at 80° C. for 240 minutes. Thereafter, a mixed solution of 4 to 6 parts by weight of ion-exchanged water and 0.5 to 1.0 parts by weight of ammonium persulfate (Changdae Chemical) was introduced into the injection funnel for 30 minutes to post-treat residual monomers. Then, the temperature of the reactor is cooled to 40° C., and 2 to 8 parts by weight of ion-exchanged water, 6 to 12 parts by weight of adipic acid dihydrazide (KJ Chemicals), and 28% by weight of aqueous ammonia solution (Zin Chemical) are mixed with 2 to 3 parts by weight. After adding parts by weight, the reaction was terminated to obtain an aqueous ethylenically unsaturated monomer copolymer emulsion resin composition having a non-volatile content of 53 to 57% by weight, a Brookfield viscosity of 900 ± 300 poise at 25 ° C, and a pH of 8 to 9.

(4) Synthesis of water-dispersible silicone-modified polyurethane resin 1

First, 170 to 180 parts by weight of Konix PP-2000 (KPX Chemical), 15 to 25 parts by weight of Konix GP-5000 (KPX Chemical), dimethylpropionic acid ( Sunjin Chemitech) 15 to 25 parts by weight and N-ethyl-2-pyrrolidone (Duruchem) 60 parts by weight were added and heated to 70 to 80 ° C. to completely dissolve dimethylolpropionic acid. Thereafter, the reactor was cooled to 50° C., 125 to 135 parts by weight of isophorone diisocyanate (Daesung Fine-Chem) was added, heated to 80 to 90° C. for 60 minutes, and maintained for 240 minutes. After that, 80 to 120 parts by weight of acetone (Kumho P&B Chemicals) was added, diluted, and NCO% was measured to confirm that the theoretical value was 1.5% to 3.5%, and the temperature of the polymerization reactor was cooled to 50 to 60 ° C. (The Chem) was neutralized by adding 10 to 15 parts by weight. Thereafter, 570 to 590 parts by weight of ion-exchanged water was put into a dispersion tank for dispersion and stirred, and the prepared polymer was added to induce additional molecular weight growth. Then, the dispersion tank is heated to 60 ℃, the used acetone is recovered with a vacuum pump and the reaction is terminated, and the non-volatile content is 33 to 37% by weight, Brookfield viscosity is 50 to 100 poise at 25 ℃, pH is 7 to 9 A phosphorus water-dispersed silicone-modified polyurethane resin composition was obtained.

(5) Synthesis of water-dispersed silicone-modified polyurethane resin 2

First, 185 to 195 parts by weight of Konix PP-2000 (KPX Chemical), 5 to 15 parts by weight of polydimethylsiloxane diol (Shin-Etsu), dimethylpropionic acid (Seonjin Chemitech) 15 to 25 parts by weight and N-ethyl-2-pyrrolidone (Duruchem) 60 parts by weight were added and heated to 70 to 80 ° C. to completely dissolve dimethylolpropionic acid. Thereafter, the reactor was cooled to 50 ° C, 122 to 132 parts by weight of isophorone diisocyanate (Daesung Fine-Chem) was added, heated to 80 to 90 ° C for 60 minutes, and maintained for 240 minutes. After that, 80 to 120 parts by weight of acetone (Kumho P&B Chemicals) was added, diluted, and NCO% was measured to confirm that the theoretical value was 1.5% to 3.5%, and the temperature of the polymerization reactor was cooled to 50 to 60 ° C. (The Chem) was neutralized by adding 10 to 15 parts by weight. Thereafter, 570 to 590 parts by weight of ion-exchanged water was put into a dispersion tank for dispersion and stirred, and the prepared polymer was added to induce additional molecular weight growth. Then, the dispersion tank is heated to 60 ℃, the used acetone is recovered with a vacuum pump and the reaction is terminated, and the non-volatile content is 33 to 37% by weight, Brookfield viscosity is 50 to 100 poise at 25 ℃, pH is 7 to 9 A phosphorus water-dispersed silicone-modified polyurethane resin composition was obtained.

(6) Synthesis of water-dispersed silicone-modified polyurethane resin 3

First, 178 to 188 parts by weight of Konix PP-2000 (KPX Chemical), 4 to 12 parts by weight of polydimethylsiloxane diol (Shin-Etsu), dimethylpropionic acid (Seonjin Chemitech) 15 to 25 parts by weight and N-ethyl-2-pyrrolidone (Duruchem) 60 parts by weight were added and heated to 70 to 80 ° C. to completely dissolve dimethylolpropionic acid. Thereafter, the reactor was cooled to 50 ° C., 128 to 138 parts by weight of dicyclohexylmethane-4,4-diisocyanate (Covestro) was added, heated to 80 to 90 ° C. for 60 minutes, and maintained for 240 minutes. After that, 80 to 120 parts by weight of acetone (Kumho P&B Chemicals) was added, diluted, and NCO% was measured to confirm that the theoretical value was 1.5% to 3.5%, and the temperature of the polymerization reactor was cooled to 50 to 60 ° C. (The Chem) was neutralized by adding 10 to 15 parts by weight. Thereafter, 570 to 590 parts by weight of ion-exchanged water was put into a dispersion tank for dispersion and stirred, and the prepared polymer was added to induce additional molecular weight growth. Then, the dispersion tank is heated to 60 ℃, the used acetone is recovered with a vacuum pump and the reaction is terminated, and the non-volatile content is 33 to 37% by weight, Brookfield viscosity is 50 to 100 poise at 25 ℃, pH is 7 to 9 A phosphorus water-dispersed silicone-modified polyurethane resin composition was obtained.

<Test method and evaluation method>

(1) Test specimen production conditions

For the preparation of the test piece, the sample is uniformly applied to a 350 mm (h) x 450 mm (w) x 1T mold without air bubbles. After that, after curing for 120 hours before demolding, demoulding and curing for 4 hours or more after 48 hours at 40±2 ℃.

(2) Manufacture of tensile strength test specimen

For the production of tensile strength test specimens, the cured samples after demolding are processed under the following conditions.

- Dumbbell No. 2: Process with a parallel part width of 10 mm, a parallel part length of 20 mm, a parallel part thickness of 3 mm or less, and a scale distance of 20 mm.

(3) Production of elongation test piece

In order to produce elongation test pieces, the cured samples after demolding are processed under the following conditions.

- Dumbbell Type No. 1: Process with a parallel part width of 10 mm, parallel part length of 40 mm, thickness of parallel part less than 3 mm, and scale distance of 40 mm.

(4) Test method

- The measurement speed is 500 ± 25 mm/min, and the load tolerance is ± 2%.

- The number of test specimens should be 3 or 4 or more, but if more than 3 cannot be collected, 2 should be used. At this time, record the number of test pieces.

- Tensile strength is measured by reading the maximum load until the test piece breaks with the device and obtaining the tensile strength using the following formula.

- For elongation measurement, read the length between the graduations until the test piece is broken with the device and calculate the elongation rate using the following formula.

[Example 1]

Prepare a test piece by blending Preparation 2 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 2 of water-dispersible silicone-modified polyurethane resin in a ratio of 9:1, and evaluate the tensile strength and elongation by the above experimental method.

[Example 2]

Prepare a test piece by blending Preparation 2 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 2 of water-dispersible silicone-modified polyurethane resin in a ratio of 8:2, and evaluate the tensile strength and elongation by the above experimental method.

[Example 3]

Prepare a test piece by blending Preparation 2 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 2 of water-dispersible silicone-modified polyurethane resin in a ratio of 7:3, and evaluate the tensile strength and elongation by the above experimental method.

[Example 4]

Prepare a test piece by blending Preparation 3 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 3 of water-dispersible silicone-modified polyurethane resin at a ratio of 9:1, and evaluate the tensile strength and elongation by the above experimental method.

[Example 5]

Prepare a test piece by blending Preparation 3 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 3 of water-dispersible silicone-modified polyurethane resin in a ratio of 8:2, and evaluate the tensile strength and elongation by the above experimental method.

[Example 6]

Prepare a test piece by blending Preparation 3 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 3 of water-dispersible silicone-modified polyurethane resin in a ratio of 7:3, and evaluate the tensile strength and elongation by the above experimental method.

[Example 7]

Prepare a test piece by blending Preparation 2 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 3 of water-dispersible silicone-modified polyurethane resin in a ratio of 9:1, and evaluate the tensile strength and elongation by the above experimental method.

[Example 8]

Prepare a test piece by blending Preparation 2 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 3 of water-dispersible silicone-modified polyurethane resin in a ratio of 8:2, and evaluate the tensile strength and elongation by the above experimental method.

[Example 9]

Prepare a test piece by blending Preparation 2 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 3 of water-dispersible silicone-modified polyurethane resin in a ratio of 7:3, and evaluate the tensile strength and elongation by the above experimental method.

[Example 10]

Prepare a test piece by blending Preparation 3 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 2 of water-dispersible silicone-modified polyurethane resin in a ratio of 9:1, and evaluate the tensile strength and elongation by the above experimental method.

[Example 11]

Prepare a test piece by blending Preparation 3 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 2 of water-dispersible silicone-modified polyurethane resin in a ratio of 8:2, and evaluate the tensile strength and elongation by the above experimental method.

[Example 12]

Prepare a test piece by blending Preparation 3 of aqueous ethylenically unsaturated monomer copolymer emulsion resin and Synthesis 2 of water-dispersible silicone-modified polyurethane resin in a ratio of 7:3, and evaluate the tensile strength and elongation by the above experimental method.

[Comparative Example 1]

A test piece of Preparation 1 of the aqueous ethylenically unsaturated monomer copolymer emulsion resin was prepared, and the tensile strength and elongation were tested and evaluated according to the above experimental method.

[Comparative Example 2]

A test piece of water-dispersed silicone-modified polyurethane resin synthesis 1 is prepared and evaluated by testing tensile strength and elongation according to the above experimental method.

The results of the above experiments are shown in the table below.

division tensile strength
(MPa) elongation
(%) Example 1 131 272 Example 2 124 282 Example 3 111 296 Example 4 100 402 Example 5 120 362 Example 6 132 298 Example 7 110 390 Example 8 120 380 Example 9 130 350 Example 10 118 361 Example 11 128 312 Example 12 131 297 Comparative Example 1 5 426 Comparative Example 2 122 272

Looking at the above results, Comparative Example 1 was a general acrylic emulsion, and the elongation rate was measured high by lowering the Tg, but the tensile strength was low. The average of the measured values and the elongation rate were measured low.

As a result, Example 5 showed the best physical properties in terms of tensile strength and elongation of the binder for waterproofing agent. In the case of blending in a proportion, 30 to 40 parts by weight of diacetone acrylamide and 6 to 12 parts by weight of adipic acid dihydrazide are used as self-crosslinking agents, and dicyanate as isocyanate or diisocyanate contained in water-dispersed silicone-modified polyurethane resin This was the case of using chlorohexylmethane-4,4-diisocinate.

Claims (6)

A liquid binder composition for a waterproofing agent comprising an aqueous ethylenically unsaturated monomer copolymer emulsion resin, a water-dispersible silicone-modified polyurethane resin, and ion-exchanged water,
The aqueous ethylenically unsaturated monomer copolymerization emulsion resin is a copolymer obtained by copolymerization of at least one hydrophobic ethylenically unsaturated monomer and at least one hydrophilic ethylenically unsaturated monomer in the presence of a surfactant and a water-soluble polymerization initiator. resin, and the aqueous ethylenically unsaturated monomer copolymer emulsion resin is a resin having a self-crosslinking function at room temperature,
The water-dispersible silicone-modified polyurethane resin includes one polyester polyol, one polydimethylsiloxane diol, one ionic group compound, one isocyanate or diisocyanate compound, and a solvent, a neutralizer, a diluting solvent, and a dispersion medium. Characterized in that it is a resin of 33 to 37% by weight,
A liquid binder composition for a waterproofing agent. According to claim 1,
The isocyanate or diisocyanate compound is a liquid binder composition for a waterproofing agent, characterized in that dicyclohexylmethane-4,4-diisocyanate. According to claim 1 or 2,
The aqueous ethylenically unsaturated monomer copolymer emulsion resin contains 30 to 40 parts by weight of diacetone acrylamide and 6 to 12 parts by weight of adipic acid dihydrazide as a room temperature self-crosslinking agent to have a self-crosslinking function at room temperature. A liquid binder composition for a waterproofing agent, characterized in that. According to claim 3,
The blending ratio of the aqueous ethylenically unsaturated monomer copolymer emulsion resin and the water-dispersible silicone-modified polyurethane resin is 8: 1.5 to 2.5 in weight ratio, a liquid binder composition for a waterproofing agent. According to claim 4,
The surfactant is a sulfate-based anionic surfactant,
The water-soluble polymerization initiator is a liquid binder composition for a waterproofing agent, characterized in that any one of sodium persulfate, potassium persulfate, ammonium persulfate. According to claim 5,
The aqueous ethylenically unsaturated monomer copolymer emulsion resin has a molecular weight of 800,000 to 1,000,000 and a viscosity of 900 to 1,200 cps,
The water-dispersible silicone-modified polyurethane resin has a molecular weight of 20,000 to 50,000 and a viscosity of 10 to 100 cps.