KR20190023280A - A Composite of organicinorganic composite cementitious materials with high-performance and high elastic properties and manufacturing method thereof - Google Patents

Abstract

The present invention relates to an interface adhesive and water retention finishing material for various concrete structures and concrete finishing materials such as a steel and a tile, which is used at interfaces such as a concrete structure, a steel, and a tile to have interfacial adhesion and high elasticity performance, and more particularly, to an organic-inorganic composite cement mortar composition of high durability and high elasticity, which uses a modified natural rubber latex having improved elasticity by modifying a natural rubber latex capable of being applied as a clean material, which is a polymer having excellent mechanical and chemical properties, and has no toxicity, and modified polyvinyl alcohol, as a base material, and is mixed with powder having properties of a natural rubber emulsion mixed solution and a fast hardening cement material by a variety of cross-linking to have a fast hardening time during the manufacturing, and to improve strength and hardness of a coating film. The organic-inorganic composite cement mortar composition of the present invention has excellent tensile strength, abrasion resistance, etc., and particularly, has excellent oxygen barrier properties, toughness, and high elasticity to be used for interface bonding of a concrete structure, surface coating for deterioration prevention, a surface finishing material for various finishing materials such as a concrete for civil engineering structure, a steel, and a tile, and an interface adhesive material, thereby having excellent finishing properties and an excellent effect for preventing deterioration of a concrete.

Description

Technical Field [0001] The present invention relates to a high-durability and high-elasticity organic-inorganic hybrid cement mortar composition and a method for producing the same,

The present invention relates to an interfacial adhesive property and a water-retaining finishing agent for various concrete structures and concrete finishing materials such as concrete, steel and tile having interfacial adhesion and high expansion and contraction performance, which are used at interfaces of concrete structures, steels and tiles, A modified natural rubber latex which is improved in elasticity by modifying a natural rubber latex which can be applied as a clean material as a non-toxic polymer having chemical properties, and a natural rubber emulsion mixture by various cross- Which is capable of improving the strength and hardness of a coating film with a rapid curing time in the case of a hard cement material, and to a method of applying the cement mortar composition.

Generally, concrete, steel, wood and the like are rapidly deteriorated due to various environmental changes in the atmosphere, that is, changes in temperature or humidity, and thus the original design life span can not be maintained.

Cement materials are very good materials in that they are economical and high-strength materials, but they have been exposed to various drawbacks due to the vulnerability of porosity. In order to compensate for the weakness of such cementitious materials, a polymer cement mortar having the function of organic matter in the cementitious material has been utilized as a surface finishing material for a concrete structure.

According to the prior art and patents relating to polymer cement mortar, Korean Patent No. 294805 discloses a waterproof cement composition comprising 23-31 wt% of acrylic resin, 23-31 wt% of cement, 30-48 wt% of silica, Mortar discloses.

Korean Patent Laid-Open No. 2000-17879 discloses a waterproof cement mortar composed of 57% of cement, 7% of silica, 1% of ethylene vinyl acetate, 1% of active silica and 34% of water.

Korean Patent Laid-Open Publication No. 2002-31684 discloses a method for producing a water-absorbent resin composition comprising a composition A consisting of emulsion-dispersed calcium stearate and an acryl emulsion copolymer and a composition B composed of white cement, silica, polyoxyethylene lauryl ether and the like at a weight ratio of 1: 0.25 And curing the surface of the cement mortar.

Korean Patent Publication No. 2004-0067060 discloses a waterproof waterproof mortar composed of cement, silica sand, magnesium stearate, EVA, Senosphere, and the like.

Polymer cement mortar is a material having a complex function of an organic material and an inorganic material. It is a useful material that can supplement the disadvantages of cementitious materials, which are inorganic materials, Various problems due to the combination of the material and the organic material have been observed, such as a decrease in surface adhesion performance and a decrease in air permeability.

With respect to the polymeric mortar composite, Korean Patent Publication No. 2000-0000485 discloses a method for producing a polymer mortar using an unsaturated polyester mortar resin as a binder and curing at 20 캜 in a mold mold, which is produced by using an unsaturated polyester resin It is difficult to cure at room temperature and it is inconvenient for application and construction in various forms in general buildings, and the range is limited to a molded product.

Korean Patent Laid-Open Publication No. 2001-0046911 discloses a method of preparing a polymer mortar and a cement mortar composite by providing a removable diaphragm at the center and then removing the diaphragm before the mortar is cured to mix the mortar. However, this form also has a disadvantage that it can not be used in various forms.

Korean Patent Publication No. 2000-0000485

SUMMARY OF THE INVENTION The present invention has been made to solve the above-mentioned problems of the prior art,

Excellent tensile strength, tensile strength, abrasion resistance, oxygen barrier property, toughness and high elasticity;

To be used at interfaces such as concrete, steel, and tiles to enhance adhesion between materials and materials and to reduce cracking of concrete structures;

It has the ability to follow cracks caused by the expansion and contraction of concrete structures, preventing cracking and peeling between structures and reducing various durability deterioration factors due to vibration, load, and environmental effects. Maintains the initial performance of;

A new high durability and high elasticity inorganic and organic cement mortar composition and its manufacture which can be used as a surface finishing material for anti-deterioration surface coating and various finishing materials to improve the water resistance and durability by protecting the inside and the outside of concrete, steel material and tile And a method thereof.

In order to achieve the above object, the present invention provides a mixed solution (A) comprising 25 to 60% by weight of an elastically modified natural rubber latex having improved elasticity by a vulcanization reaction and 40 to 75% by weight of a modified polyvinyl alcohol having improved water resistance, And 20 to 60% by weight of the mixed solution and 40 to 80% by weight of the quick-setting cement (B) are mixed uniformly to obtain the present invention.

In the above, the elastically modified natural rubber latex having improved elasticity,

The liquid latex is a natural rubber latex having a solid content of 60% by weight or more and is adjusted in pH to increase the elastic stability of the rubber latex of the liquid latex to be used. An antioxidant is used, Radical remover was added to improve elasticity. In this experiment, water was dispersed in distilled water for smooth mixing of latex and various compounding agents. The weight of the latex was measured by a mechanical stirrer (Poong Lim Co., PL-ss20D) to remove ammonia added as a stabilizer to the natural rubber latex. The latex was weighed at a rate of 100 rpm at 40 ^° C for 2 hours Lt; / RTI > If the amount of ammonia in the natural rubber latex is too high, the physical stability is lowered and also the crosslinking reaction acts as a scavenger in the crosslinking reaction, thereby inhibiting crosslinking. After the deammonia process, a small amount of residual ammonia can be removed through the mixing and aging process. After removal of ammonia, KOH, sulfur, zinc diethyldithiocarbamate (ZDEC) and 2-mercaptobenzothiazole (MBT) were added and stirred for 2 hours under the same conditions as the deammonia process. After stirring, the blended latex blend was aged for 24 hours and the physical properties were improved by aging. The aged latex blend was made to a density of less than 0.5 g / ml using a stirrer. The ZnO dispersion was added to the synthesized latex formulation and further dispersed at 1000 rpm for 2 minutes. In order to increase the elasticity, a crosslinking reaction was carried out at a temperature of 110 ^° C using an oven to prepare a latex having excellent elasticity.

In this experiment, polyvinyl alcohol (polymerization degree = 1,500, molecular weight = 66,000, hereinafter referred to as "PVA") and vinyl triethoxysilane (KBE1003, Shin-Etsu, hereinafter referred to as "VTEOS" Were used. Polyacrylic acid (molecular weight = 1,800, Aldrich, hereinafter referred to as "PAA") capable of crosslinking with PVA at a temperature above a certain temperature was used as an additive for the blend. At this time, all the materials were used without different purification and the third distilled water was used as the solvent.

On the other hand, in order to proceed with the PVA reforming reaction in the reforming reaction with PVA using VTEOS, PVA was first dissolved in distilled water to prepare an aqueous solution having a solid content of 10%. At this time, the temperature and time were gradually increased to 85 ° C and stirred for two hours to obtain a completely dissolved solution. Then, VTEOS was added under a nitrogen stream and reacted for a predetermined time. The amount of VTEODS was fixed to 20 wt% of PVA solids. Then, 40 g of Potassium persulfate as an initiator, potassium persulfate, was added to make an aqueous solution of 3% and reacted for 20 minutes, followed by cooling to obtain a silane modified PVA solution.

In addition, in the cross-linking reaction between [PVA / VTEOS] and PAA, the cross-linking reaction between the PVA / VTEOS reactant and PAA is as follows. For example, to react at a ratio of [PVA / VTEOS] / PAA = 90/10 (w / w), 90 g of [PVA / VTEOS] modified to 20 wt% and 10 g of PAA are dissolved in 900 g of distilled water So that the solid content becomes 10%. At this time, the temperature and the time are stirred at 85 ° C for 2 hours to obtain a solution. The prepared [PVA / VTEOS] / PAA solution was used after removing air bubbles at room temperature for 24 hours.

(B) is an inorganic powder mixture, which usually comprises 50-70% by weight of cement, 15-30% by weight of calcium aluminate compound, 5-10% by weight of anhydrous gypsum extender, 3-8% by weight of stearic acid, And 1 to 2% by weight of an additive.

The present invention is used in the interface of concrete, steel tile, etc. to maintain the basic performance of the high-durability and high-elasticity organic-inorganic hybrid cement mortar composition.

In one embodiment, the anhydrous gypsum expander uses powders of 2,500 to 3,500 brains, preferably 2,900 to 3,200 brains.

In one embodiment, the stearic acid salt is one or more selected from stearic zinc or stearic calcium.

The high durability and high elasticity organic-inorganic hybrid cement mortar composition of the present invention has excellent tensile strength, tensile strength, abrasion resistance, oxygen barrier property, toughness and high elasticity

To be used at interfaces such as concrete, steel, and tiles to enhance adhesion between materials and materials and to reduce cracking of concrete structures;

It has the ability to follow cracks caused by the expansion and contraction of concrete structures, preventing cracking and peeling between structures and reducing various durability deterioration factors due to vibration, load, and environmental effects. Maintains the initial performance of;

It is used as a surface coating material for preventing deterioration and as a surface finishing material for various finishing materials to provide an effect of improving water resistance and durability by protecting the inside and outside of concrete, steel, and tile.

FIG. 1 is a graph showing hysteresis loss results by repeated stretching of a polyurethane film and a modified latex film produced in Production Example 1. FIG.
2 is a graph showing the results of infrared spectroscopic analysis for identifying the PVA modified with the silane compound of the present invention.
FIG. 3 is a graph showing changes in Tm value of DSA of the PSA-10 film of Table 1 to confirm the crosslinking reaction between [PVA / VTEOS] and PAA.
FIG. 4 is a photograph showing the result of measuring the contact angle of [PVA / VTEOS] and the PAA film and the PVA / PAA film in order to confirm the degree of improvement of the water resistance of the film.
5 is a graph showing water barrier properties (WVTR) measured for the evaluation of the barrier performance of [PVA / VTEOS] / PAA film.

The present invention is described in detail below.

In order to achieve the above object, the present invention provides a mixed solution (A) comprising 25 to 60% by weight of an elastically modified natural rubber latex having improved elasticity by a vulcanization reaction and 40 to 75% by weight of a modified polyvinyl alcohol having improved water resistance, And 20 to 60% by weight of the mixed solution and 40 to 80% by weight of the quick-setting cement (B) are mixed uniformly to obtain the present invention.

In the above, the elastically modified natural rubber latex having improved elasticity,

The liquid latex is a natural rubber latex having a solid content of 60% by weight or more and is adjusted in pH to increase the elastic stability of the rubber latex of the liquid latex to be used. An antioxidant is used, Radical remover was added to improve elasticity. In this experiment, water was dispersed in distilled water for smooth mixing of latex and various compounding agents. The weight of the latex was measured by a mechanical stirrer (Poong Lim Co., PL-ss20D) to remove ammonia added as a stabilizer to the natural rubber latex. The latex was weighed at a rate of 100 rpm at 40 ^° C for 2 hours Lt; / RTI > If the amount of ammonia in the natural rubber latex is too high, the physical stability is lowered and also the crosslinking reaction acts as a scavenger in the crosslinking reaction, thereby inhibiting crosslinking. After the deammonia process, a small amount of residual ammonia can be removed through the mixing and aging process. After removal of ammonia, KOH, sulfur, zinc diethyldithiocarbamate (ZDEC) and 2-mercaptobenzothiazole (MBT) were added and stirred for 2 hours under the same conditions as the deammonia process. After stirring, the blended latex blend was aged for 24 hours and the physical properties were improved by aging. The aged latex blend was made to a density of less than 0.5 g / ml using a stirrer. The ZnO dispersion was added to the synthesized latex formulation and further dispersed at 1000 rpm for 2 minutes. In order to increase the elasticity, a crosslinking reaction was carried out at a temperature of 110 ^° C using an oven to prepare a latex having excellent elasticity.

In this experiment, polyvinyl alcohol (polymerization degree = 1,500, molecular weight = 66,000, hereinafter referred to as "PVA") and vinyl triethoxysilane (KBE1003, Shin-Etsu, hereinafter referred to as "VTEOS" Were used. Polyacrylic acid (molecular weight = 1,800, Aldrich, hereinafter referred to as "PAA") capable of crosslinking with PVA at a temperature above a certain temperature was used as an additive for the blend. At this time, all the materials were used without different purification and the third distilled water was used as the solvent.

On the other hand, in order to proceed with the PVA reforming reaction in the reforming reaction with PVA using VTEOS, PVA was first dissolved in distilled water to prepare an aqueous solution having a solid content of 10%. At this time, the temperature and time were gradually increased to 85 ° C and stirred for two hours to obtain a completely dissolved solution. Then, VTEOS was added under a nitrogen stream and reacted for a predetermined time. The amount of VTEODS was fixed to 20 wt% of PVA solids. Then, 40 g of Potassium persulfate as an initiator, potassium persulfate, was added to make an aqueous solution of 3% and reacted for 20 minutes, followed by cooling to obtain a silane modified PVA solution.

In addition, in the cross-linking reaction between [PVA / VTEOS] and PAA, the cross-linking reaction between the PVA / VTEOS reactant and PAA is as follows. For example, to react at a ratio of [PVA / VTEOS] / PAA = 90/10 (w / w), 90 g of [PVA / VTEOS] modified to 20 wt% and 10 g of PAA are dissolved in 900 g of distilled water So that the solid content becomes 10%. At this time, the temperature and the time are stirred at 85 ° C for 2 hours to obtain a solution. The prepared [PVA / VTEOS] / PAA solution was used after removing air bubbles at room temperature for 24 hours.

(B) is an inorganic powder mixture, which usually comprises 50-70% by weight of cement, 15-30% by weight of calcium aluminate compound, 5-10% by weight of anhydrous gypsum extender, 3-8% by weight of stearic acid, And 1 to 2% by weight of an additive.

The present invention is used in the interface of concrete, steel tile, etc. to maintain the basic performance of the high-durability and high-elasticity organic-inorganic hybrid cement mortar composition.

In one embodiment, the anhydrous gypsum expander uses powders of 2,500 to 3,500 brains, preferably 2,900 to 3,200 brains.

In one embodiment, the stearic acid salt is one or more selected from stearic zinc or stearic calcium.

Hereinafter, the present invention will be described in more detail with reference to Examples and Comparative Examples. However, the following examples illustrate the present invention and the present invention is not limited by the following examples, and various modifications and changes may be made. The scope of the present invention will be determined by the technical idea of the following claims.

Manufacturing example  1: Modification of natural rubber latex

Natural rubber latex was purchased from Srijaroen Latex Co. which is imported. In order to improve the elastic stability of rubber particles in liquid latex, pH adjustment was used. Kumanox 5010L (Kumho Co.) and Sonox 1010 (Songwon Co.) were used as antioxidants, and UV-351 (Need Fill) and Songsorb 1000 PW (Songwon Co.) were used as UV absorbers. Songil 6220 LD (Songwon Co.), Cyasorb UV-3529 (Cytec Co.) and DGEBA-HALS (Hikorea Co.) were added as radical scavengers to measure the effect on elasticity. In this experiment, water was dispersed in distilled water for smooth mixing of latex and various compounding agents. The weight of the latex was measured by a mechanical stirrer (Poong Lim Co., PL-ss20D) to remove ammonia added as a stabilizer to the natural rubber latex. The latex was weighed at a rate of 100 rpm at 40 ^° C for 2 hours Lt; / RTI > If the amount of ammonia in the natural rubber latex is too high, the physical stability is lowered and also the crosslinking reaction acts as a scavenger in the crosslinking reaction, thereby inhibiting crosslinking. After the deammonia process, a small amount of residual ammonia can be removed through the mixing and aging process. After removal of ammonia, KOH, sulfur, zinc diethyldithiocarbamate (ZDEC) and 2-mercaptobenzothiazole (MBT) were added according to the compounding contents shown in Table 1 and stirred for 2 hours under the same conditions as in the deammonia process. After stirring, the blended latex blend is aged for 24 hours and it is known that the physical properties are improved through the aging process. The aged latex blend was made to a density of less than 0.5 g / ml using a stirrer. The ZnO dispersion was added to the synthesized latex formulation and then further dispersed at 1000 rpm for 2 minutes. In order to increase the elasticity, a crosslinking reaction was carried out at a temperature of 110 ^° C using an oven (Jeotech Co., OF-22GW), and a latex excellent in elasticity was prepared.

Composition of Dry parts natural rubber Laex 100 10% KOH sol. 0.4 50% 1.6 50% ZDEC dispersion 1.2 50% MBT dispersion 0.4 50% ZnO dispersion 2.4

Test Example  One: Reformed  Evaluation of physical properties of natural rubber latex

In order to comparatively evaluate the mechanical properties of the latex prepared in Preparation Example 1, a tensile tester (Shimadzu Co., AGS-500D) was used at a room temperature of 100 mm / min. The hysteresis was measured by repeating the experiment three times under the condition of 100% tensile and 100 mm / min. The temperature and modulus of the film specimens prepared using a dynamic mechanical analyzer (TA instruments, 2980 DMA) were measured. The conditions used were a 1 Hz frequency and a heating rate of 5 ^o C / min. In order to confirm the physical properties of the modified latex film prepared in Production Example 1, the properties of the urethane-based films were compared as comparative examples.

< hysteresis  loss evaluation result>

The results of hysteresis loss due to repeated stretching of the polyurethane film and the modified latex film prepared in Production Example 1 are shown in FIG. Hysteresis loss of ordinary rubber materials is observed by repeated stretching, which is known as irreversible stress softening phenomenon due to the viscoelastic effect of the rubber chain. The results of three 100% repeating elongation tests showed that the hard polyurethane film exhibited the highest hysteresis loss values and the synthetic latex films prepared above exhibited the lowest values. This means that the latex film prepared in Preparation Example 1 lost less energy in repetitive deformation than the polyurethane film, and this result means that the elastic properties of the latex film prepared in Preparation Example 1 are better. The decrease in the measured value as the cycle of hysteresis loss test increases is because the creep of the rubber chain and the viscous component due to the stress relaxation attenuate with successive repeated elongation.

Manufacturing example  2: PVA  Modification

PVA was modified by using vinyltriethoxysilane among the silicate compounds having excellent hydrophobicity to improve the water resistance and moisture barrier property to the surface and at the same time to prepare the crosslinked film using PAA to obtain the water solubility and swelling degree , And tensile strength.

In addition, the process is simplified by improving water resistance and barrier properties without using post treatment or inorganic filler.

Specifically, PVA (polymerization degree = 1,500, molecular weight = 66,000, Junsei) and vinyl triethoxysilane (KBE1003, Shin-Etsu, hereinafter referred to as "VTEOS") were used for the reforming reaction. Polyacrylic acid (molecular weight = 1,800, Aldrich, hereinafter referred to as "PAA") capable of crosslinking with PVA at a temperature above a certain temperature was used as an additive for the blend. At this time, all the materials were used without different purification and the third distilled water was used as the solvent.

On the other hand, in order to carry out a reforming reaction with PVA using VTEOS, PVA was first dissolved in distilled water to prepare an aqueous solution having a solid content of 10%. At this time, the temperature and time were gradually increased to 85 ° C and stirred for two hours to obtain a completely dissolved solution. Then, VTEOS was added under a nitrogen stream and reacted for a predetermined time. The amount of VTEODS was fixed to 20 wt% of PVA solids. After that, 40 g of potassium persulfate as an initiator, 3% aqueous solution, was added and reacted for 20 minutes, followed by cooling to obtain a silane modified PVA solution.

The crosslinking reaction between PVA / VTEOS reactant and PAA was carried out as follows. For example, to react at a ratio of [PVA / VTEOS] / PAA = 90/10 (w / w), 90 g of [PVA / VTEOS] modified to 20 wt% 900 g, so as to obtain a solid content of 10% by weight. At this time, the temperature and the time are stirred at 85 ° C for 2 hours to obtain a solution. The prepared [PVA / VTEOS] / PAA solution was used after removing air bubbles at room temperature for 24 hours.

The film was prepared using modified PVA / VTEOS / PAA. The film was prepared by pouring the solution evenly onto a plastic plate with a diameter of 15 cm and leaving it at 100 ° C until the solvent was completely removed. The composition for the experiment is shown in Table 2 below.

Sample
type PVA 20wt% -VTEOS
modified PVA PAA PAA-0 100 0 PAA-5 95 5 PAA-10 90 10 PAA-15 85 15 PAA-20 80 20 PSA-0 100 0 PSA-5 95 5 PSA-10 90 10 PSA-15 85 15 PSA-20 80 20

(Unit: wt%)

Test Example  2.

<Contents of experiment>

Infrared spectroscopic analysis (MB 104, BOMEM, Canada) was used to confirm the synthesis of the hydrophobic PVA resin. Crosslinking reaction was confirmed by the shift of Tm using DSC graph. DSC (Q100, TA, US) was measured in a range of -80 to 240 占 폚 under 20 deg. The tensile strength was measured using a tensile tester (TX-0109, Hounsfield, Korea) to determine the physical properties of the film. The crosshead speed was 100 mm / min. Hardness (Shore A) was measured according to ASTM D2240 standard. TGA (TG 2950, TA, USA) was measured to examine the thermal stability of the film. The thermal stability at 30 ~ 600 ℃ was investigated at 10 ℃ for 1 minute under a stream of nitrogen.

The swelling degree and solubility of the film were measured to evaluate the water resistance of the film. This experiment was carried out by immersing a film of a certain standard (2 x 2 cm) in water at 37 DEG C for 48 hours and then measuring the value by the weight change. Weight 1 is the weight of the initial film, Weight 2 is the weight of the film after removing the surface water after immersing in water for 48 hours, Weight 3 is defined as the weight of the film re-dried at 40 ° C after soaking in water for 48 hours, (Mileshkevich, VP 1978).

[Swelling degree and solubility calculation formula]

Swelling% = (weight 2-weight 3) / weight 3 × 100

Dissolution% = (weight 1-weight 3) / weight 1 × 100

weight 1: initial film weight,

weight 2: Weight of film after surface stem removal after immersion in water for 48 hours

weight 3: weight of film after immersion in water for 48 hours and re-drying at 40 ° C

The contact angle was measured with a contact angle meter to check the hydrophobicity of the film surface. The contact angle measurement was performed by dropping a predetermined amount of water onto the film surface at room temperature and measuring the contact angle between the surface and the droplet. The higher the measured contact angle, the better the water resistance. Moisture barrier properties were determined by measuring the moisture permeability by observing the barrier property of the film against moisture (Noll W., 1968). The moisture permeability was measured according to the KS T 1305 standard. The sample was coated with a resin of 2.5 μm on a 50 μm PET film and heat-treated at 100 ° C. The values obtained at this time are the average values measured using at least three samples.

Infrared spectroscopy was performed to identify the PVA modified with the silane compound, and the results are shown in Fig. FIG. 2 shows the results of infrared spectroscopic analysis of modified PVA obtained by reacting PVA modified with 20 wt% of VTEOS with PAA at a ratio of 90:10. Compared to modification on the former by VTEOS PVA, 1020-1100 through the reforming ^reaction, the Si-CH ₂ peak, 2700 Si-O peak, 780-800 (cm ^-1) of ⁽¹ cm) (cm ^{- 1} ), a new peak of -CHO appears. It can be seen that the -CHO peak is reacted with a group formed by the reaction of -OC ₂ H ₅ group of VTEOS with -OH group of PVA, which is also seen from the result of improvement of the water resistance.

DSA of PSA-10 film in Table 2 was measured to confirm the crosslinking reaction between [PVA / VTEOS] and PAA to confirm the change of Tm value. The film used was 20 wt% of PVA modified with PVA and PAA in a ratio of 90:10. The heat treatment temperature of the film was divided into room temperature, 50, 75, 100 and 125 ℃.

When the cross-linking reaction takes place, a shift phenomenon occurs in which the Tm value slightly increases due to the crystal structure. As shown in FIG. 3, the Tm value shifts from 75 ° C to the right, which indicates that the crosslinking reaction occurs after 75 ° C . Thus, the heat treatment temperature of the film was fixed at 100 ° C. The DSC graph shows a broad peak between 100 and 150 ° C, which is interpreted to be due to water as a solvent. Here too, the solvent peak disappeared as the crosslinking reaction occurred.

The results of DSC, TGA, tensile strength and hardness measured to confirm the thermo-mechanical properties of the [PVA / VTEOS] / PAA film are shown in Table 3 below. As a result of DSC measurement, the Tg and Tm values were slightly increased when modified with VTEOS, and the effect of PAA was not observed. As a result of TGA measurement for confirming thermal stability, it is confirmed in Table 3 that PVA modified with VTEOS remained 3 times at 550 ° C than PVA. This is interpreted as the influence of silane compounds having excellent thermal stability. The reason for the slight decrease in PSA-20 was that the cross-linking points were saturated and showed the same tendency as the mechanical properties.

Tensile strength and hardness were measured to confirm the mechanical properties, and the values were shown in Table 3. The tensile strength of the film modified with the silane compound was 9.48 to 10.72 kg / mm ² , which was not significantly different from the tensile strength of the PVA film of 10.64 kg / mm ² . In the case of hardness, the PVA film modified with the silane compound had a smaller value than the PVA film, and was somewhat improved as the PAA content increased. Both tensile strength and hardness showed the highest value when PAA content was 10%, showing similar physical properties to PVA film. However, when the content of PAA was 15%, it decreased. It is interpreted that the cross - linking density of PVA and PAA is improved and the cross - linking point is saturated and phase separated when too much amount is added.

Sample
type DSC Residue at 550 ℃
(%) Tensil strength Hardness Tg Tm (kg / mm ² ) (Shorea) PAA-0 (PVA) 38.08 229.08 2.6 10.64 65 PAA-5 39.30 222.50 2.6 10.85 65 PAA-10 40.99 218.12 2.9 11.53 67 PAA-15 41.02 216.04 3.1 10.50 65 PAA-20 41.24 215.85 3.2 - - PSA-0 43.60 229.08 9.79 9.84 58 PSA-5 43.46 213.72 13.07 10.02 60 PSA-10 43.34 214.88 13.23 10.72 62 PSA-15 43.25 215.43 13.45 10.20 61 PSA-20 43.28 216.21 12.16 9.48 60

Table 4 below shows the degree of swelling (%), solubility (%) and contact angle to check the degree of improvement of the water resistance of the film. In the case of the contact angle, it can be seen that the PVA / PAA film modified with the silane compound is 63.1 ~ 76.2 ° higher than 45.3 ~ 49.6 ° of the PVA / PAA film. This is confirmed in the contact angle measurement photograph shown in Fig. (a) the contact angle of PVA is 49.6 °, (b) the contact angle of PSA-0 is 71.0 °, and the value of contact angle decreases with the content of PAA, but it is larger than that of PVA.

The degree of swelling and the solubility of the silane compound were not greatly improved by the modification reaction of the silane compound but the swelling degree (%) was 250% by the crosslinking reaction using 10 wt% of PAA 198%, and the solubility (%) was improved from 28% to 10%.

Sample
type Contact angle ( ^O ) Water
swelling ( % ) Water
solubility ( % ) (Water) PAA-0 (PVA) 49.6 250 28 PAA-5 48.2 202 22 PAA-10 47.8 149 15 PAA-15 45.3 120 10 PAA-20 - - - PSA-0 76.2 253 21 PSA-5 72.7 235 16 PSA-10 71.0 198 10 PSA-15 67.4 155 5 PSA-20 63.1 108 0

The moisture barrier properties (WVTR) of the PVA / VTEOS / PAA films were measured and shown in FIG. The barrier properties were measured by coating on the PET film. In the case of moisture barrier property, slight improvement was obtained only by PVA single coating as shown in FIG. The VTEOS modifying effect was negligible, but it was confirmed that the PVA having a water permeability of 31.5 g / m ² / day had a low permeability of 11.04 g / m ² / day in the PSA-10 film. When the PAA content was more than 10%, no improvement was observed. It is interpreted that the crosslinking point was saturated and decreased rather than the other properties.

Example  1 to 3: Preparation of elastic mortar composition

The elastic mortar composition of Examples 1 to 3 of the present invention was prepared by mixing elastically modified natural rubber latex, modified polyvinyl alcohol mixture (A) having improved water resistance, and quick-setting cement (B) . The composition ratios are shown in Table 5. In the comparative example, commercially available water-resistant mortar products were purchased and their properties were compared.

The test was carried out according to KS F 4042-2012 (Polymer Cement Mortar for Concrete Structure Maintenance).

Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Liquid Mixed liquid Liquid Mixed liquid Liquid Mixed liquid Commercial 1 Commodity 2 Modified latex 30 45 40 55 50 65 Modified PVA 70 60 50 Quick hard cement 55 45 35 Commercial product 0 0 0 100 100 Sum 100 100 100 100 100

(Unit: wt%)

Test Example 3; Shout  Performance evaluation of mortar composition

The results are shown in Table 6 according to KS F 4042-2012 (Polymer Cement Mortar for Concrete Structure Maintenance) according to the composition ratio.

unit Example 1 Example 2 Example 3 Comparative Example 1 Comparative Example 2 Elongation rate % 237 211 205 132 128 Flexural strength (N / mm ² ) 9.1 8.7 8.4 5.1 4.8 Compressive strength (N / mm ² ) 32.1 33.4 33.9 18.7 19.2 Bond strength
(Wet condition of more than 10% of base paper) (N / mm ² ) 4.9 4.7 4.1 0.8 0.9 Alkali resistance (N / mm ² ) 32 33 32 17 15 Neutralization resistance (mm) 1.2 1.3 1.1 2.1 2.0 Amount of water (g) 10.1 8.9 9.1 27 29 Water absorption coefficient ^{[kg (m 2 h 0 .5} ) 0.2 0.2 0.3 1.1 1.0 Moisture permeation resistance (Sd) 1.3 1.5 1.4 3.1 3.2 Chloride ion penetration resistance coulombs 762 812 901 1487 1501 Length change rate % 9 11 11 21 23

As can be seen from the above Table 6, the elastic mortar compositions of Examples 1 to 3 of the present invention showed remarkable effects in most of the evaluation items as compared with the commercial products of Comparative Example 1 and Comparative Example 2. Especially, since it is very superior to the commercial product of Comparative Example 1, which is an imported product, it shows a high quality, and thus it is evaluated that the possibility of exporting is very high.

Claims (4)

(A) in which 25 to 60% by weight of an elastically modified natural rubber latex having improved elasticity by a vulcanization reaction and 40 to 75% by weight of modified polyvinyl alcohol having improved water resistance are mixed, and 20 to 60% And 40 to 80% by weight of the quick-setting cement (B) are mixed evenly. The method according to claim 1,
The elastically modified natural rubber latex is a natural rubber latex prepared by using a natural rubber latex having a solid content of 60% by weight or more as a latex, adjusting the pH to increase the elastic stability of the rubber latex particles, using an antioxidant, And a radical scavenger is added to improve the elasticity. The high durability and high-elasticity organic-inorganic hybrid cement mortar composition according to claim 1, The method according to claim 1,
The modified polyvinyl alcohol is characterized by using vinyl triethoxysilane for the reforming reaction and using polyacrylic acid which is capable of crosslinking with PVA at a temperature above a certain temperature as an additive for blending Wherein the cement mortar composition has a high durability and a high elasticity. The method according to claim 1,
Rapid hard cement is an inorganic powder mixture which is usually composed of 50-70 wt% of cement, 15-30 wt% of calcium aluminate compound, 5-10 wt% of anhydrous gypsum expander, 3-8 wt% of stearic acid, By weight based on the total weight of the cement mortar composition.

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