KR101025011B1 - Water proofing treatment composition for road having self treatment and treating method for water proofing by using same - Google Patents

Abstract

PURPOSE: A bridge waterproof agent composition is provided to avoid the influence of a temperature in construction, to reduce traffic delay time, and to ensure excellent adhesive property between concrete floor and bridge. CONSTITUTION: A bridge waterproof agent composition for improving adhesion of floor and bridge comprises: 40~45 weight% of a polyisocyanate prepolymer with 10~20% of NCO content and 200~400 cps of viscosity; 40~45 weight% of polyamine-based hardener in which polyamine and chain extender are mixed in a weight ratio of 3:1 - 4:1; 1~10 weight% of a self-healing agent prepared by encapsulating isophorone diisocyanate with polyurethane; and 10 weight% of inorganic pigment consisting of titanium oxide, calcium carbonate or their mixture.

Description

Self-healing cross-linking waterproofing composition and waterproofing method using same {WATER PROOFING TREATMENT COMPOSITION FOR ROAD HAVING SELF TREATMENT AND TREATING METHOD FOR WATER PROOFING BY USING SAME}

The present invention relates to a cross-linking waterproofing composition having self-healing and a waterproofing method using the same, and more particularly, to microencapsulates an isophorone diisocyanate (IPDI) self-healing agent with a polyurethane prepolymer in a polyurea resin. The present invention relates to an excellent self-healing cross-linking waterproofing composition prepared by adding self-healing properties to a polyurea resin by addition, and a method of waterproofing a cross-linking using the same.

The bridges of concrete bridges and structures serve to protect bridge decks from impacts from traffic loads, rainwater, and other weather conditions.However, as the number of years of public use increases, the amount of rainwater or snowfall penetrates, and As the load accumulates, the bonding strength between materials decreases, and cracks are likely to occur due to changes in the volume of water due to temperature changes. The generated cracks are enlarged with time, which acts as a deterioration factor for the strength and life of the concrete deck and cause corrosion of the reinforcing bars of the deck. Accordingly, in order to prevent rainwater or snow removal materials from penetrating, the strength and lifespan of concrete decks are lowered, a bridge waterproofing agent such as a penetration type, a sheet type, a coating type, and a composite type is installed in a concrete bridge or structure.

First, penetration type waterproofing agents have been used in the past but have been rarely used in recent years due to durability and performance problems. Next, the sheet type waterproofing agent is a method of laminating synthetic rubber, resin, plastic, asphalt, etc. as a main raw material on a nonwoven fabric or woven fabric. There is a downside to falling. The composite formula has been developed to compensate for the shortcomings of the sheet waterproofing agent, but has a disadvantage of poor workability. On the other hand, in the case of a coating film based on epoxy and urethane, workability is good, and since it has excellent characteristics such as adhesion to the bottom plate and bridge, waterproofness, etc., it is widely used, but in the case of epoxy, crack tracking and cold resistance, etc. In the case of urethane, heat resistance has a weak disadvantage. In addition, there is a problem that takes a lot of curing time after construction.

Thus, after installing the waterproofing agent, there is a possibility of damage in the process of installing the cross-linked packaging material, and the mechanical action such as cyclic load, vibration, shock, shear, and shrinkage and expansion due to temperature change and shrinkage of the bottom plate And swelling, etc., are complicated, and therefore easy to be damaged. In addition, if the waterproofing layer is damaged, it is impossible to accurately search only the damaged area. Therefore, there is a case of repairing and strengthening concrete decks due to lack of timely reinforcement of damaged bridge waterproofing agents. Accordingly, when repairing or reinforcing a damaged bridge waterproofing layer, a lot of costs are required, and problems such as causing a traffic delay by partially controlling a lane during construction are pointed out.

Therefore, in order to prevent damage to the cross-linking waterproofing layer under such poor conditions, it is required to use a highly elastic coating-based waterproofing agent which has excellent cracking resistance and a short curing time after construction, which can shorten the time for controlling the lane. In particular, the self-healing ability to significantly increase the number of years of public use by the self-healing ability even if the damage to the waterproofing layer is urgently needed.

Accordingly, the present inventors can reduce the traffic delay time by shortening the construction period because the curing period is not significantly affected by the construction temperature, and the adhesiveness between the concrete deck and the bridge is excellent as well as the self-healing bridge Self-healing properties of polyurea resins were microencapsulated by adding isophorone diisocyanate (IPDI) self-healing agent with polyurethane prepolymer to polyurea resin with excellent heat resistance and cold resistance. The present invention has been completed by discovering that a crosslinking waterproofing agent having excellent self-healing properties can be manufactured by imparting to.

The object of the present invention is not significantly affected by the temperature at the time of construction, the curing period is shortened to shorten the air to reduce the traffic delay time, as well as excellent adhesion between the concrete deck and the bridge and excellent healing properties To provide a water repellent composition.

Another object of the present invention is to provide a method for waterproofing the bridge using the bridge waterproofing agent composition.

In order to achieve the above object, in the present invention, 35 to 55% by weight of polyisocyanate prepolymer, 35 to 55% by weight of polyamine curing agent, 0.5 to 10% by weight of self-healing agent and 5 to 20% of inorganic pigment as a composition using polyurea resin It provides a self-healing cross-linking waterproofing composition, characterized in that consisting of.

In order to achieve the above object another object of the present invention provides a method for waterproofing the bridge using the self-healing type bridge waterproofing agent composition.

Self-healing cross-linking waterproofing composition of the present invention is excellent in the adhesion between the bridge and the bottom plate in the concrete bridges and structures, and because of the high elasticity is excellent in crack tracking for the contraction and expansion of the bottom plate and bridge. In addition, when a crack occurs in the waterproof layer, the self-healing agent is polymerized at the cracked portion, and the cracked portion is self-healing, which can significantly increase the common years of concrete bridges and structures. .

Figure 1 shows the self-healing mechanism of the self-healing cross-linking waterproofing composition of the present invention.

The technical terms and scientific terms used in the present invention can be construed as meaning ordinary meanings understood by those of ordinary skill in the art without departing from the scope of the present invention.

The crosslinking waterproofing composition of the present invention is characterized by consisting of 35 to 55% by weight of polyisocyanate prepolymer, 35 to 55% by weight of polyamine, 0.5 to 10% by weight of self-healing agent, and 5 to 20% by weight of inorganic pigment.

The self-healing cross-linking waterproofing composition of the present invention is a composition using a polyurea resin. The polyurea resin is prepared in a two-component form of a main body and a curing agent, and the main body is composed of a polyisocyanate prepolymer and a self healing agent, and the curing agent has a polyamine and a gelation time. It consists of a chain extender for adjustment. When the two-component main body and the curing agent are uniformly mixed and applied, a polyurea coating film is formed as in Scheme 1 below.

Scheme 1

+

→

+

→

Molecular Curing Agent Polyurea

The polyisocyanate prepolymer, the subject of Scheme 1, is toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), 4,4-diphenylmethane diisocyanate (4,4-Diphenylmethane diisocyanate (MDI), 1,5-naphthalene diisocyanate (NDI) or isophorone diisocyanate (IPDI), with an NCO content of 10-20% and a viscosity range of 200-400 cps It is suitable, the polyisocyanate prepolymer can be used individually or in mixture of one or more, it is preferable to use 35 to 55% by weight of the total cross-linking waterproofing agent composition, more preferably in the range of 40 to 50% by weight It is good to do.

In the Scheme 1, a curing agent may be used by mixing one or more of each of polyamines, such as Jeffamine D-230, D-2000, T-5000, and Unilink 4200, which are generally used as curing agents of epoxy and urethane. In the polyamine curing agent, a chain extender for controlling the gelation rate is used, and this is mixed with diethyltoluenediamine (DETDA), and the polyamine and the chain extender are 3: 1 to 4: 1. It is mixed by the weight ratio of. Such a curing agent is preferably used 35 to 55% by weight of the total cross-linking waterproofing composition, more preferably 40 to 50% by weight.

In addition, the self-healing type crosslinking waterproofing composition of the present invention uses an inorganic pigment as a filler, and it is preferable to add titanium oxide or calcium carbonate to the curing agent, and the amount of the inorganic pigment is preferably 5 to 20% by weight. More preferably, it is good to use in 10 to 15weight% of a range.

In addition, the self-healing agent used in the self-healing cross-linking waterproofing composition of the present invention is to encapsulate isophorone diisocyanate with polyurethane, and the synthesis process of the self-healing agent is (1) polyurethane prepolymer synthesis step, (2) Microencapsulation of the self-healing agent, and (3) microencapsulation of the microcapsules.

(1) Synthesis of polyurethane prepolymer was carried out by heating and stirring 22 parts by weight of toluene 2,4-diisocyanate at 142 parts by weight of cyclohexanone at 80 ° C for at least 1 hour, and then dissolving 1,4-butanediol while blowing nitrogen gas. After slowly adding 4 parts by weight and reacting for 24 hours, the mixture was distilled under reduced pressure at 100 ° C. for at least 5 hours to synthesize a polyurethane prepolymer. The number average molecular weight of the synthesized polyurethane prepolymer was 1200-1400, the weight average molecular weight was 1500-1800, and the polydispersity index (PDI) was 1.2-1.4. Subsequently, in the microencapsulation step of (2) the self-healing agent, 29 parts by weight of the polyurethane prepolymer prepared in (1) was heated and stirred at 70 ° C. for 3 hours to 40 parts by weight of chlorobenzene to be completely dissolved. After complete dissolution, 95 parts by weight of isophorone diisocyanate was added, followed by stirring for 2 hours or more. A solution in which 45 parts by weight of arabic gum was dissolved was added to 300 parts by weight of distilled water, and the mixture was uniformly mixed and then cooled to 50 ° C. While cooling, 31 parts by weight of 1,4-butanediol as a chain extender was slowly added, followed by stirring for 1 hour to complete microencapsulation of the self-healing agent. Finally, in the powdering step of (3) microcapsules, the liquid prepared in (2) was washed with distilled water and vacuum filtered to obtain a powder, thereby preparing a microcapsule powder in a range of 40 to 100 μm for 48 hours. The self-healing agent thus synthesized is preferably used in addition to the polyisocyanate prepolymer, and it is preferable to use 0.5 to 10% by weight of the crosslinking waterproofing composition of the present invention, more preferably in the range of 1 to 5% by weight. It is good to use.

In the self-healing type crosslinking waterproofing composition of the present invention, when damage occurs in the waterproof layer during crosslaying or public use after construction, the polyurethane prepolymer microcapsule is decomposed and isophorone diisocyanate quickly flows to the damaged site, and water penetrates. And it reacts with the air and the like is filled with a highly elastic resin film in the damaged area to heal the cracks. Therefore, the common years of the bridge waterproof layer of concrete bridges and concrete structures can be significantly increased.

Hereinafter, the present invention will be described in more detail based on the following examples. However, the following examples are only for illustrating the present invention and the scope of the present invention is not limited thereto.

Examples 1 to 4 : preparation of self-healing cross-linking waterproofing composition

To prepare a self-healing cross-linking waterproofing composition in a weight ratio (unit weight%) as shown in Table 1.

division Example 1 Example 2 Example 3 Example 4 Self-healing One 3 5 10 4,4-diphenylmethane
Diisocyanate (MDI) 44 43 42 40 Jeffamine D-230 35 34 33 30 Diethyltoluenediamine
(DETDA) 10 10 10 10 Titanium oxide 10 10 10 10 Sum 100 100 100 100

Test Example

The performance of the self-healing type crosslinking waterproofing composition of the present invention prepared in the above example was measured based on the test method for specialized coating construction waterproofing materials for highway construction -'04, which is a commercially available urethane-based crosslinking waterproofing (comparative example 1) and Compared with the epoxy-based cross-linking waterproofing agent (Comparative Example 2), the results are shown in Table 2 below.

Item Example Comparative Example One 2 3 4 One 2 Heat resistance stability (%) 150 ℃ 1.1 1.2 1.2 1.2 2.0 1.8 Fatigue Resistance Performance -20 ° C ◎ ◎ ◎ ◎ △ △ Indentation performance 20 ℃ × × × × × × Waterproof 0.1 0.1 0.1 0.1 0.3 0.3 My chisel
Impact 10 ℃ pass pass pass pass pass pass 20 ℃ pass pass pass pass pass pass 30 ℃ pass pass pass pass pass pass Seal
Adhesive burglar
(kgf / cm2) -10 ℃ 24 23 23 22 18 17 20 ℃ 20 20 20 20 15 15 Previous
Adhesive burglar
(kgf / cm2) -10 ℃ 16 16 15 15 10 10 20 ℃ 3.4 3.4 3.3 3.3 2.0 2.1 Elongation
(%) -10 ℃ 1.0 1.1 1.1 1.1 0.7 0.5 20 ℃ 1.9 2.0 2.0 2.0 1.2 1.1 7 days after immersion
Tensile Bond Strength (kgf / cm2) 90% 90% 92% 92% 80% 84% ◎: very good, ○: good △: normal
×: no hole

In the case of the self-healing type crosslinking waterproofing composition of Examples 1 to 4 prepared from the present invention from the above results, all of the criteria of the highway construction professional specification-'04 bridge coating waterproofing test items were satisfied, and Comparative Examples 1 and 2 and In comparison, all the properties were improved. In particular, the thermal dimensional stability and tensile adhesive strength were significantly improved after 7 days of immersion. On the other hand, after artificially inducing a crack of 0.1 ~ 1mm in the coating film and observed the self-healing properties, the self-healing cross-linking waterproofing composition of Examples 1 to 4 of the present invention was observed that all the cracks are recovered within 2 days In the urethane and epoxy waterproofing agents of Comparative Examples 1 and 2, it was observed that cracks existed as they are.

The above description is merely illustrative of the technical spirit of the present patent, and those skilled in the art to which the present patent belongs may make various modifications and changes without departing from the essential characteristics of the present patent.

In addition, the embodiments disclosed in the present patent are not intended to limit the technical spirit of the present patent but to describe the technical spirit of the present patent.

Therefore, the protection scope of the present patent should be interpreted by the following claims, and all technical ideas within the equivalent scope should be interpreted as being included in the scope of the present patent.

Self-healing cross-linking waterproofing composition of the present invention is excellent in the adhesion between the bridge and the bottom plate in the concrete bridges and structures, and because of the high elasticity is excellent in crack tracking for the contraction and expansion of the bottom plate and bridge. In addition, when a crack occurs in the waterproof layer, the self-healing agent is polymerized at the cracked portion, and the cracked portion is self-healing, which can significantly increase the common years of concrete bridges and structures. .

Claims (8)

In self-healing cross-linking waterproofing compositions, toluene diisocyanate (TDI), p-phenylene diisocyanate (PPDI), 4,4-diphenylmethane diisocyanate , MDI), 1,5-Naphthalene diisocyanate (NDI) and at least one selected from the group consisting of isoporon diisocyanate (IPDI), the NCO content is 10-20%, viscosity 40 to 45 wt% of a polyisocyanate prepolymer having a value ranging from 200 to 400 cps;
At least one polyamine selected from the group consisting of Jeffamine D-230, D-2000, T-5000 and Unilink 4200 and a chain extender consisting of diethyltoluenediamine (DETDA) are mixed at a weight ratio of 3: 1 to 4: 1. 40 to 45% by weight of the prepared polyamine curing agent;
1 to 10% by weight of a self healing agent prepared by encapsulating isophorone diisocyanate with polyurethane; And
Self-healing type crosslinking waterproofing composition for improving the adhesion between the bridge and the bottom plate, characterized in that the inorganic pigment consisting of 10% by weight of titanium oxide, calcium carbonate or a mixture thereof. delete delete delete delete The method of claim 1,
Self-healing agent is the adhesion of the bridge and the bottom plate, characterized in that it is prepared by the method consisting of (1) polyurethane prepolymer synthesis step, (2) micro-encapsulation step of the self-healing agent, and (3) powder of the microcapsules Self-healing cross-linking waterproofing composition for improving the properties. delete A method of waterproofing a bridge using a self-healing bridge waterproofing agent composition for improving the adhesion between the bridge and the bottom plate according to claim 1.

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