KR101746821B1 - Anti-corrosive tape for seawater - Google Patents

Abstract

One embodiment of the present invention is a moisture curable adhesive composition comprising 40 to 70 wt% of a diisocyanate, 30 to 60 wt% of a polyol mixture, 100 wt% of a moisture curable composition comprising a balance catalyst, and 1 to 5 wt% ; And a fiber substrate impregnated with the moisture-curable adhesive composition.

Description

{ANTI-CORROSIVE TAPE FOR SEAWATER}

The present invention relates to a seawater type tape.

Typical structures such as concrete structures, steel structures, and water pipes are exposed to the risk of corrosion, oxidation, cracking and breakage due to severe external environments, such as strong ultraviolet rays, moisture, chemicals, and oxygen. In particular, offshore plants that dry, install, and supply necessary equipment for exploration, drilling and production of marine resources such as petroleum gas are exposed to salt and moisture, so they are easier to corrosion, oxidize or break down than land structures Lt; / RTI >

Accordingly, by applying a corrosion-inhibiting coating composition and a corrosion-inhibiting coating composition on the surface of the structure in the structure manufacturing process, basic corrosion resistance and corrosion resistance can be imparted. However, volatile organic solvents such as volatile organic compounds (VOC) may be generated during the coating operation, which may adversely affect the health of the operator. At the same time, safety of operations such as fire and gas poisoning can not be secured, . ≪ / RTI >

Also, even if an eco-friendly paint is used, scratches may be generated due to marine life or waves, and the anticorrosive effect may be deteriorated. Also, existing anticorrosion and rustproofing properties may be deteriorated due to aging, and periodic repair is required.

In general, if the structure is damaged, it is replaced or replaced with equipment. In such a case, it is not only cumbersome and time-consuming, but also requires the cost of replacement.

 In the case of leakage of water from a pipe such as a water supply pipe, a repair tape is wound around the pipe to perform a simple and quick repair work. However, in order to be applied to an offshore plant, mechanical properties such as corrosion resistance and rustproofing ability to withstand marine conditions must be realized.

Therefore, it is required to develop a seawater tapes which can be applied to offshore structures and can be easily and quickly repaired.

SUMMARY OF THE INVENTION The present invention has been made to solve the above problems of the conventional art, and it is an object of the present invention to provide a seawater type tape having excellent water repellency to the outside environment as well as being applicable to an offshore structure, .

One aspect of the invention is a moisture curable adhesive composition comprising 40 to 70 wt% of a diisocyanate, 30 to 60 wt% of a polyol mixture, 100 wt% of a moisture curable composition comprising a balance catalyst, and 1 to 5 wt% of a rust inhibitor; And a fiber substrate impregnated with the moisture-curable adhesive composition.

In one embodiment, the diisocyanate may be methylene diphenyl diisocyanate (MDI), or toluene diisocyanate (TDI).

In one embodiment, the polyol mixture may comprise a triol and a diol.

In one embodiment, the triol may comprise a polyether triol block copolymer and a polypropylene glycol triol.

In one embodiment, the content of polypropylene glycol triols may be 20 to 25 wt% based on the total weight of the triol.

In one embodiment, the content of the diol may be 30-40 wt% based on the total weight of the polyol mixture.

In one embodiment, the diol may be selected from the group consisting of polypropylene glycol, ethylene glycol, polyethylene glycol, and mixtures or block copolymers of two or more thereof.

In one embodiment, the rust inhibitor may be selected from the group consisting of strontium phosphosilicate-based, calcium phosphosilicate-based, zinc phosphate-based, and mixtures of two or more thereof.

In one embodiment, the moisture curable adhesive composition may further comprise 1 to 7 parts by weight of an oil component.

In one embodiment, the oil component may be selected from the group consisting of a silicone oil, a hydrocarbon oil, and mixtures thereof.

The seawater tape according to one embodiment of the present invention includes the moisture-curable adhesive composition and the rust preventive agent, so that the corrosion resistance to the external environment, particularly, seawater can be improved. In addition, a synergistic effect on the performance of the system can be realized by adding oil as needed.

In addition, the maintenance work can be performed quickly and easily, thereby improving the convenience of the user's operation and reducing the maintenance cost.

It should be understood that the effects of the present invention are not limited to the effects described above, but include all effects that can be deduced from the description of the invention or the composition of the invention set forth in the claims.

Hereinafter, the present invention will be described. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements, not excluding other elements unless specifically stated otherwise.

One aspect of the invention is a moisture curable adhesive composition comprising 40 to 70 wt% of a diisocyanate, 30 to 60 wt% of a polyol mixture, 100 wt% of a moisture curable composition comprising a balance catalyst, and 1 to 5 wt% of a rust inhibitor; And a fiber substrate impregnated with the moisture-curable adhesive composition.

The seawater tape may comprise a moisture curable composition comprising a diisocyanate, a polyol mixture, and a balance of catalyst. The moisture curable composition can form a urethane bond by the polymerization reaction of the diisocyanate and the polyol mixture, whereby a polyurethane prepolymer can be formed.

The term " prepolymer " as used herein refers to a polymer having a relatively low degree of polymerization, in which the polymerization reaction is stopped at a middle stage so as to facilitate the formation of the final polymer. The synthesis route through such a prepolymer may be advantageous in that a part of the reaction heat is already generated in the synthesis of the prepolymer to reduce the exothermicity of the substantial polymer synthesis.

Generally, polyurethane refers to a polymer produced by a reaction between a compound having a hydroxyl group (-OH) and a compound having an isocyanate group (-NCO), and in the present invention, a polymer obtained by a polymerization reaction of a diisocyanate and a polyol mixture .

In the urethane bond, the isocyanate group is composed of a hard segment and the polyol group is composed of a soft segment. The higher the ratio of the stiffness structure, the higher the hardness and the greater the stiffness. The higher the ratio is, the lower the hardness and the soft rubber-like structure is formed, and the elongation can be improved due to the tangled structure of the soft structure. Therefore, the isocyanate group and the polyol group can be controlled at appropriate ratios according to the application and purpose to obtain desired properties.

The diisocyanate may be methylene diphenyl diisocyanate (MDI), or toluene diisocyanate (TDI).

The methylene diphenyl diisocyanate and the toluene diisocyanate are relatively superior in physical properties and processability to aliphatic diisocyanates such as hexamethylene diisocyanate (HMDI) or isophorone diisocyanate (IPDI) , The mutual cohesion energy is high, which is also excellent in heat resistance. In addition, the storage stability can be improved as compared with a polyurethane prepolymer made of p-phenylene diisocyanate (PPDI) or naphthalene diisocyanate (NDI) having a high melting point.

The content of the diisocyanate in the moisture curable composition may be 40 to 70% by weight. If the content of the diisocyanate is less than 40% by weight, the adhesive performance of the adhesive may deteriorate. If it exceeds 70% by weight, have.

The polyol mixture may comprise a triol and a diol. Polyols are generally classified into polyether polyols and polyester polyols. The polyether-type polyol is excellent in flexibility, hydrolysis resistance and solvent resistance, and low in cost. On the other hand, the adhesion property to an adherend having low energy is relatively lower than that of the polyester-type polyol, and mechanical properties are insufficient.

The polyester-type polyol has an excellent adhesion property to an adherend having a low energy as compared with a polyether-type polyol, but has a disadvantage that it is low in solvent resistance and expensive, and can be selected and used as needed.

The triol may include a polyether triol block copolymer and a polypropylene glycol triol. Examples of the triol include polyether triol, acrylic triol, The same known triol may be included as needed.

The content of the polypropylene glycol triol may be 20 to 25% by weight based on the total weight of the triol. If the content of the polypropylene glycol triol is less than 20% by weight, The effect may be lowered.

The diol may be selected from the group consisting of polypropylene glycol, ethylene glycol, polyethylene glycol, and a mixture or block copolymer of two or more thereof, preferably polypropylene A mixture containing a glycol, an ethylene glycol, and a polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer, and may further include a known diol such as polytetramethylene glycol, if necessary.

Particularly, the polypropylene glycol is a substance having a hydroxyl group (-OH) at both terminals of the polypropylene chain, and can be used as a main polymerization raw material of the polyurethane together with polyethylene glycol. Since the polypropylene glycol is remarkably low in toxicity to polyethylene glycol, human health hazards can be reduced and environmental suitability can be improved.

The content of the diol may be 30 to 40% by weight based on the total weight of the polyol mixture. If the content of the diol is less than 30% by weight, the anticorrosiveness and adhesion performance may be deteriorated. The effect may be deteriorated.

If the content of the triol and the diol is out of the above range, for example, when the proportion of the diol is large, the crosslinking density of the polyurethane prepolymer is lowered and the overall physical properties such as mechanical properties, water resistance and heat resistance are lowered, When the proportion of the allyl is too large, the crosslinking density excessively increases excessively and it may be difficult to obtain sufficient mechanical properties.

On the other hand, the polyurethane prepolymer may include unreacted NCO groups. As used herein, the term " unreacted NCO group " refers to the unreacted, remaining isocyanate group in the polyurethane prepolymer following polymerization of the diisocyanate with the polyol mixture.

The unreacted isocyanate group may form a crosslinked structure by reacting with water when the final product is exposed to seawater or water, and may form a polyurea while being cured. The polyurea is excellent in water resistance and corrosion resistance, and can maximize the performance of the conventional method of the polyurethane.

The moisture curable composition may comprise a balance of catalyst and the catalyst is selected from the group consisting of organometallic compounds comprising dibutyltin dilaurate, triethylenediamine or 2,2'-dicumylphenododecylether Amines, and mixtures of two or more thereof, but is not limited thereto.

On the other hand, the moisture-curable adhesive composition may contain 1 to 5 parts by weight of rust-inhibiting agent per 100 parts by weight of the moisture-curable composition.

The rust preventive agent may be added to prevent adherence, especially metal surface rust, and it is preferable to use a non-toxic rust preventive agent. The rust inhibitor may be selected from the group consisting of strontium phosphosilicate, calcium phosphosilicate, calcium borosilicate, barium metaborate, zinc phosphate, Aluminum triphosphate, and mixtures of two or more thereof.

Preferably, it may be selected from the group consisting of a strontium phosphosilicate type, a calcium phosphosilicate type, a zinc phosphate type, and a mixture of two or more thereof, more preferably a strontium phosphosilicate type .

The content of the rust inhibitor may be 1 to 5 parts by weight, and if it is less than 1 part by weight, the antirust effect may be insufficient. If the amount is more than 5 parts by weight, the adhesion performance may be deteriorated.

The moisture curable adhesive composition may be impregnated into the fiber substrate. The fibrous base material may be fiber woven with glass fiber, nylon, polyester, or nonwoven fabric, but is not limited thereto. It is preferable that the fibers are woven in a directional manner to have elasticity and excellent in fixing force so that the adherend can be firmly pressed.

Meanwhile, the moisture-curable adhesive composition may further include an additive, and the additive may be an oil or a stabilizer.

Oils are generally used as lubricants and emulsifiers. They are easy to migrate and improve the physical properties of the material, which reduces the friction between the materials and softens the movement.

When the tape is adhered to the adherend and hardened, the oil migrates to the surface of the tape to form a hydrophobic layer. The hydrophobic layer improves the waterproof effect and prevents the inflow of seawater into the adherend have.

The oil may be selected from the group consisting of a silicone oil, a hydrocarbon oil, and a mixture thereof.

The silicone oil generally has a linear molecular structure and can be classified according to the kind of organic (R, R ₁ , R ₂ ) bonded to the silicon atom and the degree of polymerization of the siloxane. Specifically, it can be divided into a linear silicone oil and a modified silicone oil depending on the type of the organic solvent.

The silicone oil may be selected from the group consisting of dimethyl silicone oil, methylphenyl silicone oil, methylhydrogen silicone oil, Fluoro silicone oil, Alkyl modified silicone oil, silicone oil, amino-modified silicone oil, and epoxy-modified silicone oil, and mixtures of two or more thereof. However, the present invention is not limited thereto.

The hydrocarbon-based oil may be selected from the group consisting of Paraffin oil, Naphthalene oil, Polybutene oil, Hydrogenated polybutene, Polyisobutene, Hydrogenated polyisobutene, Hydrogenated polyisobutene, and hydrogenated polydecene, and mixtures of two or more thereof, but is not limited thereto.

Thus, the polyurethane, polyurea, rust preventive agent, and oil of the moisture-curable adhesive composition can impart seaweed performance to the seawater-based tape through different mechanisms, respectively, A synergistic effect can be realized.

The stabilizer may be added to prevent discoloration of direct sunlight and heat during the manufacture of the adhesive. If the content of the stabilizer is less than 0.1% by weight, the effect may be insignificant and the heat resistance and discoloration resistance may be deteriorated. If the content is more than 0.5% by weight, the mechanical properties of the adhesive may be deteriorated.

Hereinafter, embodiments of the present invention will be described in detail.

Example  One

Polypropylene glycol, polyethylene glycol-polypropylene glycol-polyethylene glycol block, polypropylene glycol-polypropylene glycol-polypropylene glycol-polypropylene glycol- 100 parts by weight of a moisture-curable composition prepared by mixing 35.7% by weight of a diol mixture (32% by weight of a diol mixture containing a copolymer), 0.3% by weight of a stabilizer and 1% by weight of 2,2'- 1.5 parts by weight of silicate was added to prepare a moisture-curable adhesive composition. The prepared adhesive composition was impregnated with glass fiber to prepare a sea water type tape.

Example  2

A seawater tape was prepared in the same manner as in Example 1, except that 4 parts by weight of paraffin oil was further added to the moisture-curable adhesive composition.

Example  3

A mixture of 44% by weight of toluene diisocyanate, a polyol mixture (48% by weight of polyether triol block copolymer, 21% by weight of polypropylene glycol triol), polypropylene glycol, ethylene glycol and polyethylene glycol-polypropylene glycol-polyethylene glycol block copolymer , 31% by weight of diol mixture), 0.2% by weight of a stabilizer, and 1.1% by weight of 2,2'-dicumyl polydioethyl ether was added to 100 parts by weight of a moisture-curable composition. Strontium phosphosilicate 1.5 By weight to prepare a moisture-curable adhesive composition. The prepared adhesive composition was impregnated with glass fiber to prepare a sea water type tape.

Example  4

A seawater tape was prepared in the same manner as in Example 3, except that 4 parts by weight of paraffin oil was further added to the moisture-curable adhesive composition.

Comparative Example  One

A seawater system tape was prepared in the same manner as in Example 1, except that strontium phosphosilicate was not added to the moisture-curable adhesive composition.

Comparative Example 2

A seawater tape was prepared in the same manner as in Example 2, except that the amount of strontium phosphosilicate added was adjusted to 7 parts by weight.

Comparative Example  3

A seawater tape was prepared in the same manner as in Example 2, except that the addition amount of paraffin oil was adjusted to 10 parts by weight.

Comparative Example  4

A seawater-type tape was prepared in the same manner as in Example 3, except that strontium phosphosilicate was not added to the moisture-curable adhesive composition.

Comparative Example  5

A seawater tape was prepared in the same manner as in Example 3 except that the amount of strontium phosphosilicate added was adjusted to 7 parts by weight.

Comparative Example  6

A seawater tape was prepared in the same manner as in Example 4, except that the addition amount of paraffin oil was adjusted to 10 parts by weight.

The compositions of the moisture-curable adhesive compositions according to Examples 1 to 4 and Comparative Examples 1 to 6 are shown in Table 1 below.

division MDI
(weight%) TDI
(weight%) Polyol mixture
(weight%) stabilizator
(weight%) catalyst
(weight%) Anti-rust agent
(Parts by weight) oil
(Parts by weight) Example 1 63 - 35.7 0.3 One 1.5 - Example 2 63 - 35.7 0.3 One 1.5 4 Example 3 - 44 54.7 0.2 1.1 1.5 - Example 4 - 44 54.7 0.2 1.1 1.5 4 Comparative Example 1 63 - 35.7 0.3 One - - Comparative Example 2 63 - 35.7 0.3 One 7 4 Comparative Example 3 63 - 35.7 0.3 One 1.5 10 Comparative Example 4 - 44 54.7 0.2 1.1 - - Comparative Example 5 - 44 54.7 0.2 1.1 7 4 Comparative Example 6 - 44 54.7 0.2 1.1 1.5 10 -MDI: methylene diphenyl diisocyanate
-TDI: toluene diisocyanate
- Antirust agent: Strontium phosphosilicate
- oil: paraffin oil
Catalyst: 2,2 ' -dimopolinodaiethyl ether

Experimental Example  One: Improvisation

The seawater tape was applied to the steel plate and cured at room temperature for 24 hours to prepare specimens, and the surface of the specimens was arbitrarily damaged using a knife.

A sodium chloride reagent according to KS M ISO 6353-2 and a 5% sodium chloride aqueous solution prepared from third distilled water were prepared. The pH of the prepared sodium chloride aqueous solution is 6.5 to 7.2, and the specific gravity at 25 DEG C is 1.029 to 1.036.

The specimens were immersed in a 5% aqueous solution of sodium chloride for 4 hours and allowed to stand in air at 50 ° C or more for 20 hours to induce corrosion, which was repeated for 30 days. During the experiment, the pH and specific gravity of 5% aqueous sodium chloride solution were measured before immersing the specimens to check whether the solution was kept constant.

After 30 days of testing, the tape was removed from the specimen, and the corrosion was assessed by observing the degree of corrosion at the damaged surface of the specimen. The corrosion resistance evaluation is divided into 1 ~ 5 according to the degree of corrosion, 1 is indicated when there is little corrosion, and 2 ~ 5 according to the degree of corrosion.

Experimental Example  2: Attachment

The seawater tapes were prepared for a single lap joint test conforming to ASTM D 1002 method, and the specimens were cured for 48 hours and the shear strength was measured by UTM (Universal testing machine).

Experimental Example  3: Curable

The curability was evaluated by measuring the set-time which is the time at which curing starts when the seawater tapes are exposed to water or moisture.

The results of Experimental Examples 1 to 3 for the seawater type tape specimens of Examples 1 to 4 and Comparative Examples 1 to 6 are shown in Table 2 below.

division Improvisation Shear strength (N / mm2) Set-time Example 1 One 15.0 4 minutes 3 seconds Example 2 One 14.8 4 minutes Example 3 One 14.3 4 minutes 1 second Example 4 One 14.7 4 minutes 2 seconds Comparative Example 1 5 13.9 3 minutes 50 seconds Comparative Example 2 3 13.5 3 minutes 53 seconds Comparative Example 3 4 13.7 3 minutes 40 seconds Comparative Example 4 5 13.4 3 minutes 10 seconds Comparative Example 5 3 13.6 3 minutes 52 seconds Comparative Example 6 4 13.2 3 minutes 45 seconds - Antiseptic: 1 ~ 5 according to degree of method
- Adhesiveness: Measuring and evaluating shear strength
- Set time: Time when the tape hardening starts

First, referring to Table 2, when 1.5 parts by weight of strontium phosphosilicate was added to the moisture-curable adhesive composition (Examples 1 and 3), 1.5 parts by weight of strontium phosphosilicate and 4 parts by weight of oil were added 2, and 4), and corrosion resistance was the lowest.

On the contrary, when the strontium phosphosilicate and the oil were not added, or when any one component was added in excess (Comparative Examples 1 to 6), the corrosion inhibiting effect was lowered and the degree of corrosion was more severe than in Examples 1 to 4.

On the other hand, in the adhesion evaluation, the shear strengths (N / mm 2) of Examples 1 to 4 were 15 N / mm 2, 14.8 N / mm 2, 14.3 N / The adhesion was superior to that of seawater tape.

In addition, the set-up times of Examples 1 to 4 are somewhat longer than those of Comparative Examples 1 to 6, but when the difference is only within 20 seconds at most and the moisture-curable adhesive composition further contains rust inhibitor and / or oil It is anticipated that the hardening of the epoxy resin will not be unduly delayed, thus allowing rapid application and construction.

It will be understood by those skilled in the art that the foregoing description of the present invention is for illustrative purposes only and that those of ordinary skill in the art can readily understand that various changes and modifications may be made without departing from the spirit or essential characteristics of the present invention. will be. It is therefore to be understood that the above-described embodiments are illustrative in all aspects and not restrictive. For example, each component described as a single entity may be distributed and implemented, and components described as being distributed may also be implemented in a combined form.

The scope of the present invention is defined by the appended claims, and all changes or modifications derived from the meaning and scope of the claims and their equivalents should be construed as being included within the scope of the present invention.

Claims (10)

100 parts by weight of a moisture-curable composition comprising 40 to 70% by weight of a diisocyanate and 30 to 60% by weight of a polyol mixture, 1 to 5 parts by weight of a strontium phosphosilicate-based rust inhibitor, and 1 to 7 parts by weight of an oil component Composition; And
Wherein the moisture-curable adhesive composition comprises a fiber substrate impregnated with the moisture-curable adhesive composition. The method according to claim 1,
Wherein the diisocyanate is methylene diphenyl diisocyanate (MDI), or toluene diisocyanate (TDI). The method according to claim 1,
Wherein said polyol mixture comprises a triol and a diol. The method of claim 3,
Wherein said triol comprises polyether triol block copolymer and polypropylene glycol triol. 5. The method of claim 4,
Wherein the content of the polypropylene glycol triol is 20 to 25% by weight based on the total weight of the triol. The method of claim 3,
Wherein the content of the diol is 30 to 40% by weight based on the total weight of the polyol mixture. The method of claim 3,
Wherein the diol is one selected from the group consisting of polypropylene glycol, ethylene glycol, polyethylene glycol, and a mixture or block copolymer of two or more thereof. delete delete The method according to claim 1,
Wherein the oil component is one selected from the group consisting of a silicone oil, a hydrocarbon oil, and a mixture thereof.