KR101573230B1 - Solvent-free epoxy fire resistive paint composition having improved gas toxicity on fire - Google Patents
Solvent-free epoxy fire resistive paint composition having improved gas toxicity on fire Download PDFInfo
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- KR101573230B1 KR101573230B1 KR1020110108845A KR20110108845A KR101573230B1 KR 101573230 B1 KR101573230 B1 KR 101573230B1 KR 1020110108845 A KR1020110108845 A KR 1020110108845A KR 20110108845 A KR20110108845 A KR 20110108845A KR 101573230 B1 KR101573230 B1 KR 101573230B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/18—Fireproof paints including high temperature resistant paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
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Abstract
The present invention relates to a two-pack type foamable epoxy refractory coating composition which comprises 5 to 70% by weight of an epoxy resin, 1 to 50% by weight of a phosphorus flame retardant, 1 to 50% by weight of expandable graphite, 0.2 to 20% by weight of a fiber, And 1 to 20% by weight of an additive (A); And a curing agent composition containing 10 to 80% by weight of an amine type curing agent, 1 to 40% by weight of a phosphorus-based flame retardant, 0.05 to 20% by weight of a fiber, 1 to 40% by weight of a filler, 0.1 to 10% by weight of a pigment and 1 to 20% (B), and the expandable graphite is an expandable graphite coated with a silane compound. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an epoxy resin composition. The composition according to the present invention improves the emission of harmful gas when the coating film expands in case of fire, thereby reducing the risk of suffocation in the event of a fire. Thus, not only facilities for handling oil and gas such as offshore structure or plant, It is effective as a refractory coating for space.
Description
The present invention relates to a two-component foamable epoxy refractory coating composition for use in oil or gas industry facilities such as offshore structures and plants, and more particularly to a foamable epoxy refractory coating composition for use in expanding graphite, which is coated with a silane compound, The present invention relates to an epoxy-based refractory coating composition having improved solubility.
Offshore structures, plants, and other oil fires are characterized by a rapid rise in temperature up to 945 ° C within 5 minutes. Although hardening type epoxy fireproof paints are mainly used as refractory paints in fields where oil fires can occur, existing fireproof paints have a disadvantage in that a large amount of harmful gas is released when the paint film expands.
The following three U.S. patents are the basis for epoxy-based refractory coatings.
US Patent No. 4,529,467 suggests that the epoxy-based fire-resistant paint of fire-proof form is formed by allowing zinc (Zn) to form a foam layer having a small pore size at the time of expansion of paint in case of fire, Can be improved. However, if zinc is used in an excess amount, the coating film can not expand, which may adversely affect the heat insulating performance.
U.S. Patent No. 5,108,832 proposes an epoxy-based refractory coating excellent in flexibility by synthesizing an epoxy resin having excellent flexibility. The epoxy resin was synthesized by using an epoxy monomer having a chain structure, and a refractory paint was prepared using the epoxy resin. The flexural properties were predicted by a low temperature cycle test.
US Pat. No. 6,096,812 suggests that by using hydrophobic fumed silica, the density of the coated film can be lowered and the fire resistance performance can be ensured while reducing the amount of paint used.
All of these US patents disclose the foaming mechanism of refractory paints using boric acid and ammonium polyphosphate. Boric acid emits gas while dehydrating at about 170 ° C, allowing these gases to expand. However, such a foaming mechanism has a problem that all of the foaming mechanism releases harmful gas upon foaming.
On the other hand, Korean Patent Laid-Open Publication No. 2011-0051395 proposes a foam-type refractory material which has a high expansion ratio due to heat, is excellent in heat insulation property and can prevent the refractory paint layer (foam layer) from falling off due to wind pressure . The patent discloses a foamed refractory coating technology which comprises an anti-scattering agent, which is an inorganic substance having a melting point of up to 100 DEG C in relation to the expansion temperature of expanded graphite, and further contains 1 to 20 wt% of a foaming agent. However, the above patent has a problem that a separate foaming agent should be used. Further, since the back surface temperature was measured with an infrared laser thermometer for a circular coating film having a thickness of 10 mm and a diameter of 70 mm without forming a coating film on the iron specimen, it is difficult to objectively confirm the heat shielding effect from the above patent.
A common feature of the patented technologies proposed so far is that the material inside the coating film reacts in the event of a fire to release additional gas. At this time, as the gas is released, unreacted substances, decomposed substances, or substances having a small molecular weight are present together in the coating film, resulting in a problem that the generated gas contains a large amount of harmful components. Therefore, there is a need for a new technique that allows less harmful gas to be released when the refractory paint is expanded upon fire.
DISCLOSURE OF THE INVENTION In order to solve the problems of the prior art as described above, the present invention proposes a new method of expansible graphite, which is a plate-like material, like an accordion, thereby reducing harmful gases emitted during a fire and securing excellent fire resistance To provide a solvent-free epoxy-based refractory coating composition.
The epoxy resin composition according to the present invention is a two component foamable epoxy resin composition which comprises 5 to 70% by weight of an epoxy resin, 1 to 50% by weight of a phosphorus-containing flame retardant, (A) comprising 1 to 50% by weight of expandable graphite, 0.05 to 30% by weight of fibers, 0.01 to 10% by weight of pigment and 1 to 20% by weight of an additive; And a curing agent composition containing 10 to 80% by weight of an amine curing agent, 1 to 40% by weight of a phosphorus-based flame retardant, 0.05 to 20% by weight of a fiber, 1 to 40% by weight of a filler, 0.01 to 10% by weight of a pigment and 0.5 to 20% (B), and the expandable graphite is extensible graphite coated with a silane compound.
The mixing ratio of the subject composition (A) to the curing agent composition (B) of the present invention is preferably in a weight ratio of 3.0: 1 to 2.0: 1.
The expandable graphite coated with the silane compound of the present invention is preferably expansive graphite coated with a silane compound selected from the group consisting of epoxy silane having a molecular weight of 100 to 400, aminosilane, phenyl silane, and mixtures thereof.
The expandable graphite coated with the silane compound of the present invention is preferably expanded graphite coated with the silane compound in an amount of 0.1 to 30 wt% based on the total weight of the expandable graphite, and the silane compound is used in an amount of 0.3 to 25 wt% Coated expanded graphite is particularly preferred.
The subject composition (A) according to the present invention comprises 10 to 60% by weight of an epoxy resin having a weight average molecular weight of 200 to 800, selected from bisphenol A type epoxy resin, phenol novolak epoxy resin or a mixture thereof; 5 to 40% by weight of a phosphorus-based flame retardant selected from the group consisting of triphenyl phosphate, tris (2,3-dichloropropyl) phosphate, ammonium polyphosphate, phosphoric acid ester, tricresyl phosphate, trichloroethyl phosphate, ; 2 to 40% by weight of expandable graphite coated with a silane compound; 0.1 to 20% by weight of fibers having a length of 0.1 to 6.0 mm selected from the group consisting of mineral fibers, glass fibers, ceramic fibers, organic fibers and mixtures thereof; 0.02 to 8% by weight of pigment; And 1 to 20% by weight of an additive selected from the group consisting of thickeners, dispersants, defoamers, plasticizers, and mixtures thereof.
The curing agent composition (B) of the present invention is selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 3,3-aminobispropylamine, m-xylenediamine, and mixtures thereof 20 to 70% by weight of an amine-based curing agent; 5 to 30% by weight of a phosphorus-containing flame retardant selected from the group consisting of triphenyl phosphate, tris (2,3-dichloropropyl) phosphate, ammonium polyphosphate, phosphoric acid ester, tricresyl phosphate, trichloroethyl phosphate, ; 0.1 to 15% by weight of fibers having a length of 0.1 to 6.0 mm selected from the group consisting of mineral fibers, glass fibers, ceramic fibers, organic fibers and mixtures thereof; Spherical type selected from calcium carbonate, vinastonite and mixtures thereof having an average particle size of 0.1 to 20 占 퐉 or a hollow filler type selected from alumina, glass, ceramics and mixtures thereof having an average particle size of 0.1 to 2 占 퐉 2 to 30% by weight of a filler; 0.02 to 8% by weight of pigment; And 0.5-20% by weight of an additive selected from the group consisting of thickeners, dispersants, defoamers, plasticizers and mixtures thereof.
The epoxy-based refractory coating composition of the present invention having improved gas harmfulness in the case of fire has a gas harmfulness of 11 minutes or more when measured by the gas harmfulness test method (KSF 2271).
The non-solvent type epoxy refractory coating composition according to the present invention improves the gas harmfulness in case of fire. The use of expansive graphite coated with a silane compound as a foaming agent of a solvent-free epoxy refractory coating enables to control the expansion rate when the film expands in case of fire, The risk of suffocation in a fire can be reduced. In addition, it is an environmentally friendly paint that does not generate VOC because it is a high durability durable formulation type. Accordingly, the composition of the present invention can be effectively used as a refractory coating material in an enclosed space such as a tunnel, a basement, as well as a facility for handling oil or gas such as an offshore structure or a plant.
The epoxy resin composition according to the present invention is a two component foamable epoxy resin composition which is divided into a main composition (A) and a curing agent composition (B). The epoxy resin composition comprises 5 to 70% by weight of an epoxy resin, (A) containing 1 to 50% by weight of an amorphous graphite, 1 to 50% by weight of expandable graphite, 0.05 to 30% by weight of a fiber, 0.01 to 10% by weight of a pigment and 1 to 20% by weight of an additive; And a curing agent composition containing 10 to 80% by weight of an amine curing agent, 1 to 40% by weight of a phosphorus-based flame retardant, 0.05 to 20% by weight of a fiber, 1 to 40% by weight of a filler, 0.01 to 10% by weight of a pigment and 0.5 to 20% (B), and the expandable graphite is extensible graphite coated with a silane compound.
DETAILED DESCRIPTION OF THE INVENTION
The subject composition (A)
1) Epoxy resin
The epoxy resin of the present invention exhibits durability in a dry film, and when exposed to a high temperature in the event of fire, it changes the state of the film to a fluid state so that the film can expand. In the present invention, one or both of bisphenol A type epoxy resin based on bisphenol A monomer and phenol novolac epoxy resin based on phenol novolak can be used in combination, and those having a weight average molecular weight of 200 to 800 can be used do.
The content of the epoxy resin is 5 to 70% by weight, preferably 10 to 60% by weight, based on the total weight of the base composition (A). If the content is less than 5% by weight, the adhesion of the coating film may be deteriorated due to insufficient resin content. If the content is 70% by weight or more, the viscosity of the coating material becomes low and the coating material may flow down during coating film expansion.
2) Phosphorous flame retardant
The phosphorus-based flame retardant to be used in the present invention is a conventional flame retardant commonly used in refractory paints and the like, and is preferably a material capable of forming a carbonized film during fire to enhance heat resistance. The phosphorus-containing flame retardant may include phosphate, phosphite, phosphonate, and phosphonium groups, and specifically includes triphenyl phosphate, tris (2,3-dichloropropyl) phosphate, ammonium polyphosphate, Esters, tricresyl phosphate, trichloroethyl phosphate and the like are preferably used alone or in combination of two or more.
The content of the flame retardant is 1 to 50 wt%, preferably 5 to 40 wt%, based on the total weight of the base composition (A), and if the content is less than 1 wt%, the strength of the carbonized layer is insufficient, Can be easily broken or the heat resistance performance may be deteriorated. If it exceeds 50% by weight, the carbonized layer becomes too hard and the carbonized layer is easily broken, so that the heat-shielding performance can not be exhibited.
3) Expandable graphite coated with silane compound
In order for expandable graphite to be well wetted to the coating composition, surface treatment with a silane compound is required. If the surface treatment is not carried out, the wetting in the coating composition is not performed well, and the durability can be rapidly lowered and the mechanical properties can also be lowered. In order to produce expandable graphite coated with the silane compound, the expandable graphite is put into a mixer such as a Henschel mixer or a container mixer, and then stirred with one or more of epoxysilane, aminosilane, and phenyl silane having a molecular weight of about 100 to 400, . In this case, the epoxy or amino component on the surface of the expandable graphite is crosslinked with the binder of the resin, so that excellent wettability can be provided.
The amount of the silane compound to be used is 0.1 to 30% by weight, preferably 0.3 to 25% by weight based on the total weight of the expandable graphite. When the content is less than 0.1% by weight, the surface coating effect is poor and the wettability can be deteriorated. , The free flowability of the expandable graphite tends to fall, so that it is not dispersed well in the coating material and the wettability can be deteriorated.
The content of the expandable graphite coated with the silane compound is 1 to 50% by weight, preferably 2 to 40% by weight based on the total weight of the base composition (A), and when the content is less than 1% by weight, If the ratio exceeds 50% by weight, the paint may excessively expand, causing a crack in the carbonized layer, resulting in a decrease in strength and deteriorating the heat shielding performance.
4) Fiber
The fiber used in the present invention serves to prevent cracking of the carbonized layer and to prevent the carbonized layer from falling off when foaming. Minerals, glass, ceramics, organic components and the like can be used as the component of the fiber, and the length of the fiber is 0.05 to 8.0 mm, preferably 0.1 to 6.0 mm. When the length of the fiber is less than 0.05 mm, the length of the fiber is too short to prevent the crack, and when the length of the fiber is more than 8.0 mm, the length of the fiber is too long.
The content of the fiber is 0.05 to 30% by weight, preferably 0.1 to 20% by weight based on the total weight of the base composition (A), and if the content is less than 0.05% by weight, the proportion of fibers is low, If the content is more than 30% by weight, the content of the fibers may be too large and the paint may not be expanded, resulting in a poor heat-shielding performance.
5) Pigment
Pigments are generally used to impart color to paints, and black and colored pigments are used.
The content of the pigment is 0.01 to 10% by weight, preferably 0.02 to 8% by weight based on the total weight of the base composition (A). If the content is less than 0.01% by weight, the hue of the coating composition may be uneven And if it exceeds 10% by weight, there is a problem that the refractory performance may be deteriorated due to an increase in the pigment content.
6) Additive
As additives, at least one of a thickener, a dispersant, a defoaming agent, a plasticizer and the like may be mixed in an appropriate ratio so as to exhibit optimum coating and film performance, and the additive may be added in an amount of 1 to 20 wt% Is preferably used. When the content of the additive is less than 1% by weight, dispersion of the coating material is undesirable and bubbles may be generated in the coating film. If the content of the additive exceeds 20% by weight, adhesion of the coating film may be deteriorated.
The curing agent composition (B)
1) Amine-based curing agent
The curing agent used in the present invention is used for curing the epoxy resin of the subject composition. Amine-based curing agents of the amine, polyamide, amidoamine type may be used, and specific examples thereof include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 3,3-aminobispropylamine, m- Mixtures of these are preferred.
The content of the amine-based curing agent is 10 to 80% by weight, preferably 20 to 70% by weight based on the total weight of the curing agent composition (B). When the content is less than 10% by weight, the content of the curing agent is small, If the content exceeds 80% by weight, the content of the curing agent is large, and coating film defects such as amine brushing may occur.
2) Phosphorous flame retardant
The phosphorus-based flame retardant to be used in the present invention is a conventional flame retardant commonly used in refractory paints and the like, and is preferably a material capable of forming a carbonized film during fire to enhance heat resistance. These phosphorylated flame retardants may include phosphate, phosphite, phosphonate, and phosphonium groups, and specifically include triphenyl phosphate, tris (2,3-dichloropropyl) phosphate, ammonium polyphosphate, Cresyl phosphate, trichloroethyl phosphate, or a mixture of two or more thereof.
The content of the phosphorus flame retardant is 1 to 40% by weight, preferably 5 to 30% by weight based on the total weight of the curing agent composition (B), and if the content is less than 1% by weight, Can easily break down or the heat resistance performance may deteriorate. If it exceeds 40% by weight, the carbonized layer becomes too hard and the carbonized layer is easily broken, so that the heat-shielding performance can not be exerted.
3) Fiber
The fiber used in the present invention serves to prevent cracking of the carbonized layer and to prevent the carbonized layer from falling off when foaming. Minerals, glass, ceramics, and organic components can be used as the component of the fiber, and the fiber having a length of 0.05 to 6.0 mm, preferably 0.1 to 5.0 mm, is used. When the length of the fiber is less than 0.05 mm, the length of the fiber is too short to prevent the crack, and when the length of the fiber exceeds 6.0 mm, the length of the fiber is too long.
The content of the fiber is 0.05 to 20% by weight, preferably 0.1 to 15% by weight based on the total weight of the curing agent composition (B). If the content is less than 0.05% by weight, the fiber ratio is low, If the content is more than 20% by weight, the content of the fibers may be too much, which may cause the paint to undergo less expansion, resulting in poor heat-shielding performance.
4) Filler
The filler used in the present invention is used to supplement the refractory performance, and one or two hollow fillers, which are generally spherical and hollow, can be used in combination. In the general spherical type, one or two of calcium carbonate and vinastonite having an average particle size of about 0.1 to 20 탆 may be used. The hollow filler type may contain one or more components such as alumina, glass, and ceramic And the particle size range is 0.1 to 2 탆.
The content of the filler is preferably 1 to 40% by weight, and more preferably 2 to 30% by weight, based on the total weight of the curing agent composition (B). If the content of the filler is less than 1 wt%, the heat shielding performance at high temperature may be deteriorated. If the content exceeds 40 wt%, the coating film may become hard and cracks may be generated.
5) Pigment
Pigments are generally used to impart color to paints, and white and colored pigments are used.
The content of the pigment is 0.01 to 10% by weight, preferably 0.02 to 8% by weight based on the total weight of the curing agent composition (B), and if the content is less than 0.01% by weight, the hue of the coating material may be uneven And if it exceeds 10% by weight, there is a problem that the refractory performance may be deteriorated due to an increase in the pigment content.
6) Additive
Additives may be mixed in a proper ratio of the thickener, dispersing agent, anti-foaming agents, one or more plasticizers, etc. for optimal coating material and coating film performance, and the additive is 0.5 to 20% by weight based on the total weight of the light agent composition (B) Is preferably used. If the content of the additive is less than 0.5% by weight, dispersion of the coating material may be undesirable, and bubbles may be generated in the coating film. If the content of the additive exceeds 20% by weight, adhesion of the coating film may deteriorate.
Meanwhile, in order to form a coating film using the composition of the present invention, a coating composition can be formed by mixing a base composition and a curing agent composition at a predetermined ratio using a high-temperature one-component type or two-component type coating machine or using a hera or the like. For example, in a high-temperature liquid type coating machine, a coating film can be formed by coating a mixture of a subject and a curing agent at a predetermined ratio through a static mixer. At this time, the mixing ratio of the subject composition (A) to the curing agent composition (B) of the present invention is preferably in a weight ratio of 3.0: 1 to 2.0: 1.
In addition, it is preferable to coat the coating film with a thickness of about 2 to 8 mm at the time of coating once. However, when the coating is less than 2 mm, the coating efficiency is very poor and the sagging occurs when the coating exceeds 8 mm .
Hereinafter, the present invention will be described in detail by way of examples. However, it should be understood that the present invention is not limited thereto.
Manufacturing example 1: Epoxy resin production
472 g of epichlorohydrin and 25 g of 2-methoxyethanol were added to a four-necked flask. The temperature of the solution was maintained at 55 to 60 캜, and 177 g of bisphenol A type resin was slowly added thereto for 3 hours while stirring well. After the addition, the temperature was lowered to 50-60 ° C, the pressure was lowered, and epichlorin and water were distilled off. The temperature was gradually increased to about 120 ° C with distillation for 4 hours. The amount of distillation was about 300 g. After lowering the temperature of the reaction mixture remaining in the flask to 110 ° C, 240 g of water was added to remove NaCl, and the mixture was stirred well and separated into two layers. The water layer was removed and once again extracted with 360 g of water. The remaining compound in the flask was heated to 140 占 폚 and 256 g of liquid epoxy resin was synthesized by removing low-boiling compounds which might be left at low pressure for 30 minutes. The weight average molecular weight of the synthesized resin was 250 to 800.
Manufacturing example 2: Epoxy With silane Manufacture of Coated Expandable Graphite
500 g of expandable graphite (EG58, ZJGHI Co.) was added to a mixer such as a Henschel mixer or a container mixer, and then 50 g of epoxy silane was slowly added to the expandable graphite for 30 minutes by spraying while slowly stirring. The mixture was further stirred for 1 hour to allow the epoxy silane to be well coated with the expandable graphite, and then filtered and packed into 20 mesh.
Example 1, 2, and Comparative Example 1, 2: Preparation of Components of Refractory Coating Composition
(1) Topical composition (A)
The refractory coatings were prepared in the compositions shown in Table 1 below. The preparation method was a planar mixer or a high speed dissolver, and the mixture was stirred at a low speed or a high speed so as to be well dispersed after each raw material was added, and the mixture was stirred at low speed or high speed even after all the raw materials were added.
(Unit: g)
1) YDPN631: Manufacturer National Chemical
2) AP422: Manufacturer Clariant
3) EG58: Manufacturer ZJGHI
4) Melamine: Manufacturer AMI
5) AS-70C: Manufactured by KCS
6) MA-100: Manufacturer Mitsubishi
7) BYK108: Manufactured by Big Chemie
8) DMP: Manufacturer LANXESS
(2) Curing agent composition (B)
A refractory paint curing agent part was prepared with the composition shown in Table 2 below. The preparation method was a planar mixer or a high speed dissolver, and the mixture was stirred at a low speed or a high speed so as to be well dispersed after each raw material was added, and the mixture was stirred at low speed or high speed even after all the raw materials were added.
(Unit: g)
1) GA0432: Manufacturer National Chemical
2) R-9930: Manufactured by KCS
3) AP422: Manufacturer Clariant
4) AS-70C: Manufactured by KCS
5) FAS-10: Manufacturer ZJGHI
6) CR-95: Move the manufacturer
7) BYK108: Manufactured by Big Chemie
Experimental Example : Measurement of physical properties after painting
The above-prepared base composition and curing agent composition were applied to the containers of the liquid type coating machine at a weight ratio of 2.4: 1, respectively, followed by painting. The temperature of the container was controlled within the range of 50 ~ 70 ℃. For the gas harmfulness test, 4 ㎜ * 220 ㎜ * 220 ㎜ specimens were used and coated until the film thickness was 6 ㎜. In addition, in the fire resistance performance test, it was heated with the temperature curve of the heating heating of ISO834. The size of the test specimen was 6 ㎜ * 320 ㎜ * 500 ㎜ and coated with 10 ㎜ film thickness. After coating, the coating was dried and tested for gas toxicity and fire resistance as follows.
(1) Gas hazard test
The gas hazard test was conducted according to the KSF 2271 test method. The main test contents are burning the specimen by applying heat to the specimen painted with refractory paint, and then collecting the generated smoke and sending the smoke to the room where the mouse is, to measure the average behavioral stopping time of the mouse. If the harmfulness of the gas improves, the average behavioral downtime of the mice may be so long. As a result of comparing the gas harmfulness with the painted specimen, the results shown in Table 3 were obtained.
Stop time
When the test results are compared, the average behavior stopping time average of the comparative example is 7 minutes to 8 minutes, and the average of the examples is 11 minutes to 12 minutes. Therefore, the gas hazard was improved by 35% or more. Through the improvement of the gas harmfulness, it is possible to reduce the suffocation by the toxic gas during the fire, and the gas harmfulness can be improved by this.
(2) Fire resistance performance test
In the fire resistance performance test, the heating temperature curve (ISO834) simulating the oil fire heating temperature was used and the backside temperature of the test body was measured. This heating curve is characterized by the fact that it is heated up to 945 ° C within 5 minutes, and it is a heating temperature graph which is internationally standard in oil fire test. The evaluation method can secure the performance as a refractory structure if the average temperature of the test specimen at the start of the test is not more than 140 캜 after the end of the test. As a result of comparing the fire resistance performance with the painted samples, the results shown in Table 4 below were obtained.
Temperature
(° C)
(60 minutes - 0 minutes)
The fire resistance performance of the example satisfies the specification of IMO A754 because the difference between the temperature after the end of the test and the initial temperature of the test is less than 140 ° C. However, Exceeding 140 占 폚 will not satisfy the specification of IMO A754. Therefore, it has been confirmed that the refractory coatings of the examples can satisfy the standard of IMO A754, which is internationally applicable to refractory coatings such as marine structures, and thus can be commercialized.
Claims (8)
(1) to (20), wherein the composition comprises 5 to 70% by weight of an epoxy resin, 1 to 50% by weight of a phosphorus flame retardant, 1 to 50% by weight of expandable graphite, 0.05 to 30% by weight of a fiber, A); And
A curing agent composition containing 10 to 80% by weight of an amine curing agent, 1 to 40% by weight of a phosphorus-based flame retardant, 0.05 to 20% by weight of a fiber, 1 to 40% by weight of a filler, 0.01 to 10% by weight of a pigment and 0.5 to 20% B)
Wherein the expandable graphite is an expansive graphite coated with a silane compound.
Wherein the mixing ratio of the base composition (A) to the curing agent composition (B) is from 3.0: 1 to 2.0: 1 by weight.
The expandable graphite coated with the silane compound,
Wherein the epoxy resin is an expansive graphite coated with a silane compound selected from the group consisting of an epoxy silane having a molecular weight of 100 to 400, an amino silane, a phenyl silane and a mixture thereof. .
The expandable graphite coated with the silane compound,
Wherein the silane compound is an expansive graphite coated with 0.1-30 wt% based on the total weight of the expandable graphite.
The expandable graphite coated with the silane compound,
Wherein the silane compound is an expansive graphite coated with 0.3 to 25 wt% based on the total weight of the expandable graphite.
The subject composition (A)
10 to 60% by weight of an epoxy resin having a weight average molecular weight of 200 to 800 and selected from a bisphenol A type epoxy resin, a phenol novolak epoxy resin or a mixture thereof;
5 to 40% by weight of a phosphorus-based flame retardant selected from the group consisting of triphenyl phosphate, tris (2,3-dichloropropyl) phosphate, ammonium polyphosphate, phosphoric acid ester, tricresyl phosphate, trichloroethyl phosphate, ;
2 to 40% by weight of expandable graphite coated with a silane compound;
0.1 to 20% by weight of fibers having a length of 0.1 to 6.0 mm selected from the group consisting of mineral fibers, glass fibers, ceramic fibers, organic fibers and mixtures thereof;
0.02 to 8% by weight of pigment; And
1 to 20% by weight of an additive selected from the group consisting of a thickener, a dispersant, a defoamer, a plasticizer and a mixture thereof.
The curing agent composition (B)
20 to 70% by weight of an amine-based curing agent selected from the group consisting of diethylenetriamine, triethylenetetramine, tetraethylenepentamine, 3,3-aminobispropylamine, m-xylenediamine and mixtures thereof;
5 to 30% by weight of a phosphorus-containing flame retardant selected from the group consisting of triphenyl phosphate, tris (2,3-dichloropropyl) phosphate, ammonium polyphosphate, phosphoric acid ester, tricresyl phosphate, trichloroethyl phosphate, ;
0.1 to 15% by weight of fibers having a length of 0.1 to 6.0 mm selected from the group consisting of mineral fibers, glass fibers, ceramic fibers, organic fibers and mixtures thereof;
A spherical type selected from calcium carbonate, vinastonite and mixtures thereof having an average particle size of 0.1 to 20 占 퐉 or a hollow filler type selected from alumina, glass, ceramics and mixtures thereof having an average particle size of 0.1 to 2 占 퐉 2 to 30% by weight of a filler;
0.02 to 8% by weight of pigment; And
Wherein the composition contains 0.5-20 wt% of an additive selected from the group consisting of a thickener, a dispersant, a defoamer, a plasticizer, and a mixture thereof.
Wherein the gas harmfulness is at least 11 minutes measured by the gas harmfulness test method (KSF 2271).
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020110108845A KR101573230B1 (en) | 2011-10-24 | 2011-10-24 | Solvent-free epoxy fire resistive paint composition having improved gas toxicity on fire |
| SG11201401821PA SG11201401821PA (en) | 2011-10-24 | 2012-10-24 | Solvent-free flame-resistant epoxy paint composition, the toxicity of the smoke of which is reduced in the event of an outbreak of a fire |
| PCT/KR2012/008739 WO2013062295A1 (en) | 2011-10-24 | 2012-10-24 | Solvent-free flame-resistant epoxy paint composition, the toxicity of the smoke of which is reduced in the event of an outbreak of a fire |
| CN201280052096.5A CN104011153B (en) | 2011-10-24 | 2012-10-24 | Solvent-free flame-resistant epoxy paint composition, the toxicity of the smoke of which is reduced in the event of an outbreak of a fire |
| RU2014118502/05A RU2570058C9 (en) | 2011-10-24 | 2012-10-24 | Solvent-free fire-resistant epoxy paint composition having low smoke toxicity in case of fire |
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| KR1020110108845A KR101573230B1 (en) | 2011-10-24 | 2011-10-24 | Solvent-free epoxy fire resistive paint composition having improved gas toxicity on fire |
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| KR20130044669A KR20130044669A (en) | 2013-05-03 |
| KR101573230B1 true KR101573230B1 (en) | 2015-12-02 |
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| KR (1) | KR101573230B1 (en) |
| CN (1) | CN104011153B (en) |
| RU (1) | RU2570058C9 (en) |
| SG (1) | SG11201401821PA (en) |
| WO (1) | WO2013062295A1 (en) |
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| WO2019156326A1 (en) * | 2018-02-09 | 2019-08-15 | 주식회사 케이씨씨 | Solvent-free coating composition |
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- 2012-10-24 SG SG11201401821PA patent/SG11201401821PA/en unknown
- 2012-10-24 WO PCT/KR2012/008739 patent/WO2013062295A1/en active Application Filing
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| KR102121812B1 (en) * | 2018-02-09 | 2020-06-11 | 주식회사 케이씨씨 | Solvent free paint composition |
Also Published As
| Publication number | Publication date |
|---|---|
| CN104011153B (en) | 2017-02-08 |
| KR20130044669A (en) | 2013-05-03 |
| RU2570058C1 (en) | 2015-12-10 |
| WO2013062295A1 (en) | 2013-05-02 |
| RU2570058C9 (en) | 2016-09-10 |
| CN104011153A (en) | 2014-08-27 |
| SG11201401821PA (en) | 2014-08-28 |
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