KR101789533B1 - Manufacturing method of nonflamable fiber reinforced plastics and nonflamable fiber reinforced plastics using thereof - Google Patents

Abstract

One aspect of the present invention relates to a method for producing a nonflammable fiber-reinforced plastic, and more particularly, to a method for producing a nonflammable fiber-reinforced plastic by cooling methylolmelamine or methylated melamine obtained by reacting melamine and formalin to produce a reaction product; Mixing the resulting reaction product with a flame retardant filler and a noxious gas reducing agent to prepare a mixture; Impregnating the mixture with an inorganic reinforcement; A drying step of drying after passing through the impregnation step; And a shaping step of shaping after the drying step.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a non-combustible fiber reinforced plastic

The present invention relates to a method for producing a nonflammable fiber-reinforced plastic having excellent flame retardancy and minimizing the generation of harmful gases such as volatile organic compounds (VOCs) and having a high tensile strength, and a non-combustible molded article using the same.

In recent years, there has been an increasing demand for non-combustible fiber-reinforced plastics widely used in construction materials, etc. In accordance with this trend, researches on non-combustible fiber-reinforced plastics have been tried in various aspects. However, , There is a case that the standard of 'Flame retardant performance of building finishing material and fire prevention standard of fire prevention structure' (Ministry of Land, Infrastructure and Transport notice 2015-744) is met. However, mass production system When applied as building materials, most of the technologies are not applicable because they do not meet the nonflammability criteria or there are many problems that excessive gas is generated.

The Ministry of Land, Infrastructure and Transport's Notice 2015-744 (Ministry of Land Transport and Duties Notification No. 2015-744), "Fire retardant performance and fire prevention structure of building finishing materials", is designed to prevent the generation of toxic fumes and fire spreading in materials, Fireproof performance test methods, performance standards and fire prevention standards for materials. In this standard, the flame retardant grade is classified into flame retardant grade 3 (flame retardant material), flame retardant grade 2 (semi-fire retardant material), and flame retardant grade 1 (fire retardant material).

First, the generation of combustion gas should be small during combustion. This is because the gas generated during combustion can increase the heat release rate or raise the temperature in the furnace and adversely affect the behavior stopping time of the mouse in the gas toxicity test.

Second, the generated gas must be less toxic. This is because the toxic gas generated during combustion is the most important factor to shorten the downtime of the mouse.

More specifically, according to the above-mentioned criteria, as a result of the test according to Korean Industrial Standard KS F ISO 1182 (Non-flammability test method of building materials), the maximum temperature in the heating furnace for 20 minutes after the start of the heating test, , The mass reduction rate of the test specimen after heating was 30% or less, and the gas harm test result of KS F 2271 (non-combustibility test method of internal materials and structures of buildings) (See Article 2 of the same standard).

Korean Patent Registration No. 1,049,879 discloses a method for preparing a resin aqueous solution by mixing a thermosetting resin containing a methylol group and a flame retardant filler and dispersing the mixture by adding a solvent and then diluting with water to prepare a resin aqueous solution, A step of drying the impregnated flame retardant fiber, a step of molding the dried flame retardant fiber, and a step of cooling the molded plastic. However, in practice, the resin aqueous solution And the flame-retardant filler material is impregnated with the aqueous resin solution to produce a non-combustible fiber-reinforced plastic article, a large amount of construction When applied to the site as a material, it exhibits uniform incombustibility. There is a problem that can not be done.

Particularly, the above problem is due to failure in obtaining a uniform molded product sheet by continuous drawing of fiber-reinforced plastic (FRP). As a fundamental cause, firstly, since the effective combination of the flame retardant composition and the glass fiber can not be performed, And it failed to secure the uniformity of the continuous performance of the sheet, and the sheet itself could not be formed completely. Secondly, the VOCs could not be reduced in the drying and molding steps. Therefore, the mice should be active for at least 9 minutes at the time of gas toxicity examination. However, the results were less than those of the mice. Also, the shape of the edges of the sheet and the middle part of the sheet were different, have.

SUMMARY OF THE INVENTION The present invention has been made in order to solve the above-mentioned problems, and it is an object of the present invention to provide a method of manufacturing a semiconductor device capable of uniformly maintaining a high level of incombustibility with respect to all plastic materials, Which is capable of minimizing the generation of harmful gas such as dust and the like.

Further, the present invention provides a method for producing a nonflammable fiber-reinforced plastic improved in tensile strength, tensile elastic modulus and adhesion strength to a level that can be practically applied to repair and reinforcement methods of concrete structures in addition to suppression of generation of incombustible and noxious gases .

One aspect of the present invention for solving the above-mentioned problems relates to a method for producing a nonflammable fiber-reinforced plastic, and more particularly, to a method for producing a nonflammable fiber-reinforced plastic by cooling a methylol melamine or methylated melamine obtained by reacting melamine and formalin to produce a reaction product; Mixing the resulting reaction product with a flame retardant filler and a noxious gas reducing agent to prepare a mixture; Impregnating the mixture with an inorganic reinforcement; A drying step of drying after passing through the impregnation step; And a shaping step of shaping after the drying step.

Another aspect of the present invention relates to a method for producing a nonflammable fiber-reinforced plastic, and more particularly, to a method for producing a nonflammable fiber-reinforced plastic, comprising the steps of: cooling a methylol melamine or methylated melamine obtained by reacting melamine and formalin to produce a reaction product by adding a harmful gas- Mixing the resulting reaction product with a flame retardant filler to prepare a mixture; Impregnating the mixture with an inorganic reinforcement; A drying step of drying after passing through the impregnation step; And a shaping step of shaping after passing through the drying step.

According to the manufacturing method of the present invention, it is possible to uniformly maintain a high level of nonflammability with respect to the entire plastic material without deviations even if it is applied to an actual site through mass production, and it is possible to prevent harmful gases such as volatile organic compounds (VOCs) It is possible to manufacture a nonflammable fiber-reinforced plastic having a tensile strength, a tensile elastic modulus and an adhesion strength that can be practically applied to a repair and reinforcement method of a concrete structure, , Subway, railway tunnels, road tunnels, reinforced incombustibles under firepower, joints, substations and bridges with high fire risk, structural reinforcement of general buildings and remodeling work.

FIG. 1 is a test report showing the result of requesting the Korea Shipbuilding & Marine Engineering Research Institute for the incombustibility and gas harmfulness test of the embodiment of the present invention.

BRIEF DESCRIPTION OF THE DRAWINGS The present invention is capable of various modifications and various embodiments, and specific embodiments are illustrated in the drawings and will be described in detail in the detailed description. It is to be understood, however, that the invention is not to be limited to the specific embodiments, but includes all modifications, equivalents, and alternatives falling within the spirit and scope of the invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The terminology used in this application is used only to describe a specific embodiment and is not intended to limit the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises" or "having" and the like are used to specify that there is a feature, a number, a step, an operation, an element, a component or a combination thereof described in the specification, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, components, or combinations thereof.

The terms first, second, etc. may be used to describe various components, but the components should not be limited by the terms. The terms are used only for the purpose of distinguishing one component from another.

One aspect of the present invention relates to a method for producing a nonflammable fiber-reinforced plastic, and more particularly, to a method for producing a nonflammable fiber-reinforced plastic by cooling methylolmelamine or methylated melamine obtained by reacting melamine and formalin to produce a reaction product; Mixing the resulting reaction product with a flame retardant filler and a noxious gas reducing agent to prepare a mixture; Impregnating the mixture with an inorganic reinforcement; A drying step of drying after passing through the impregnation step; And a shaping step of shaping after the drying step.

In one embodiment of the present invention, the step of producing the reaction product is a step of cooling a methylol melamine or methylated melamine obtained by reacting melamine and formalin to produce a reaction product. When the melamine and formalin are reacted under neutral or alkaline conditions Methylol melamine is produced, and when melamine and formalin are reacted under acidic conditions methylated melamine is produced. That is, when reacting melamine with formalin, the reaction is partially proceeded using an acid catalyst to neutralize with alkali to produce methylol melamine, or when melamine and formalin are reacted in an alkaline condition, methylated melamine May be generated. In an embodiment of the present invention, a considerable part of harmful gas such as volatile organic compounds (VOCs) can be removed through the reaction product generating step. Although the composition ratio of the reaction product during the reaction of the melamine and formalin is not particularly limited, the reaction product can maintain an appropriate viscosity, and when the flame retardant filler is mixed with the reaction product, the binding force to the flame retardant filler is high, In order to minimize the unreacted formalin, it is preferable to react with 80 to 200 parts by weight of formalin with respect to 100 parts by weight of melamine, more preferably 90 to 150 parts by weight of formalin with respect to 100 parts by weight of melamine Can be.

In one embodiment of the present invention, the viscosity of the reaction product is not particularly limited, but it is preferably from 5 to 1000 cps in view of maintaining a high viscosity and dispersibility higher than a certain level in order to secure sufficient bonding force to the flame- And more preferably 20 to 50 cps.

In an embodiment of the present invention, the step of preparing the mixture comprises mixing the flame retardant filler and the noxious gas reducing agent to the reaction product to prepare a mixture. In the case of the prior art, The function as a binder of melamine is greatly deteriorated by obtaining a melamine resin to be distributed and re-dissolving it in water as it is to produce an aqueous solution of melamine resin. As a result, the function as a binder of melamine is greatly deteriorated, There is a problem that the viscosity and dispersibility of the aqueous solution of the melamine resin is lowered, resulting in a problem that non-uniform incombustibility of the final molded plastic article results. In particular, when a melamine resin is dissolved in water to obtain a melamine resin, which is circulated in a state in which moisture is almost removed before it is marketed, the melamine resin solution is prepared by adding an additive such as a flame retardant filler, Due to the characteristics of the melamine resin which is not melted, it takes a long time of 3 hours or longer to sufficiently dissolve the flame-retardant filler without separation of the flame-retardant filler added thereto, resulting in a problem that the production efficiency is remarkably inferior.

On the other hand, in the present invention, the reaction product obtained by reacting melamine with formalin is mixed with a flame retardant filler to the reaction product immediately without drying or dissolving in water, so that the melamine can sufficiently exhibit its function as a binder, Can maintain the high viscosity, and thus has a high bonding strength to the mixed flame-retardant filler, so that it is possible to maintain a high dispersibility without separation of layers for a long time, which is advantageous in storage stability.

Particularly, in the step of producing the mixture, a noxious gas reducing agent is added to the reaction product in addition to the flame retardant filler. In the step of producing the reaction product, the volatile organic compounds (VOCs) Additional harmful gases can be removed. In the present invention, the noxious gas reducing agent is preferably a melamine mixture in which any one selected from the group consisting of melamine, melamine, guanamine, urea, and phenol is mixed. Examples of the above-mentioned amines include benzoguanamine, acetoguanamine, and CTU-guanamine.

The ratio of mixing the flame retardant filler and the noxious gas reducing agent to the reaction product in the step of preparing the mixture is not particularly limited. However, in order to ensure uniform and excellent nonflammability of the incombustible fiber-reinforced plastic according to the present invention, It is preferable to mix 20 to 100 parts by weight of the flame-retardant filler with respect to the weight part. When the noxious gas reducing agent is used, 0.01 to 5 parts by weight of the noxious gas reducing agent is preferably mixed with 100 parts by weight of the reaction product. Particularly, when the content of the noxious gas reducing material is less than 0.01 part by weight, the residual noxious gas present in the mixture can not be sufficiently removed. When the content is more than 5 parts by weight, to be.

In order to maximize the incombustibility in the reaction product of the present invention, an inorganic flame-retardant filler such as aluminum hydroxide, magnesium hydroxide, antimony pentoxide, etc., gypsum, alumina powder, Filler type flame retardant fillers such as zinc borate, blast furnace slag, biotite, vermiculite, magnesium oxide, sodium silicate, titanium oxide, carbon black, alkali metal silicate, melamine phosphate, melamine cyanurate, triammonium phosphate, ammonium pyrophosphate, The flame-retardant fillers may be used alone or in combination of two or more thereof. However, the magnesium hydroxide is excellent in the fire retardant effect per blending amount and may be more preferable as the flame retardant filler of the present invention.

In one embodiment of the present invention, the impregnating step is a step of impregnating an inorganic reinforcement into the prepared mixture to improve tensile strength of the product, wherein the inorganic reinforcement is glass fiber, carbon fiber, aramid fiber, and basalt fiber And the glass fiber, the carbon fiber, the aramid fiber or the basalt fiber all have the advantages of high strength. Particularly, the glass fiber has a low cost of the material, The color is white, which is advantageous in various coloring. Further, in the present invention, a yarn or a fiber form woven with the inorganic reinforcement can be used.

The kind of the glass fiber is not particularly limited, and roving glass, gilded strand glass, and milled glass can be used. These may be used alone or in combination of two or more. The length (L) of the glass fiber is not particularly limited, but is preferably 0.3 mm to 10 mm, more preferably 2 mm to 7 mm, and further preferably 2 mm to 5 mm from the viewpoint of workability. However, since the glass fiber may be broken in the extrusion molding when preparing the resin composition, the average fiber diameter (D) of the glass fiber may be 1 to 25 탆, preferably 5 to 17 탆.

In addition, the aspect ratio (average fiber length / average fiber diameter = L / D) of the glass fiber is in the range of 1 to 100, preferably 5 to 70, more preferably 50 or less, The fibers may be mixed at an appropriate ratio. When the aspect ratio is in the above range, a nonflammable fiber-reinforced plastic product having excellent tensile strength can be obtained. The cross-sectional shape of the glass fiber is not particularly limited, and may be circular, cocoon-like, gourd-like, oval or the like.

In the present invention, the glass fibers may be those which have been subjected to a converging treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like, The letine resin can be used in a range that does not affect the physical properties of the molding composition. The glass fiber may be coated with a metal such as nickel, copper, cobalt, silver, aluminum, iron, or an alloy thereof by a plating method, a vapor deposition method, or the like.

The shape and type of the carbon fiber are not particularly limited, and the shape of the carbon fiber is in the form of a cord strand, a roving strand, a milled fiber, and the like, and the type may be a pitch type or a polyacrylonitrile type. The fiber diameter of the carbon fibers is preferably 0.5 to 15 탆, more preferably 1 to 10 탆. The fiber diameter of the carbon fiber is generally 6 to 18 占 퐉 in many cases. The cut length of the carbon fiber strand is preferably 1 to 15 mm, more preferably 2 to 10 mm, and particularly preferably 3 to 8 mm. Also, the stranded strands are broken during molding.

The aspect ratio (L / D), which is the ratio of the length L to the fiber diameter D of the carbon fiber in the fiber axis direction, is preferably in the range of 15 to 100, more preferably in the range of 20 to 50.

The carbon fiber may be obtained by spinning or molding the raw material composition and subsequently carbonizing it. Alternatively, the carbon fiber may be carbon fiber obtained by the vapor phase growth method without being subjected to the spinning process.

In particular, the carbon fiber obtained by the vapor phase growth method has a smaller fiber diameter and a larger aspect ratio (L / D), so that the use of the carbon fiber obtained by the vapor phase growth method can further enhance the tensile strength.

The aramid fiber is an aromatic polyamide, which is developed to improve the heat resistance of nylon, which is an aliphatic polyamide. The aromatic polyamide, which is well known for trade names such as Nomex and Kevlar, And has high heat resistance and high tensile strength which can be used for textiles such as cords. A typical aliphatic polyamide is a synthetic resin having an aliphatic hydrocarbon bonded between amide groups, and an aramid is a synthetic resin having an amide bond having 85% of benzene groups bonded to two aromatic rings between amide groups. The aliphatic hydrocarbon of the aliphatic polyamide easily undergoes molecular motion when heat is applied, whereas the benzene ring of the aromatic polyamide is stable to heat and has a high elastic modulus because the molecular chain is rigid and molecules do not easily move even when heat is applied. And there are many differences in characteristics.

In the present invention, it is more preferable to use an aramid fiber mixed with any one of glass fiber and carbon fiber as the inorganic reinforcement material in terms of improvement of tensile strength of the incombustible fiber-reinforced plastic product.

However, since the inorganic reinforcement as described above has a characteristic that it is not easily bonded to a resin mixture such as the mixture, the inorganic reinforcement is impregnated with a coupling agent in a surface coating It is possible to increase the bonding force with respect to the inorganic reinforcement by impregnating the treated inorganic reinforcement or by adding the coupling agent to the mixture and then impregnating the inorganic reinforcement. As a result, even if the plastic molded article is mass-produced, It may have uniform nonflammability.

The kind of the coupling agent is not particularly limited, but it is preferably at least one selected from the group consisting of a silane coupling agent, a titanate coupling agent and an aluminate coupling agent for application to the inorganic reinforcement material. Examples of the silane coupling agent include An amino group coupling agent, an epoxy group coupling agent, a mercapto group coupling agent and the like. Specifically, vinyl trichlorosilane, vinyltriethoxysilane, vinyltrimethoxysilane,? -Methacryloxypropyltrimethoxysilane,? - (Aminoethyl) -? - aminopropyltrimethoxysilane,? -Aminopropyltriethoxysilane,? -Aminopropyltrimethoxysilane,? -Aminopropyltrimethoxysilane, N- Silane, N-phenyl- gamma -aminopropyltrimethoxysilane, gamma-mercaptopropyltrimethoxysilane, and gamma -chloropropyltrimethoxysilane.

In an embodiment of the present invention, the impregnating step may be carried out by immersing the object to be treated in a water tank as in the prior art. However, in order to uniformly impregnate the entire inorganic reinforcing material, And in some cases it may be desirable to apply the mixture to the inorganic reinforcement in a spray mode using a nozzle.

According to an embodiment of the present invention, the drying step is a step of drying after passing through the impregnation step. In order to minimize the generation of additional noxious gas, It is important to let them know. However, in the case of the existing non-combustible fiber-reinforced plastic manufacturing technology, a semi-cured layer is formed on the surface due to drying at a high temperature in the early stage, a sufficient amount of noxious gas is generated due to insufficient drying, It acts as a factor to lower the physical properties. In addition, since a single drying chamber having a short length within 10 m is used in the conventional case, there is a problem that sufficient drying is not performed.

Therefore, in the present invention, it is preferable to apply a multi-step drying method in which the drying step is sequentially performed while passing through a plurality of drying chambers having different temperature ranges, rather than a uniform drying method in a single drying chamber. Drying is carried out at a temperature of from 70 to 80 ° C in order to prevent the surface from being semi-cured and in a drying range of from 105 to 130 ° C in order to increase the strength of the drying in the middle- In the drying section, it is preferable to carry out drying at a low temperature of 60 to 70 ° C again to prevent weakening of binding force due to overdrying.

According to an embodiment of the present invention, the molding step is a step of molding the molding step at a high temperature and a high pressure after the drying step. In the present invention, the molding condition of the molding step is a temperature of 120 to 200 DEG C and a pressure of 15 to 200 kgf / Various types of compression presses may be used, but it may be desirable to use roll-type presses to achieve more even molding.

Another aspect of the present invention relates to a method for producing a nonflammable fiber-reinforced plastic, and more particularly, to a method for producing a nonflammable fiber-reinforced plastic, comprising the steps of: cooling a methylol melamine or methylated melamine obtained by reacting melamine and formalin to produce a reaction product by adding a harmful gas- Mixing the resulting reaction product with a flame retardant filler to prepare a mixture; Impregnating the mixture with an inorganic reinforcement; A drying step of drying after passing through the impregnation step; And a shaping step of shaping after passing through the drying step.

In another aspect of the present invention, the step of producing the reaction product is a step of cooling a methylol melamine or methylated melamine obtained by reacting melamine and formalin, and adding a harmful gas reducing material to produce a reaction product, And further adding a harmful gas reducing material during the process of adding the harmful gas. According to another aspect of the present invention, there is provided a method for producing a reaction product, comprising the steps of: adding a noxious gas reducing agent during cooling of methylol melamine or methylated melamine to obtain a reaction product; The bonding force of the final product can be further increased and the nonflammability of the final product can be further increased while being uniformly maintained throughout the product. In addition, harmful gas such as volatile organic compounds (VOCs) can be sufficiently removed from the reaction product producing step And the amount of remaining harmful gas can be minimized.

In the step of producing the reaction product according to another aspect of the present invention, the composition ratio of the reaction of melamine and formalin and the addition ratio of the harmful gas reducing material are not particularly limited, but the reaction product may maintain a certain level of viscosity In order to allow the mixture to maintain a high dispersibility for a long period of time and also to be able to sufficiently remove harmful gas during the reaction product production step, a mixture of 100 parts by weight of melamine And 80 to 200 parts by weight of formaldehyde are reacted to obtain methylol melamine or methylated melamine, and 0.01 to 10 parts by weight of a noxious gas reducing agent is preferably added while cooling the methylol melamine or methylated melamine. More preferably, melamine 100 Weight And 90 to 150 parts by weight of the dried product are reacted to obtain methylolmelamine or methylated melamine, and 0.1 to 2.0 parts by weight of a noxious gas reducing agent is added while cooling the obtained methylol melamine or methylated melamine.

In another embodiment of the present invention, the viscosity of the reaction product is not particularly limited. However, considering that it is necessary to maintain a high viscosity and a dispersibility higher than a certain level in order to ensure a sufficient bonding force to the flame-retardant filler, And more preferably 20 to 50 cps.

In another aspect of the present invention, the step of preparing the mixture comprises a step of mixing a flame retardant filler with a reaction product to prepare a mixture, wherein the reaction product obtained by reacting melamine with formalin is immediately dried By mixing the reaction product with a flame retardant filler to prepare a mixture, melamine can sufficiently exhibit its function as a binder, so that the mixture can maintain a high viscosity and a high bonding strength to a mixed flame-retardant filler can be maintained for a long time There is an advantage to be able to.

In another embodiment of the present invention, the mixing ratio of the flame retardant filler to the reaction product is not particularly limited. However, in order to ensure uniform and excellent nonflammability of the incombustible fiber-reinforced plastic article according to the present invention, It is preferable to mix 20 to 100 parts by weight of the flame-retardant filler with respect to 100 parts by weight.

In another embodiment of the present invention, the impregnation step, the drying step and the molding step are the same as the impregnation step, the drying step and the molding step according to an embodiment of the present invention.

Another aspect of the present invention relates to a nonflammable fiber-reinforced plastic molded article produced using the manufacturing method according to the present invention, which is mass-produced by a mass production system and is excellent in nonflammability even when put into the field, Uniformity over the whole, discharge of noxious gas during combustion can be minimized, and tensile strength is excellent.

Hereinafter, the present invention will be described by way of examples. The following examples are merely examples for helping understanding of the present invention, and thus the scope of the present invention is not limited thereto.

<Examples>

Example 1

Melamine and formalin were reacted at a ratio of 1: 1.2 part by weight, ammonium chloride was added at the beginning of the reaction, and the reaction was partially carried out for 5 minutes. After neutralization with sodium hydroxide to produce methylol melamine, the methylol melamine was reacted at room temperature And cooled to produce a reaction product having a viscosity of 38 cps.

60 parts by weight of magnesium hydroxide and 0.5 parts by weight of melamine were added to the reaction product to prepare a mixture.

Next, the prepared mixture was impregnated with glass fiber for 8 minutes to apply the mixture to the glass fiber.

The glass fiber coated with the mixture was first dried in a first drying chamber at a temperature of 73 ° C for 20 minutes, then dried at a temperature of 110 ° C for 20 minutes in a second drying chamber, and finally dried for 20 minutes Lt; RTI ID = 0.0 &gt; 65 C. &lt; / RTI &gt;

The dried glass fibers were put into a compression mold and molded at a pressure of 150 kgf / cm &lt; 2 &gt; at a temperature of 140 DEG C to produce a nonflammable fiber-reinforced plastic according to the present invention

Example 2

Melamine and formalin were reacted at a ratio of 1: 1.2 part by weight, ammonium chloride was added at the beginning of the reaction, and the reaction was partially carried out for 5 minutes. After neutralization with sodium hydroxide to produce methylol melamine, the methylol melamine was reacted at room temperature 0.02 part by weight of melamine was added while cooling to form a reaction product.

60 parts by weight of magnesium hydroxide was mixed with 100 parts by weight of the reaction product to prepare a mixture.

Next, the prepared mixture was impregnated with glass fiber for 8 minutes to apply the mixture to the glass fiber.

The glass fiber coated with the mixture was first dried in a first drying chamber at a temperature of 73 ° C for 20 minutes, then dried at a temperature of 110 ° C for 20 minutes in a second drying chamber, and finally dried for 20 minutes Lt; RTI ID = 0.0 &gt; 65 C. &lt; / RTI &gt;

The dried glass fibers were put into a compression mold and molded at a temperature of 140 ° C at a pressure of 150 kgf / cm 2 to produce a nonflammable fiber-reinforced plastic according to the present invention.

Experimental Example

In order to test the incombustibility and gas harmfulness of the above Examples 1 and 2, the test was commissioned to the Korea Shipbuilding & Marine Equipment Research Institute (see FIG. 1). The following experimental example is based on the report of the test report of the Korea Shipbuilding & Explain it.

1. Nonflammability test

1) Experimental environment and experimental equipment

- Temperature: 23.4 ± 0.3 ℃

- Humidity: 35 ± 5% R.H.

- Non-combustible tester model: EN-ISO 1182

2) Specifications

- Ministry of Land, Infrastructure and Transport Notice No. 2015-744 [Fire retardant performance and fire prevention structure of building finishing materials]

- KS F ISO 1182: 2004 Non-combustibility test method of building materials

3) Experimental procedure

(1) The above Examples 1 and 2 were each kept at 60 ° C and 5 ° C for 24 hours in a circulating air bath prior to the test, and then cooled to an ambient temperature in a desiccator.

② The power supply to the furnace was adjusted so that the average temperature of the furnace could be maintained at 750 ± 5 ° C for at least 10 minutes.

(3) The above Examples 1 and 2 were respectively inserted into the furnace and burned for 20 minutes, and the loss rate of the mass was measured.

4) Experimental results

Table 1 shows the results of the experiment according to the above experimental procedure.

Specimen classification

Example  One

Sime  2
Non-combustible material
( Flame retardant grade 1 )
Conformance standard Diameter × height (mm) 43.05 x 49.01 43.07 x 48.72 -


Mass (g) Before the test 132.66 136.35 - After the test 104.87 108.71 -
mass
Loss g 27.79 27.64 - % 20.9 20.3 30% or less Density of core material (kg / m3) 1877.7 Maximum temperature (℃) 816.7 816.2 - Drift at end (℃) 811.0 806.3 - Temperature rise (℃) 5.7 9.9 Do not exceed 20 ℃

The test results shown in Table 1 are the test results shown in the test report (see FIG. 1) of the Korea Shipbuilding & Marine Equipment Research Institute (see FIG. 1) requested by the applicant of the present invention. Examples 1 and 2 according to the present invention show the mass loss rate and temperature When the degree of elevation is confirmed, it is found that all of the nonflammable materials (flame retardant grade 1) satisfies the criteria.

2. Gas hazard test

1) Experimental environment and experimental equipment

- Temperature: 23.4 ± 0.3 ℃

- Humidity: 35 ± 5% R.H.

- Gas Hazard Tester Model: KO MOUSE TESTER

2) Specifications

- Ministry of Land, Infrastructure and Transport Notice No. 2015-744 [Fire retardant performance and fire prevention structure of building finishing materials]

- KS F 2271: 2006 Flame Retardancy Test Methods for Interior Materials and Structures of Buildings / Section 6 Gas Hazard Test

2) Curing of the specimen

- The test pieces (Examples 1 and 2) were allowed to stand for one month or more, and they were dried in a drier at 35 to 45 ° C for at least 24 hours and cured in a desiccator for 24 hours.

3) Experimental procedure

(1) The size of the heating surface of the test piece for each of Examples 1 and 2 was set 180 mm in both the width and the length, and was first heated for 3 minutes with a sub-heat source, and then heated again with a main heat source for 3 minutes.

② The air was supplied for one year during heating, and was set at 3.0 L per minute by the primary feeder and 25.0 L per minute by the secondary feeder. The exhaust port of the test box was opened for a heating time of 6 minutes, and after the heating, exhaust gas was shut off so that gas in the test box was not discharged.

③ The gas emitted by the discharge device of the test box was discharged only during heating, and the discharge amount was 10.0 L / min.

④ The heating test was started by preheating using a standard plate, then removing the back cover and dropping the exhaust temperature to about 50 ° C.

(5) The temperature in the test box was set at 30 ° C, and a total of eight experimental white rats (female: ICR female, 5 weeks of age, weight: 18-22 g) were placed in a spinning basket.

⑥ The time from the initiation of the heating to the time when the experimental white rat stopped the action was measured and each white rat was administered for 15 minutes after the start.

4) Experimental results

Table 2 shows the results of the experiment according to the above experimental procedure.

Example 1 Example 2 Nonflammable material (flame retardant grade 1)
Conformance standard Thickness (mm) 4.0 4.0

Experimental white rat
Average Behavior Time
Must be more than 9 minutes Weight before test (g) 389.75 395.78 Weight after test (g) 383.57 390.12 Weight loss (g) 6.18 5.66 Downtime 14 minutes 13 seconds 13 minutes 59 seconds Standard Deviation 1 minute 7 seconds 32 seconds Average Behavior Time 13 minutes 6 seconds 13 minutes 27 seconds

The test results shown in Table 2 are the test results shown in the test report (refer to FIG. 1) of the Korea Shipbuilding & Marine Equipment Research Institute (see FIG. 1) requested by the applicant of the present invention. In Examples 1 and 2 according to the present invention, The average behavioral downtime of the experimental white rats exceeded 9 minutes, indicating that all of the noncombustible materials (flame retardant grade 1) met the criteria.

3. Tensile strength test

In order to test the tensile strength of Example 1, the test was commissioned to the Korea Chemical Fusion Test Institute. The tensile strength was measured according to the KSM ISO 527-4: 2002 test method by the Korea Chemical Fusion Test Institute, As shown in Fig.

2, the nonflammable fiber-reinforced plastic according to the present invention has a tensile strength of 488 MPa, which indicates that the tensile strength is high enough to be applicable to the repair and reinforcement method of a concrete structure.

As described above, those skilled in the art will understand that the present invention may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. It will be understood by those skilled in the art that the present invention may be embodied in many other specific forms without departing from the spirit or scope of the invention as defined by the appended claims and their equivalents. .

Claims (19)

Cooling methylolmelamine or methylated melamine obtained by reacting melamine and formalin to produce a reaction product;
Mixing the resulting reaction product with a flame retardant filler and a noxious gas reducing agent to prepare a mixture;
Impregnating the mixture with an inorganic reinforcement;
A drying step of applying a multi-step drying method in which a plurality of drying chambers having different temperature ranges are passed through the impregnating step and then sequentially dried; And
And a molding step of molding the resin after the drying step.
The method according to claim 1,
Wherein the reaction product has a viscosity of 5 to 1000 cps.
The method according to claim 1,
Wherein the reaction product is produced by reacting 80 to 200 parts by weight of formalin with respect to 100 parts by weight of melamine.
The method according to claim 1,
Wherein the mixture is prepared by mixing 20 to 100 parts by weight of a flame retardant filler and 0.01 to 5 parts by weight of a noxious gas reducing agent with respect to 100 parts by weight of the reaction product.
The method according to claim 1,
Wherein the impregnating step comprises impregnating an inorganic reinforcement surface-coated with a coupling agent.
The method according to claim 1,
Wherein the impregnating is performed by adding a coupling agent to the mixture and then impregnating the inorganic reinforcement.
delete The method according to claim 1,
In the multi-step drying method, drying is performed at a temperature of 70 to 80 ° C. in an initial drying section, drying is performed at a temperature of 105 to 130 ° C. in a middle drying section, and drying is performed at a temperature of 60 to 70 ° C. And drying the resultant fiber-reinforced plastic.
The method according to claim 1,
Wherein the inorganic reinforcing material is one obtained by mixing any one of glass fiber and carbon fiber with aramid fiber.
Adding methyl alcohol melamine or methylated melamine obtained by reacting melamine and formalin with a noxious gas reducing agent to produce a reaction product;
Mixing the resulting reaction product with a flame retardant filler to prepare a mixture;
Impregnating the mixture with an inorganic reinforcement;
A drying step of applying a multi-step drying method in which a plurality of drying chambers having different temperature ranges are passed through the impregnating step and then sequentially dried; And
And a molding step of molding the resin after the drying step.
11. The method of claim 10,
Wherein the reaction product has a viscosity of 5 to 1000 cps.
11. The method of claim 10,
The reaction product is produced by reacting 80 to 200 parts by weight of formalin with 100 parts by weight of melamine to obtain methylolmelamine or methylated melamine and 0.01 to 10 parts by weight of a noxious gas reducing agent while cooling the obtained methylol melamine or methylated melamine By weight based on the total weight of the non-combustible fiber-reinforced plastic.
11. The method of claim 10,
Wherein the mixture is prepared by mixing 20 to 100 parts by weight of a flame retardant filler with respect to 100 parts by weight of the reaction product.
11. The method of claim 10,
Wherein the impregnating step comprises impregnating an inorganic reinforcement surface-coated with a coupling agent.
11. The method of claim 10,
Wherein the impregnating is performed by adding a coupling agent to the mixture and then impregnating the inorganic reinforcement.
delete 11. The method of claim 10,
In the multi-step drying method, drying is performed at a temperature of 70 to 80 ° C. in an initial drying section, drying is performed at a temperature of 105 to 130 ° C. in a middle drying section, and drying is performed at a temperature of 60 to 70 ° C. And drying the resultant fiber-reinforced plastic.
11. The method of claim 10,
Wherein the inorganic reinforcing material is one obtained by mixing any one of glass fiber and carbon fiber with aramid fiber.
A nonflammable fiber-reinforced plastic molded article produced by the method of any one of claims 1 to 6, 8 to 15 and 17 to 18.

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