KR102146169B1 - Composition for flame-retardant treatment for refractory structure of wood-framed composite wood and fire-retardant wood using the composition - Google Patents

Abstract

In the flame-retardant composition according to an embodiment of the present invention, a composition for flame-retardant treatment comprising an N,N'-bis[(alkyl)aminomethyl]phosphinic acid compound, a water-soluble inorganic compound, and a solvent Can provide.

Description

Composition for flame-retardant treatment for refractory structure of wood-framed composite wood and fire-retardant wood using the composition}

The present invention relates to a composition for flame-retardant treatment for the fire-resistant structure of a composite wood for wooden buildings, and a method for manufacturing a flame-retardant wood using the composition, and more particularly, to a compound having water solubility as small molecules that can be absorbed into the pores of wood. It is manufactured, and is treated simultaneously with antiseptic and flame retardant treatment to provide a flame retardant composition for a fireproof structure of a composite timber for a wooden building, which is effective for flame retardancy, and to a flame retardant wood manufactured using the composition.

In recent years, consumers' preference for natural wood has been greatly increased, especially in the case of building materials in which natural wood is in high demand, and consumers' preference for natural wood has greatly increased in various fields such as furniture and construction.

The natural wood is widely used for indoor and outdoor decoration of buildings because it creates a soft and cozy atmosphere due to its excellent appearance and texture and the unique material of wood. However, due to the absolute lack of forest resources, more than 70% of the wood used is imported. In the case of Korea, which is dependent on the past, the supply of natural timber is absolutely insufficient due to forest damage caused by logging of timber in the past.

In particular, natural wood has a problem that it is difficult to use as exterior materials of buildings due to its deterioration in water resistance, heat resistance, impact strength, bending strength, dimensional stability, flame retardancy, weather resistance, and antibacterial properties due to its intrinsic properties. It is shortened, and copper, arsenic, and chromium-based preservatives (also referred to as CCA preservatives) are mixed and used for the purpose of enhancing antimicrobial properties.

Accordingly, when a fire occurs, toxic substances are discharged from the combustion of the copper, arsenic, and chromium-based preservatives, which is harmful to the human body, and there is a problem that the fire spreads due to no flame retardant function.

In addition, conventional wood is largely composed of three components such as cellulose, hemicellulose, and lignin, and the components are pyrolyzed at 180°C to start releasing combustible gases, and pyrolysis occurs around 225°C, making it difficult to stop the fire. It is necessary to develop a first flame retardant that can stop the flame before 180°C and a composition that generates char (burnt part) at about 200°C to stop gas emission.

The present invention devised to solve the above problems is a non-halogen-based environment-friendly and flame-retardant N,N'-bis[(alkyl)aminomethyl]phosphinic acid compound and a water-soluble inorganic compound in the form of an aqueous solution containing no halogen element. It is to provide a composition for flame retardant treatment for the fire resistance structure of a laminated wood for wooden buildings and a flame retardant wood manufactured using the composition.

In the composition for flame retardant treatment according to an embodiment of the present invention for solving the above problems, it is characterized in that it is prepared including a N,N'-bis[(alkyl)aminomethyl]phosphinic acid compound, a water-soluble inorganic compound, and a solvent do.

In addition, the N,N'-bis[(alkyl)aminomethyl]phosphinic acid compound is an N,N'-bis[(dimethyl)aminomethyl]phosphinic acid compound, N,N'-bis[(diethyl)amino It is characterized in that it is one of a methyl] phosphinic acid compound and an N,N'-bis[di(2-hydroxyethyl)aminomethyl]phosphinic acid compound.

In addition, the water-soluble inorganic compound may include boric acid, sodium borate, and a flame retardant auxiliary material, and the flame retardant auxiliary material may include phosphate or sulfate.

In addition, the water-soluble inorganic compound, with respect to the total weight of the composition for flame retardant treatment, boric acid 2 to 10 wt%, borate 2 to 10 wt%, a flame retardant auxiliary phosphate salt 1 to 5 wt% or sulfate 5 to 20 wt% To do.

In addition, the phosphate salt is characterized in that the ammonium dibasic (Ammonium phosphate dibasic).

In addition, the borate salt is characterized in that it is ammonium borate (Ammonium borate octahydrate) or sodium borate (Natriumborat).

In addition, the solvent is characterized in that water.

In addition, the composition for flame-retardant treatment further includes a fragrance, and the fragrance is characterized in that it is a vegetable natural fragrance or an animal natural fragrance.

It is possible to provide a flame retardant wood produced by using the flame retardant composition of the present invention.

The flame retardant composition for the fireproof structure of the laminated wood for wooden buildings according to the embodiment of the present invention and the method of manufacturing the flame retardant wood using the composition improves flame retardancy by 10% or more compared to the untreated laminated wood.

In addition, high adhesion and flame retardancy can be realized at the same time.

1 is an image showing the results for Experimental Example 1 of the present invention.

Hereinafter, the description of the present invention with reference to the drawings is not limited to a specific embodiment, and various transformations may be applied and various embodiments may be provided. In addition, the content described below should be understood to include all conversions, equivalents, and substitutes included in the spirit and scope of the present invention.

In the following description, terms such as first and second are terms used to describe various elements, and their meanings are not limited thereto, and are used only for the purpose of distinguishing one element from other elements.

The same reference numbers used throughout this specification denote the same elements.

The singular expression used in the present invention includes a plural expression unless the context clearly indicates otherwise. In addition, terms such as "include", "include", or "have" described below are intended to designate the presence of features, numbers, steps, actions, components, parts, or combinations thereof described in the specification. It is to be construed and to be understood as not precluding the possibility of the presence or addition of one or more other features, numbers, steps, actions, components, parts, or combinations thereof.

The present invention is prepared for a compound having water solubility as small molecules that can be absorbed into the pores of wood, and the composition and the composition for flame retardant treatment for the fire resistance structure of a composite wood for wooden buildings that are effective for flame retardation by simultaneously performing antiseptic and flame retardant treatment It relates to a method of manufacturing a flame-retardant wood using, and the composition for flame-retardant treatment of the present invention is prepared and provided in a liquid form including an N,N'-bis[(alkyl)aminomethyl]phosphinic acid compound, a water-soluble inorganic compound, and a solvent. I can.

Specifically, the composition for flame-retardant treatment of the present invention may be prepared in the form of an aqueous solution comprising an N,N'-bis[(alkyl)aminomethyl]phosphinic acid compound, a water-soluble inorganic compound, and a solvent represented by the following Formula 1. .

[Formula 1]

In Formula 1, R ₁ and R ₂ may be the same or different, and one of C ₁ to C ₃ alkyl, C ₁ to C ₃ alkanol having a hydroxy group at the terminal, phenyl and alkyl substituted phenyl is applied. However, considering the economy and effect, R ₁ and R ₂ are most preferably C ₁ to C ₃ alkyl and C ₁ to C ₃ alkanols having a hydroxy group at the terminal.

That is, the compound derivative represented by Formula 1 may be a compound represented by Formula 2 or a compound represented by Formula 3.

The compounds of Formulas 2 and 3 may be prepared as phosphinic acid and amine derivatives, wherein the amine derivative in Formula 2 may be N,N-dimethylamine or N,N-diethylamine, and amine in Formula 3 The derivative may be N-methyl-N-ethanolamine or N,N-diethanolamine.

Chemical Formulas 2 and 3 used in the present invention are suitable as flame retardants for wood using water as a solvent because they are soluble in water by themselves. In addition, as a phosphorus-based compound, it has flame retardancy and is particularly useful for extinguishing early fires because it acts with a vapor-phase flame retardant mechanism.

Therefore, in the present invention, it is possible to provide a flame retardant composition using the compound of the following [Chemical Formula 2] or [Chemical Formula 3].

[Formula 2]

The compound of [Chemical Formula 2] may be prepared as a phosphinic acid and an amine derivative, wherein the amine derivative may be one of N,N-dimethylamine and N,N-diethylamine, and N,N'-bis It is called [(dimethyl)aminomethyl]phosphinic acid or N,N'-bis[(diethyl)aminomethyl]phosphinic acid compound.

[Chemical Formula 3]

The compound of [Chemical Formula 3] may be prepared as a phosphinic acid and an amine derivative, wherein the amine derivative may be one of N-methyl-N-ethanolamine and N,N-dietanolamine, and N,N' -Bis[di(2-hydroxyethyl)aminomethyl]phosphinic acid compound.

In the present invention, it is preferable to use 5 to 35 wt% of the compounds of Formula 2 or 3 based on the total weight of the flame retardant composition. If it is less than 5wt%, flame retardancy is not sufficient, and if it exceeds 35wt%, stickiness occurs.

The water-soluble inorganic compound includes boric acid and borate, and may selectively include one of phosphate and diammonium sulfate.

Specifically, boric acid is used not only for its excellent flame retardancy, but also for the use of insect repellents such as ants. The amount of boric acid to be used is preferably 2 to 10 wt% based on the total weight of the flame retardant composition of the present invention. If it is less than 2wt%, the effect is small, and if it exceeds 10wt%, it is difficult to dissolve the flame retardant composition of the present invention in water, and crystals may precipitate. It is preferable to use 3wt% to 7wt% boric acid. More preferably, it is preferable to use 4wt% to 5wt% boric acid.

Also, since boric acid is not well soluble in water, it is better to dissolve it by mixing it with borate. The borate salt may be used by selecting from ammonium borate octahydrate and sodium borate.

Boric acid and boric acid salt form a network structure, penetrate into the cellulose of wood, and form a boric acid glass film by heating in the event of a fire, thereby preventing combustion by oxidation of cellulose and forming carbonization, showing excellent flame retardancy. It is suitable to use the ratio of boric acid and boric acid salt to be easily dissolved in water in a ratio of 4:5 to 5:4.

The amount of borate is preferably 4 to 5 wt% based on the total weight of the flame retardant composition of the present invention.

In addition, the flame retardant auxiliary material may include phosphate or sulfate, and diammonium sulfate may be used as diammonium sulfate or disodium sulfate. The sulfate salt can be used by neutralizing the sulfuric acid catalyst used to prepare the compounds of [Chemical Formula 2] and [Chemical Formula 3]. Sulfate salt can be used to prevent the spread of fire by carbonizing the cellulose of wood by heating in the event of a fire and escaping the flammable gas inside by heating to the outside.

That is, sulfate is a catalyst used when preparing compounds of [Chemical Formula 2] and [Chemical Formula 3], and can be used as it is without additional addition, since it can be produced and used while neutralizing the catalyst to remove the catalyst during purification, Gives a flame retardant effect.

The amount of sulfate is preferably 5 wt% to 20 wt% based on the total weight of the flame retardant composition of the present invention. To this end, it is recommended to control the amount of use by removing some of the compounds of [Chemical Formula 2] and [Chemical Formula 3] after preparing. If it is less than 5wt%, flame retardancy may be deteriorated, and if it exceeds 20wt%, it may precipitate as a solid or cause clouding after drying.

Further, when the sulfate salt is excessively or completely removed, a phosphate salt may be added.

As the phosphate, it is one of ammonium phosphate monobasic, ammonium phosphate dibasic, sodium phosphate monobasic, and sodium phosphate dibasic. However, it is preferable to use ammonium phosphate dibasic having basicity, sodium phosphate dibasic, and preferably ammonium phosphate dibasic.

Ammonium phosphate dibasic (Ammonium phosphate dibasic) exhibits foaming properties due to heat in a fire, but excessive use may cause white turbidity after wood drying, so there is a limit on the amount of use. In the present invention, the amount of ammonium phosphate dibasic is preferably 1 to 5 wt% based on the total weight of the flame retardant composition.

In addition, as described above, since the present invention is manufactured in a liquid state, it is preferable to use water as a solvent.

Therefore, it is possible to prepare a flame retardant composition of the present invention by mixing the compound of Formula 2 or Formula 3 with the water-soluble inorganic compound and a solvent.

In addition, the composition for flame retardant treatment of the present invention may further include a fragrance material capable of giving a fragrance effect when using wood.

The fragrance of the present invention may be a vegetable natural fragrance or an animal natural fragrance.

Natural botanical fragrances are rose, jasmine, bell quill, saffron, hyasis, violet, juros, heliotrope, lavender, mint, rosemary, pyrethrum, leaf and stem fragrances. Kliss, citronella, eucalyptus, cinnamon, black letters, geranium, patchouli, cassia, cedar, fragrant, camphor, cedar, fir tree, vechipa, orris, and ginger belonging to the root and subsoil flavors It may contain more than one.

The animal natural fragrance may include one or more of musk, haeri, and yongyeon, which belong to the fragrance of animal gonadal secretions.

It is recommended to add 5 to 15 wt% of the fragrance to the total weight of the flame retardant composition, and when it is added in less than 5 wt%, the fragrance effect is insufficient, and when it is added in excess of 15 wt%, it may play a role.

By further adding the above aromatic substances, it is possible to have an effect on removing bad wood odor.

Next, as a method for manufacturing a flame-retardant wood according to an embodiment using the composition for flame-retardant treatment of the present invention, the type approval and product of the flame retardant of the Republic of Korea [Fire Protection Notice No. 2017-1, 2017. 7. 26, other law revised] It can be carried out by a method conforming to the method of measuring flame retardant performance for synthetic resin boards and plywood according to the technical standards for inspection.

That is, the composition for flame retardant treatment may be treated by surface coating through spraying, immersion, brushing on interior materials, laminated wood, and industrial materials for flame retardant processing. The surface-coated flame-retardant wood can be dried at room temperature or using hot air drying, or a heat dryer, and then coated three times for flame retardant treatment. The coated wood can be used as a material for flame retardants applied to fields that are not exposed to moisture from the outside, such as rain.

Next, as a method of manufacturing a flame-retardant wood according to another embodiment, a method of injecting into the wood by vacuum decompression and pressurization may be used as a method of treating an insect repellent solution.

Specifically, through the first drying step of controlling the moisture content to 17% by drying the wood by the flame-retardant treatment method, the first vacuum treatment step of vacuuming the dried wood through the first drying step, and the first vacuum treatment step. The flame-retardant wood of the present invention can be prepared by impregnating the vacuum-treated wood into the flame-retardant composition and pressing the composition to inject the flame-retardant treatment composition into the injection and drying steps.

The flame-retardant wood treated with the flame-retardant composition can prevent ignition and spread of fire, so it can be used as flame-retardant and fire-resistant composite wood related to wood, flame-retardant and fire-resistant interior materials, industrial flame-retardant and fire-resistant materials that require flame-retardant processing. I can.

Hereinafter, the content of the present invention will be described in detail through Examples, Comparative Examples, and Experimental Examples.

Hereinafter, the experimental examples to be carried out are presented to aid understanding, and are merely illustrative of the present invention, and the scope of the present invention is not limited to the following experimental examples.

[Example]

[Example 1]

Formula 2 compound (N,N'-bis[(dimethyl)aminomethyl]phosphinic acid compound) 7wt%, boric acid 4wt%, ammonium phosphate dibasic 5wt%, sodium borate 5wt A liquid flame retardant composition was prepared with the residual amount of the solvent.

[Example 2]

Formula 2 compound (N,N'-bis[(dimethyl)aminomethyl]phosphinic acid compound) 10 wt%, boric acid 4 wt%, ammonium phosphate dibasic 5 wt%, sodium borate 5 wt% A liquid flame retardant composition was prepared with the residual amount of the solvent.

[Example 3]

Formula 2 compound (N,N'-bis[(dimethyl)aminomethyl]phosphinic acid compound) 15wt%, sulfate 10wt%, boric acid 4wt%, sodium borate 5wt% for liquid flame retardant treatment with the remaining amount of solvent The composition was prepared.

Ammonium sulfate was used as the sulfate.

[Example 4]

A liquid flame retardant composition was prepared with 10 wt% of the compound of Formula 3, 4 wt% of boric acid, 5 wt% of ammonium phosphate dibasic, and 5 wt% of sodium borate.

[Example 5]

A liquid flame retardant composition was prepared with 15 wt% of the compound of Formula 3, 4 wt% of boric acid, 2 wt% of ammonium phosphate dibasic, and 5 wt% of sodium borate.

[Comparative Example]

A liquid flame retardant composition was prepared with 4 wt% of boric acid, 15 wt% of ammonium phosphate dibasic, and 5 wt% of sodium borate.

Example 1 Example 2 Example 3 Example 4 Example 5 Comparative example [Chemical Formula 2] Compound 7 10 15 - - - [Chemical Formula 3] Compound - - - 10 15 - Boric acid 4 4 4 4 4 4 Borate 5 5 5 5 5 5 Ammonium dibasic 10 5 - 5 2 15 sulfate - - 10 - - - water 74 76 76 76 74 76

The flame retardant composition prepared by mixing as in Examples 1 to 5 and Comparative Example was painted 1 to 3 times with a brush to sufficiently wet the dried wood through the drying step at a moisture content of 17%, and left for 20 minutes to shade After standing on the ground and sufficiently dried for 18 hours, a flame-retardant wood was prepared through the step of applying and drying the flame retardant composition to the dried specimen again three times.

[Experimental Example 1] Flame retardancy test

The flame retardancy test of wood was conducted according to the technical standards of the fire retardant type approval and product inspection of Fire Protection Agency Notification No. 2017-1 (2017. 7. 26), and the carbonization area, carbonization length, residual time, and residual flame time were measured.

Hereinafter, the results are shown in Table 2 and FIG. 1.

Flame retardant test
Item unit Flameproof treatment standard Comparative example Example 1 Example 2 Example 3 Example 4 Example 5 Carbonization length cm 12 7 5 6 9 7 Within 20 Bulletproof cm ² 64 40.26 39.7 37.4 41.4 37.8 Within 50 After salt time second 16 5 4 5 3 4 Within 10 Residual time second 30 6 5 6 4 5 Within 30 result fail pass pass pass pass pass

As can be seen from Table 2 above, Examples 1 to 5 are considered to have an excellent flame retardant effect of wood since the carbonization length and area are smaller than that of the comparative example, and the residual flame time and residual time are also less.

[Experimental Example 2] Directional test

For the aroma test, in Examples 1 to 3, respectively, aroma substance 1 (jasmine, mint, eucalyptus, cassia, ginger), aroma substance 2 (rose, lavender, lemon kleece, cedar, orris), and aroma substance 3 (Tangerine flower, haricot, yongyeonhyang) 10wt% was added, and a comparative example was used.

That is, the amount of solvent in Examples 1 to 3 was changed, and 100 experimenters belonging to each different age group stayed for 30 minutes in a room of 1 pyeong prepared in Examples 1 to 3 and Comparative Example 1, respectively, and felt points (scent, The experiment was conducted to convert comfort and dizziness) into scores.

In this case, a 10-point scoring method was applied to each item, and the average was calculated.

The results are shown in Table 3 below.

Item Example 1 Example 2 Example 3 Comparative example incense 9 9.2 8.8 4 Comfort 9.2 9.5 8.9 3 whirl none none none has exist

As can be seen from Table 3, Examples 1 to 3 are shown to have better effects in terms of fragrance and comfort than in Comparative Examples, and, unlike Comparative Examples, they do not complain of dizziness, and thus have excellent effects from both aroma and comfort. It is believed to be.

The embodiments of the present invention have been described above with reference to the accompanying drawings, but those of ordinary skill in the art to which the present invention pertains can be implemented in other specific forms without changing the technical spirit or essential features of the present invention. You can understand. Therefore, the embodiments described above are illustrative and non-limiting in all respects.

Claims (9)

It is prepared including a N,N'-bis[(alkyl)aminomethyl]phosphinic acid compound and a water-soluble inorganic compound and a solvent,
The water-soluble inorganic compound,
Contains boric acid, sodium borate and flame retardant aids,
The flame retardant auxiliary material is a flame retardant composition comprising a sulfate (sulfate).
The method of claim 1,
The N,N'-bis[(alkyl)aminomethyl]phosphinic acid compound,
N,N'-bis[(dimethyl)aminomethyl]phosphinic acid compound, N,N'-bis[(diethyl)aminomethyl]phosphinic acid compound, N,N'-bis[di(2-hydroxyethyl) A composition for flame retardant treatment, characterized in that one of aminomethyl] phosphinic acid compounds.
delete The method of claim 1,
The water-soluble inorganic compound,
A flame retardant composition comprising 2 to 10 wt% of boric acid, 2 to 10 wt% of borate, 1 to 5 wt% of phosphate as a flame retardant auxiliary material, or 5 to 20 wt% of sulfate based on the total weight of the flame retardant composition.
delete The method of claim 1,
The borate is,
Ammonium borate (Ammonium borate octahydrate) or sodium borate (Natriumborat), characterized in that the flame retardant composition.
The method of claim 1,
The composition for flame retardant treatment, characterized in that the solvent is water.
The method of claim 1,
The composition for flame retardant treatment,
It further contains a fragrance,
The composition for flame retardant treatment, characterized in that the fragrance is a vegetable natural perfume or an animal natural perfume.
It is prepared using the flame retardant composition of any one of claims 1 to 2, 4, 6 to 8,
It is manufactured through a flame retardant treatment method of injecting the flame retardant composition into the wood by vacuum decompression and pressure,
The flame retardant treatment method,
A first drying step of drying the wood to adjust the moisture content to 17%;
A first vacuum treatment step of vacuum treatment on the wood dried through the first drying step;
Injecting the composition for flame treatment by impregnating and pressing the wood vacuum-treated through the first vacuum treatment step into the composition for flame retardant treatment and injecting the composition for flame retardant treatment; and
Flame-resistant wood, characterized in that it comprises a drying step.

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