KR20190012430A - Flame retardant composition for wood and method for flame retarding treatment of wood - Google Patents

Abstract

Disclosed are a flame-retardant composition having excellent permeation into a porous structure of wood and a flame-retardant treatment method using the same. The flame-retardant composition includes: at least one organic phosphate selected from a group comprising (nitrilotris (methylene)) triphosphonic acid ammonium salt and dimethyl methylphosphonate; a penetrant including a glycol ether compound indicated in Chemical formula 2 below; a hydroxy silicone compound precursor indicated in Chemical formula 3 below; and water as a solvent. [Chemical formula 2] In Chemical formula 2, n is a natural number from 1 to 3. [Chemical formula 3] H2N-R1-Si(OR2)3, In Chemical formula 3, R1 is an alkyl radical, of which the carbon number is from 1 to 5, including at least one amine radical, and R2 is independently an alkyl group, with a carbon number from 1 to 3.

Description

FIELD OF THE INVENTION The present invention relates to flame retardant compositions for wood,

More particularly, the present invention relates to a flame retardant composition for wood having excellent permeability to a porous structure of wood, and a flame retarding method of wood using the same.

Some flammable objects used in daily life need to be flame retarded. For example, for interior and exterior materials such as curtains, partitions and doors, interior and exterior materials for various transportation means such as vehicles, trains, ships and aircraft, combustible parts for various electric and electronic products, toys, clothes, furniture, Flame retarding treatment shall be carried out in order to prevent the spread of fire or in accordance with legal regulations. In Korea, plywood, fiberboard, carpets, curtains, etc. used in special places such as high-rise buildings, theaters, hotels, hospitals, etc. are prescribed to be subject to fire protection in the Fire Service Act. The Cultural Properties Bureau strongly recommends flame-retarding treatment separately. The materials to be flame-treated are classified into three categories, wood, fiber and plastic. Flame-retarding methods vary greatly depending on the type and material of the object to be flame-treated.

As can be seen from the existing wooden treasures of Korea, if the proper preservation method is adopted, the lifespan of the timber is known to be over 1,000 years. However, the preservation technology of such superior wooden treasures is very weak to date. Wooden cultural properties are very vulnerable to fire and weak resistance to fungi and insects because they are wood. Wooden cultural properties are very dangerous for fire and biological deterioration if they are not effective for flame retarding, anti-bacterial, antiseptic and insecticide treatment.

Water-soluble inorganic salts such as phosphates, sulphates, and boric acids are commonly used as wood flame retardants. Water soluble inorganic salts have relatively high flame retarding effect, but when applied to wooden cultural properties, crystalline powder or white powder remains on the surface of wood after drying, or reacts with calcium carbonate of fugitive, Or the like, causing a whitening phenomenon, so that the appearance of the mono-chrome is deteriorated and the flame retardancy is lowered. Korean Unexamined Patent Publication Nos. 2010- 0074444 and 2007-0103884 and Korean Patent No. 776377 disclose flame-retardant compositions of such wooden buildings. On the other hand, organophosphate used as a flame retardant for fibers does not cause problems such as white residues and whitening phenomenon, but it is not used as a flame retardant for wood because of its low permeability to wood, and is used only for flame retarding of wood surface.

Patent Document 1: Korean Patent Publication No. 10-2010-0074444 Patent Document 2: Korean Patent Registration No. 10-0776377 Patent Document 3: Korean Patent Laid-Open No. 10-2007-0103884

It is an object of the present invention to provide a flame retardant composition for wood which is excellent in permeability to a porous structure of wood, and a flame retarding method of wood using the same.

Another object of the present invention is to provide a flame retardant composition for wood, which is particularly useful for flame-retarding treatment of wooden cultural properties, without causing contamination such as whitening, peeling and unevenness on wood subjected to flame-retardant treatment, and a flame retarding method of wood using the same .

In order to accomplish the above object, the present invention provides a process for producing an organic phosphoric acid salt, comprising: at least one organic phosphate selected from the group consisting of (ammonium nitrilotris (methylene)) triphosphonic acid ammonium salt and dimethyl methylphosphonate; A penetrating agent comprising a glycol ether compound represented by the following formula (2); A hydroxy silicone compound precursor represented by the following formula (3); And water as a solvent.

(2)

In Formula 2, n is an integer of 1 to 3.

(3)

H ₂ NR ₁ -Si (OR ₂ ) ₃

In the above formula (3), R ₁ is an alkyl group having 1 to 5 carbon atoms, which may contain at least one amine group, and each R ₂ is independently an alkyl group having 1 to 3 carbon atoms.

Further, the present invention provides a method for producing a wood-based fireproofing composition, comprising the steps of: applying or dispersing the flame-retardant composition for wood on the surface of wood or dipping wood in the flame-retardant composition; And drying the infiltrated flame-retardant composition.

The flame retardant composition for wood according to the present invention is excellent in permeability to the porous structure of wood and is particularly useful for flame-retarding treatment of wooden cultural properties because it does not cause contamination such as whitening, peeling, and stain on wood subjected to flame-retarding treatment.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a photograph for explaining a process of forming a heat-radiating / flame-retarding film foamed on the surface of a wood to suppress the diffusion of flame, according to the fire-proofing composition for wood according to the present invention.

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings.

The flame retardant composition for wood according to the present invention comprises an organic phosphate salt, a penetrant and a hydroxy silicon compound precursor as a flame retardant.

In the flame retardant composition for wood of the present invention, an organic phosphonate used as a flame retardant is an organic compound containing phosphorus (P), preferably phosphorus (P) and nitrogen (N) (Nitrilo tris (methylene)] trisphosphonic acid, ammonium salt), dimethyl methyl phosphonate (CH ₃ P (O) (OCH ₃ ) ₂ ) May be used alone or in combination.

[Chemical Formula 1]

The organophosphate represented by the above formula (1) is used as a flame retardant exhibiting flame retardancy and is generally used as a flame retardant for various fibers or fabrics such as synthetic fibers, woolen fabrics, cellulose fibers and blend fabrics , It is not practically used as a flame retardant for wood because of insufficient permeability to wood.

The flame retardant composition for wood of the present invention comprises a glycol ether compound represented by the following formula (2) as a penetrating agent for penetrating a flame retardant into wood.

(2)

In Formula 2, n is an integer of 1 to 3, preferably an integer of 1 to 2. When n in the above formula (2) is 1, the compound represented by the formula (2) is butyl cellosolve (ethylene glycol monobutyl ether) and when n is 2, the compound represented by the formula (2) is diethylene glycol monobutyl ether , and when n is 3, the compound represented by the general formula (2) is triethylene glycol monobutyl ether. In the flame retardant composition for wood of the present invention, it is preferable to use a mixture of butyl cellosolve having n of 1 in formula (2) and ethylene glycol monobutyl ether of n = 2 as the penetrant. When they are used in combination, the mixing ratio of butyl cellosolve: diethylene glycol monobutyl ether is 50 to 70:30 to 50 (weight ratio), preferably 55 to 65:35 to 45 (weight ratio). Here, when the mixing ratio of butyl cellosolve and ethylene glycol monobutyl ether is out of the above range, the penetration effect of the flame retardant on the wood may be lowered.

The flame retardant composition for wood of the present invention comprises a hydroxy silicon compound precursor represented by the following general formula (3).

(3)

H ₂ NR ₁ -Si (OR ₂ ) ₃

In the above formula (3), R ₁ is an alkyl group having 1 to 5 carbon atoms, which may optionally contain one or more amine groups, and each R ₂ is independently an alkyl group having 1 to 3 carbon atoms.

The hydroxysilicon compound precursor is subjected to a hydrolysis reaction with water in the flame retardant composition to form a hydroxysilicon compound, which is then impregnated into the wood in the form of a hydroxy silicone compound. Since the surface tension of the hydroxy silicone compound is low, it is excellent in permeability to wood, and not only promotes penetration of organic phosphate used as a flame retardant agent, but also bridges with wood when a flame is generated, . Examples of the hydroxysilicon compound precursor include 3-aminopropyl triethoxysilane, N- [3- (trimethoxysilyl) propyl] ethylenediamine (N- [3- (Trimethoxysilyl) propyl ] ethylenediamine), mixtures thereof, and the like.

The flame retardant composition for wood of the present invention dissolves a flame retardant, a penetrant, and a hydroxysilicon compound precursor, and includes water as a solvent for promoting penetration of the flame retardant composition into wood. In the wood flame retardant composition of the present invention, the content of the organic phosphate flame retardant is 10 to 40% by weight, preferably 15 to 35% by weight, the content of the penetrating agent is 1 to 10% by weight, preferably 3 to 8% By weight and the content of the hydroxysilicon compound precursor is 1 to 10% by weight, preferably 3 to 8% by weight, the remainder being water, the water content is 40 to 88% by weight, 79% by weight. If the content of the flame retardant is too small, there is a possibility that the flame retardancy of the flame retardant composition may be deteriorated. If the content of the flame retardant is too large, the permeability of the flame retardant composition to the wood may be deteriorated. If the content of the penetrating agent is too small, the permeability of the flame retardant composition to the wood may be lowered. If the content of the penetrating agent is too large, the composition may not be sufficiently mixed and flaking may occur due to the layer separation phenomenon. If the content of the hydroxy silicone compound precursor is too small, there is a fear that the formation of the heat radiation / flame retardant foam coating film becomes insufficient. If the content of the hydroxy silicone compound precursor is too large, A white light phenomenon may occur).

In the flame-retardant composition of the present invention, the surface treatment property and the dispersibility of the flame-retardant composition can be improved by using a mixture of a hydroxy silicone compound having a lower surface tension and an organic phosphate flame retardant and using a glycol ether compound penetrant However, the crosslinking property between the hydroxy silicone compound and the organic phosphate flame retardant and the wood is improved, and a harder carbonized film can be formed on the wood surface upon heating.

The method for flame-retarding wood by using the flame-retardant composition of the present invention can be carried out by coating or dispersing the flame-retardant composition of the present invention on the surface of wood or immersing the wood in the flame-retardant composition of the present invention, By infiltrating the flame retardant composition of the present invention, and drying the infiltrated flame retardant composition. The flame retardant composition penetrated into the porous structure of the wood is coated on the pores of the porous structure to form a flame retardant compound layer. When exposed to the flame, a foam film is formed to exhibit flame retardant performance.

Specifically, when the wood to which the flame-retardant composition of the present invention is impregnated is heated by the flame, the flame-retardant composition of the flame-retardant composition is thermally decomposed to form phosphoric acid, and the phosphoric acid is condensed to form pyrophosphate, And water. Phosphoric acid and pyrophosphate thus formed carbonize the wood layer to form a heat radiation / flame retarding film as shown in the following reaction formula (1).

[Reaction Scheme 1]

More specifically, the phosphoric acid and the pyrophosphate produced by heating the organic phosphoric acid flame retardant are used for dehydration reaction of terminal alcohol groups contained in cellulose, hemicellulose, lignin and the like, which are main components of wood. To produce water and to produce carbon-carbon double bonds in the wood, which are crosslinked at high temperatures to form a carbonized layer to form heat and flame retardant layers. The heat radiation and flame retardant layer thus formed can suppress the generation of radicals associated with ignition, volatilization of the plastic material and oxygen diffusion, and the surface of the wood can be separated and protected from the flame. In addition, the water generated during the formation of the carbonized film also serves to dilute the oxidizing gas to help ignite.

The hydroxy silicone compound of the flame-retardant composition according to the present invention is crosslinked with wood in the form of the following reaction formula 2 to form a foamed heat-radiating / flame-retarding film on the surface of the wood as shown in Fig. 1, .

[Reaction Scheme 2]

In the above reaction scheme 2, "Hydroxy silicone" is a compound formed by condensation of a hydroxy silicone compound used in the composition of the present invention, wherein X is a hydroxyl group, an alkyl group having 1 to 5 carbon atoms, an alkoxy group having 1 to 5 carbon atoms, (-NH ₂ ), m is an integer of 1 to 4, and n is an integer of 0 to 3, preferably 1 to 3.

The wood to which the flameproofing composition of the present invention can be applied is a wooden building interior and exterior material such as a bench, a railing, a window frame, a deck, a door, a fence and a playground; Wooden buildings such as temples and wooden cultural properties; Wood engravings, wooden blocks such as wooden blocks, and the like. Particularly, the flameproofing composition of the present invention can be applied to woody cultural properties such as whiteness, lacquer, and stain on light blue (erythroderma, amphipatite, rhododendron, And thus it is particularly useful for flame treatment of wooden cultural properties. In the present invention, the term "wooden cultural property" means all wooden buildings and wooden structures having preserved value as well as cultural properties designated as national treasures, treasures, tangible cultural properties, etc., which are managed by the Cultural Properties Protection Act.

Hereinafter, the present invention will be described in more detail by way of specific examples and comparative examples. The following examples illustrate the present invention and are not intended to limit the scope of the present invention. In the following examples and comparative examples, test methods for the respective properties are as follows.

(1) VOCs (Volatile Organic Compounds) Content : 10 mL of the flame retardant was placed in a headspace vial (Perkin-Elmer, USA) and heated at 90 ° C for 30 minutes. MS (Tarac GC / DSQIIMS, ThermoFinnigan, USA).

(2) Formaldehyde Discharge : The flame retardant is applied on both sides of a test piece (70 mm x 150 mm, 8 sheets) and placed in a desiccator with 300 mL of distilled water. The temperature was maintained at 23 DEG C for 24 hours to form formaldehyde contained in distilled water, and the resultant was measured with a UV absorption spectrophotometer (UV-1650PC, SHIMADZU).

(3) Heavy metal content (Pb, Cd, Hg, Cr ⁶⁺ ) : Add acetone to the flame retardant and centrifuge to separate the solid. Add the hydrochloric acid to the solid content and stir at 30 ° C for 15 minutes. The liquid sample is dried by adding nitric acid and then filled with 50 mL of distilled water. Each solution was analyzed using ICP, AAS, UV absorption spectrophotometer.

(4) Hydrogen ion concentration (pH) : The flame retardant was measured with a pH meter.

(5) Specific gravity : The flame retardant was filled in the light weight bottle and the weight difference between before and after was measured.

(7) Evaluation of weatherability

(a) Test conditions: The test specimens coated with the flame retardant were dried for 7 days or more, and then installed in an accelerated weathering tester (UV2000, ATLAS, USA) and colorimeter (McBath, UK).

- Test cycle: UV 50 ° C, 4 h → condensation 40 ° C, 4 h

- Cycle repeat: 25 times, total 200 hours

- Radiance: 0.63 W / m ² , Lamp type: UV-A 340 nm

(b) Measurement items

- Appearance: Comparing before and after the accelerated weathering test, judge the whiteness, peeling, smudge and gloss phenomenon with the naked eye of the tester to check for any abnormality.

- Comparison color difference: The test piece coated with the flame retardant and the blank test piece not coated with the flame retardant are measured for chromaticity before and after the test using a color difference meter to obtain a color difference value. The difference between the color difference value of the test specimen coated with the flame retardant and the color difference value of the blank test specimen not coated with the flame retardant should be less than 3.0 for each specimen and the average for each monochrome color should be less than 1.5.

(8) Evaluation of flame retardancy

(a) Test conditions: Evaluation was made using a flame-proofing tester (FL-45MC, SUGA test instrument) at a flame length of 65 mm and a heating time of 2 minutes.

(b) Metrics and criteria

- Residual flame time: The time from the burner's flame is removed to the time when the flame is raised and the burning is stopped. Within 10 seconds

- Seduction time: The time from when the burner's flame is removed to when the flame is not raised and the burning state is stopped, within 30 seconds

- Carbonization area: the area of the carbonized part of the test piece (wood) after the test, 50 cm ²

(Measuring device: PLANIX EX (TAMAYA technics Inc., JAPAN))

- Carbonization length: The length of the carbonized part of the test piece (wood) after the test, 20 cm

(9) Persistence evaluation

(a) Test conditions

(1) Weatherability test: A test piece coated with a flame retardant was installed in an accelerated weathering tester (UV 2000, ATLAS, USA) and subjected to accelerated weathering test under the following conditions.

② Flame resistance test: The flame retardancy test was carried out on the test pieces subjected to accelerated weathering resistance test by using a flame proofing tester (FL-45MC, SUGA test instrument).

- Test cycle: UV 50 ° C, 4 h → condensation 40 ° C, 4 h

- Cycle repeat: 25 times, total 200 hours

- Radiance: 0.63 W / m ² , Lamp type: UV-A 340 nm

- Flame length: 65 mm, Heating time: 2 minutes

(b) Metrics and criteria

- Residual flame time: The time from the burner's flame is removed to the time when the flame is raised and the burning is stopped. Within 10 seconds

- Seduction time: The time from when the burner's flame is removed to when the flame is not raised and the burning state is stopped, within 30 seconds

- Carbonization area: the area of the carbonized part of the test piece (wood) after the test, 55 cm ²

(Measuring device: PLANIX EX (TAMAYA technics Inc., JAPAN))

- Carbonization length: the length of the carbonized part of the test piece (wood) after the test, 25 cm

(10) Evaluation of hygroscopicity and dryness : The test specimens coated with the flame retardant and the blank specimens not coated were placed in a thermostatic chamber (WK-340, WEISS, German) and colorimeter (McBath, UK) .

(a) Constant temperature and humidity test conditions

(50 ± 2) ° C, (95 ± 3)% RH, 4 h → (20 ± 2) ° C, 1 h → (Cycle repeat: 10 times, total of 140 hours)

(b) Measurement items

- Appearance: Comparing before and after the accelerated weathering test, judge the whitening, peeling, and smear phenomenon by the tester's eyes and check for any abnormality.

- Comparison color difference: The test piece coated with the flame retardant and the blank test piece not coated with the flame retardant are measured for chromaticity before and after the test using a color difference meter to obtain a color difference value. The difference between the color difference value of the test specimen coated with the flame retardant and the color difference value of the blank test specimen not coated with the flame retardant should be less than 3.0 for each specimen and the average for each monochrome color should be less than 1.5.

[Example 1] Preparation of flame retardant composition for wood and evaluation of flame retarding effect

In a flask equipped with a stirrer, 65 parts by weight of water and 25 parts by weight of (ammonium) triphosponic acid ammonium salt (AMGUARD DR) represented by the formula (1) were added and mixed for 2 hours with stirring. 5 parts by weight of 3-aminopropyl triethoxysilane was added to the prepared mixed solution, stirred for 1 hour and 45 minutes, and 4: 1 by weight of diethylene glycol monobutyl ether and butyl cellosolve, 6 (weight ratio), and the mixture was stirred for 2 hours and 30 minutes to prepare a wood flame retardant composition.

The results are shown in Table 2, and the results are shown in Table 2. The flame resistance was evaluated, and the results are shown in Table 3 Respectively.

Test Items unit result standard Test Methods VOCs g / L Not detected 50 KS M ISO 11890-2 Formaldehyde dissipation mg / L Not detected 1.0 KS M 1998-4 Lead (Pb) mg / kg Not detected Sum
0.1%
Below KS M ISO 3856-1 Cadmium (Cd) mg / kg Not detected KS M ISO 3856-4 Mercury (Hg) mg / kg Not detected KS M ISO 3856-7 Hexavalent chromium (Cr ⁶⁺ ) mg / kg Not detected KS M ISO 3856-5 Hydrogen ion concentration (pH, 21 ℃) - 7.1 6 to 8 KS M 0011 Constituent - clear clear FTIR, XRD Density (specific gravity, 23 ℃) g / mL 1.14 1.08 to 1.16 KS M ISO 2811-1

sample
(Monochromatic pigment) Sample (flame retardant application)
The color difference (? E * ab) Blank test (no flame retardant applied) Color difference (ΔE * ab) Comparison color difference Individual color difference Average color difference Eruption One 2.13 1.23 0.90 0.83 2 2.06 1.86 0.21 3 3.31 1.93 1.38 Yang One 0.68 1.01 0.33 0.64 2 0.95 1.40 0.45 3 1.06 2.19 1.13 Long One 0.60 0.87 0.27 1.03 2 1.47 0.99 0.47 3 0.70 3.03 2.33 County Office One 0.78 2.04 1.26 1.05 2 0.67 1.89 1.22 3 1.09 1.74 0.65 Samcheong One 1.47 1.73 0.26 1.30 2 3.29 1.50 1.80 3 3.61 1.76 1.85 Saturn One 3.46 5.81 2.35 1.03 2 2.79 2.94 0.14 3 2.18 2.76 0.58 Masonry One 3.27 3.59 0.32 0.41 2 2.56 3.25 0.69 3 2.31 2.08 0.22 scarlet One 7.45 6.00 1.45 3.24 2 10.15 6.64 3.51 3 9.29 4.54 4.75 Party One 1.36 0.83 0.53 0.93 2 0.90 1.37 0.47 3 1.78 3.57 1.79 Lower One 1.52 0.67 0.82 1.05 2 1.49 1.11 0.38 3 2.39 4.32 1.94 Multilateral One 0.60 0.25 0.35 0.28 2 0.54 0.24 0.30 3 0.46 0.28 0.18 Color One 1.58 1.56 0.02 0.47 2 2.32 1.38 0.94 3 1.51 1.07 0.44 Indian ink One 0.81 1.02 0.21 0.23 2 0.92 0.94 0.01 3 1.45 0.97 0.48

sample Time (in seconds) Burst time (seconds) Carbonization area (㎠) Carbonization length (cm) Eruption 2 0 33.4 8.0 Yang One 0 35.8 7.7 Long 3 0 36.8 8.7 County Office One 0 32.7 10.0 Samcheong One 0 28.3 8.7 Saturn 0 0 35.2 8.3 Masonry One 0 33.8 7.7 scarlet 3 0 33.3 9.3 Party 0 0 32.8 9.0 Lower 5 0 39.5 7.3 Multilateral 0 0 25.9 8.7 Color 0 0 32.6 8.3 Indian ink 2 0 35.6 7.7 Unapplied 0 0 27.5 8.3

[Example 2] Preparation of flame retardant composition for wood and evaluation of flame retarding effect

Except that 5 parts by weight of diethylene glycol monobutyl ether was used instead of 5 parts by weight of a 4: 6 (by weight) mixture of diethylene glycol monobutyl ether and butyl cellosolve as a penetrating agent, A composition was prepared.

The produced flame retardant composition was evaluated for the presence of harmful substances and basic properties, and the results are shown in Table 4. The results are shown in Table 5, and the flame retardancy was evaluated. The results are shown in Table 6 Respectively.

Test Items unit result standard Test Methods VOCs g / L Not detected 50 KS M ISO 11890-2 Formaldehyde dissipation mg / L Not detected 1.0 KS M 1998-4 Lead (Pb) mg / kg Not detected Sum
0.1%
Below KS M ISO 3856-1 Cadmium (Cd) mg / kg Not detected KS M ISO 3856-4 Mercury (Hg) mg / kg Not detected KS M ISO 3856-7 Hexavalent chromium (Cr6 +) mg / kg Not detected KS M ISO 3856-5 Hydrogen ion concentration (pH, 21 ℃) - 7.1 6 to 8 KS M 0011 Constituent - clear clear FTIR, XRD Density (specific gravity, 23) ℃ g / mL 1.14 1.08 to 1.16 KS M ISO 2811-1

sample
(Monochromatic pigment) Sample (flame retardant application)
The color difference (? E * ab) Blank test (no flame retardant applied) Color difference (ΔE * ab) Comparison color difference Individual color difference Average color difference Eruption One 1.57 0.67 0.9 1.00 2 1.38 1.11 0.27 3 2.48 4.32 1.84 Yang One 3.77 5.81 2.04 0.86 2 2.82 2.94 0.12 3 2.35 2.76 0.41 Long One 1.80 1.73 0.07 1.38 2 3.44 1.50 1.94 3 3.90 1.76 2.14 County Office One 3.64 3.59 0.05 0.35 2 2.55 3.25 0.7 3 2.37 2.08 0.29 Samcheong One 1.24 0.83 0.41 0.83 2 0.99 1.37 0.38 3 1.87 3.57 1.7 Saturn One 7.10 6.00 1.10 1.30 2 7.87 6.64 1.23 3 6.12 4.54 1.58 Masonry One 0.71 0.87 0.16 0.26 2 1.35 0.99 0.36 3 2.78 3.03 0.25 scarlet One 0.87 2.04 1.17 0.78 2 0.98 1.89 0.91 3 1.48 1.74 0.26 Party One 0.97 1.02 0.05 0.23 2 0.99 0.94 0.05 3 1.55 0.97 0.58 Lower One 1.68 1.56 0.12 0.71 2 2.88 1.38 1.50 3 1.58 1.07 0.51 Multilateral One 0.99 1.01 0.02 0.20 2 1.23 1.40 0.17 3 1.78 2.19 0.41 Color One 2.86 1.23 1.63 1.02 2 2.22 1.86 0.36 3 2.99 1.93 1.06 Indian ink One 0.77 0.25 0.52 0.60 2 0.98 0.24 0.74 3 0.82 0.28 0.54

sample Time (in seconds) Burst time (seconds) Carbonization area (㎠) Carbonization length (cm) Eruption One 0 35 9 Yang 0 0 37 8 Long 0 0 38 9 County Office 0 0 40 8 Samcheong One 0 36 8 Saturn 6 0 34 10 Masonry 0 0 39 9 scarlet 0 0 37 9 Party 0 0 39 10 Lower 0 0 36 9 Multilateral 0 0 35 9 Color One 0 36 8 Indian ink 0 0 38 11 Unapplied 0 0 35 8

[Example 3] Preparation of flame retardant composition for wood and evaluation of flame retardant effect

Except that 5 parts by weight of butyl cellosolve was used instead of 5 parts by weight of a 4: 6 (by weight) mixture of diethylene glycol monobutyl ether and butyl cellosolve as a penetrating agent, to prepare a wood flame retardant composition .

The results are shown in Table 8, and the flame resistance was evaluated. The results are shown in Table 9, and the results are shown in Table 8. The results are shown in Table 8, Respectively.

Test Items unit result standard Test Methods VOCs g / L Not detected 50 KS M ISO 11890-2 Formaldehyde dissipation mg / L Not detected 1.0 KS M 1998-4 Lead (Pb) mg / kg Not detected Sum
0.1%
Below KS M ISO 3856-1 Cadmium (Cd) mg / kg Not detected KS M ISO 3856-4 Mercury (Hg) mg / kg Not detected KS M ISO 3856-7 Hexavalent chromium (Cr6 +) mg / kg Not detected KS M ISO 3856-5 Hydrogen ion concentration (pH, 21 ℃) - 7.1 6 to 8 KS M 0011 Constituent - clear clear FTIR, XRD Density (specific gravity, 23) ℃ g / mL 1.14 1.08 to 1.16 KS M ISO 2811-1

sample
(Monochromatic pigment) Sample (flame retardant application)
The color difference (? E * ab) Blank test (No flame retardant applied)
The color difference (? E * ab) Comparison color difference Individual color difference Average color difference Eruption One 1.50 0.67 0.83 0.87 2 1.68 1.11 0.57 3 3.10 4.32 1.22 Yang One 3.55 5.81 2.26 1.09 2 2.64 2.94 0.30 3 2.05 2.76 0.71 Long One 1.07 1.73 0.66 1.42 2 3.33 1.50 1.83 3 3.54 1.76 1.78 County Office One 3.03 3.59 0.56 0.56 2 2.84 3.25 0.41 3 2.78 2.08 0.70 Samcheong One 1.94 0.83 1.11 1.07 2 0.99 1.37 0.38 3 1.85 3.57 1.72 Saturn One 7.64 6.00 1.64 1.53 2 7.89 6.64 1.25 3 5.99 4.54 1.45 Masonry One 0.61 0.87 0.26 0.66 2 1.77 0.99 0.78 3 2.10 3.03 0.93 scarlet One 0.79 2.04 1.25 1.06 2 0.67 1.89 1.22 3 1.03 1.74 0.71 Party One 0.87 1.02 0.15 0.31 2 0.54 0.94 0.40 3 1.34 0.97 0.37 Lower One 1.08 1.56 0.48 0.67 2 2.11 1.38 0.73 3 1.88 1.07 0.81 Multilateral One 0.45 1.01 0.56 0.71 2 0.36 1.40 1.04 3 1.66 2.19 0.53 Color One 2.03 1.23 0.80 0.65 2 2.07 1.86 0.21 3 2.86 1.93 0.93 Indian ink One 0.99 0.25 0.74 0.59 2 0.88 0.24 0.64 3 0.67 0.28 0.39

sample Time (in seconds) Burst time (seconds) Carbonization area (㎠) Carbonization length (cm) Eruption 0 0 39 8 Yang 0 0 38 9 Long 0 0 39 9 County Office 0 0 39 9 Samcheong 0 0 38 8 Saturn 6 0 40 8 Masonry 0 0 37 9 scarlet 0 0 37 10 Party 0 0 40 9 Lower 0 0 38 10 Multilateral One 0 38 9 Color 0 0 40 9 Indian ink 0 0 37 9 Unapplied 0 0 34 8

[Example 4] Preparation of flame retardant composition for wood and evaluation of flame retardant effect

Except that 5 parts by weight of N- [3- (trimethoxysilyl) propyl] ethylenediamine was used instead of 5 parts by weight of 3-aminopropyl triethoxysilane. A flame retardant composition was prepared.

The results are shown in Table 11, and the flame resistance was evaluated. The results are shown in Table 12 below. Respectively.

Test Items unit result standard Test Methods VOCs g / L Not detected 50 KS M ISO 11890-2 Formaldehyde dissipation mg / L Not detected 1.0 KS M 1998-4 Lead (Pb) mg / kg Not detected Sum
0.1%
Below KS M ISO 3856-1 Cadmium (Cd) mg / kg Not detected KS M ISO 3856-4 Mercury (Hg) mg / kg Not detected KS M ISO 3856-7 Hexavalent chromium (Cr6 +) mg / kg Not detected KS M ISO 3856-5 Hydrogen ion concentration (pH, 21 ℃) - 7.1 6 to 8 KS M 0011 Constituent - clear clear FTIR, XRD Density (specific gravity, 23) ℃ g / mL 1.14 1.08 to 1.16 KS M ISO 2811-1

sample
(Monochromatic pigment) Sample (flame retardant application)
The color difference (? E * ab) Blank test (No flame retardant applied)
The color difference (? E * ab) Comparison color difference Individual color difference Average color difference Eruption One 3.44 0.67 2.77 2.87 2 3.83 1.11 2.72 3 7.44 4.32 3.12 Yang One 7.89 5.81 2.08 2.36 2 5.64 2.94 2.70 3 5.06 2.76 2.30 Long One 4.37 1.73 2.64 3.13 2 4.64 1.50 3.14 3 5.38 1.76 3.62 County Office One 6.09 3.59 2.50 2.98 2 5.81 3.25 2.56 3 5.96 2.08 3.88 Samcheong One 3.97 0.83 3.14 2.67 2 4.76 1.37 3.39 3 5.04 3.57 1.47 Saturn One 9.31 6.00 3.31 3.02 2 9.36 6.64 2.72 3 7.56 4.54 3.02 Masonry One 3.34 0.87 2.47 2.82 2 4.66 0.99 3.67 3 5.36 3.03 2.33 scarlet One 5.96 2.04 3.92 3.46 2 5.87 1.89 3.98 3 4.23 1.74 2.49 Party One 3.75 1.02 2.73 2.93 2 4.65 0.94 3.71 3 3.33 0.97 2.36 Lower One 4.28 1.56 2.72 3.37 2 5.46 1.38 4.08 3 4.39 1.07 3.32 Multilateral One 4.84 1.01 3.83 3.33 2 4.64 1.40 3.24 3 5.12 2.19 2.93 Color One 4.33 1.23 3.10 2.57 2 4.05 1.86 2.19 3 4.34 1.93 2.41 Indian ink One 3.77 0.25 3.52 3.37 2 3.64 0.24 3.40 3 3.47 0.28 3.19

sample Time (in seconds) Burst time (seconds) Carbonization area (㎠) Carbonization length (cm) Eruption 0 0 39 8 Yang 0 0 38 9 Long 0 0 39 9 County Office 0 0 39 9 Samcheong 0 0 38 8 Saturn 6 0 40 8 Masonry 0 0 37 9 scarlet 0 0 37 10 Party 0 0 40 9 Lower 0 0 38 10 Multilateral One 0 38 9 Color 0 0 40 9 Indian ink 0 0 37 9 Unapplied 0 0 34 8

[Comparative Example] Preparation of flame retardant composition for wood and evaluation of flame retardant effect

A flame retardant composition for wood was prepared in the same manner as in Example 1 except that 5 parts by weight of ethanolamine was used instead of 5 parts by weight of a 4: 6 (by weight) mixture of diethylene glycol monobutyl ether and butyl cellosolve as a penetrating agent .

The results are shown in Table 14, and the flame retardancy was evaluated. The results are shown in Table 15 Respectively.

Test Items unit result standard Test Methods VOCs g / L Not detected 50 KS M ISO 11890-2 Formaldehyde dissipation mg / L Not detected 1.0 KS M 1998-4 Lead (Pb) mg / kg Not detected Sum
0.1%
Below KS M ISO 3856-1 Cadmium (Cd) mg / kg Not detected KS M ISO 3856-4 Mercury (Hg) mg / kg Not detected KS M ISO 3856-7 Hexavalent chromium (Cr6 +) mg / kg Not detected KS M ISO 3856-5 Hydrogen ion concentration (pH, 21 ℃) - 7.1 6 to 8 KS M 0011 Constituent - clear clear FTIR, XRD Density (specific gravity, 23) ℃ g / mL 1.14 1.08 to 1.16 KS M ISO 2811-1

sample
(Monochromatic pigment) Sample (flame retardant application)
The color difference (? E * ab) Blank test (No flame retardant applied)
The color difference (? E * ab) Comparison color difference Individual color difference Average color difference Eruption One 2.32 0.67 1.65 3.00 2 4.90 1.11 3.79 3 7.89 4.32 3.57 Yang One 8.97 5.81 3.16 3.38 2 4.24 2.94 3.40 3 6.34 2.76 3.58 Long One 4.48 1.73 2.75 3.32 2 5.64 1.50 4.14 3 4.82 1.76 3.06 County Office One 5.45 3.59 1.86 2.30 2 5.61 3.25 2.36 3 4.76 2.08 2.68 Samcheong One 3.90 0.83 3.07 2.20 2 3.64 1.37 2.27 3 4.84 3.57 1.27 Saturn One 8.91 6.00 2.91 2.58 2 8.99 6.64 2.35 3 7.03 4.54 2.49 Masonry One 2.29 0.87 1.42 1.97 2 3.44 0.99 2.45 3 5.06 3.03 2.03 scarlet One 0.16 2.04 2.24 1.78 2 0.32 1.89 1.57 3 0.23 1.74 1.51 Party One 3.56 1.02 2.54 2.62 2 3.28 0.94 2.34 3 3.96 0.97 2.99 Lower One 4.18 1.56 2.62 2.86 2 3.96 1.38 2.58 3 4.46 1.07 3.39 Multilateral One 3.76 1.01 2.75 2.24 2 3.68 1.40 2.28 3 4.96 2.19 1.69 Color One 3.88 1.23 2.65 2.08 2 4.04 1.86 2.18 3 3.34 1.93 1.41 Indian ink One 3.76 0.25 3.51 3.50 2 3.75 0.24 3.51 3 3.76 0.28 3.48

sample Time (in seconds) Burst time (seconds) Carbonization area (㎠) Carbonization length (cm) Eruption 0 0 39 8 Yang 0 0 38 9 Long 0 0 40 10 County Office 0 0 39 9 Samcheong 0 0 39 9 Saturn 6 0 40 8 Masonry 0 0 37 9 scarlet 0 0 37 10 Party 0 0 40 9 Lower 0 0 38 10 Multilateral One 0 39 9 Color 0 0 40 9 Indian ink 0 0 37 9 Unapplied 0 0 34 8

Evaluation of Physical Properties of Flame Retarding Composition : The flame retarding compositions of Examples 1 to 4 and Comparative Examples were evaluated for their residual properties , and their moisture absorption and dryness were evaluated. The results are shown in Table 16 together with the above-described evaluation results of harmfulness, weatherability, Respectively.

Hazard Weatherability Flammability Persistence Dry and hygroscopic Example 1 ○ ○ ○ ○ ○ Example 2 ○ ○ ○ ○ ○ Example 3 ○ ○ ○ ○ ○ Example 4 ○ △ ○ △ △ Comparative Example ○ X ○ X X

In Table 16, "○" in the flame resistance category indicates a case where all the specimens pass carbonization, "X" indicates a case in which one of 13 colors of carbon monoxide is carbonated, and in the items of weatherability, Represents a case where color difference is good without whitening,? Represents glossiness, and X represents whitening.

As shown in Table 16, the flame retardancy of the flame retardant composition according to the present invention varies depending on the type of the penetrating agent. That is, in the case where butyl cellosolve, diethylene glycol monobutyl ether or the like is used as the penetrating agent (Examples 1 to 4), the penetration performance of the flame retardant composition is excellent and the flame proofing property is excellent. In the case of using ethanolamine (Comparative Example 1), the drying of the wood is slow due to the hygroscopic property and whitening occurs.

Although the flame-retardant composition according to the present invention has been described with reference to specific examples, the present invention is not limited to the specific examples described above, and various modifications are possible within the scope of the following claims.

Claims (5)

(Nitrilotris (methylene)) triphosphonic acid ammonium salt, and dimethyl methylphosphonate;
A penetrating agent comprising a glycol ether compound represented by the following formula (2);
A hydroxy silicone compound precursor represented by the following formula (3); And
A flame retardant composition for wood comprising water as a solvent.
(2)

In Formula 2, n is an integer of 1 to 3.
(3)
H ₂ NR ₁ -Si (OR ₂ ) ₃
In the above formula (3), R ₁ is an alkyl group having 1 to 5 carbon atoms, which may contain at least one amine group, and each R ₂ is independently an alkyl group having 1 to 3 carbon atoms. [Claim 2] The method according to claim 1, wherein the penetrating agent comprises diethyleneglycol monobutyl ether having a ratio of butylcellosolve n = 2 in which n is 1 in Formula 2 at a mixing ratio of 50 to 70:30 to 50 (weight ratio) , Fire retardant composition for wood. 2. The wood flame retardant composition according to claim 1, wherein the hydroxysilicon compound precursor is selected from the group consisting of 3-aminopropyltriethoxysilane and N- [3- (trimethoxysilyl) propyl] ethylenediamine. . The method of claim 1, wherein the content of the organic phosphate flame retardant is 10 to 40% by weight, the content of the penetrating agent is 1 to 10% by weight, the content of the hydroxy silicone compound precursor is 1 to 10% And the content is 40 to 88% by weight. Infiltrating the flame retardant composition into the porous structure of the wood by applying or dispersing the flame retardant composition for wood according to any one of claims 1 to 4 on the surface of the wood or by immersing the wood in the flame retardant composition; And
And drying the infiltrated flame retardant composition.

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