JPH0585587B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides (1) a condensed polymer compound or/and a compound having the ability to form a condensed polymer, (2) an amide group,
Water resistance and weather resistance can be improved by treating wood with a reaction product or mixture consisting of phosphonic acids having a methylolamide group, epoxy group, or hydroxyl group and (3) a silicon atom-containing inorganic compound (excluding oxides). The present invention relates to a treatment method for producing a wood material having excellent rust resistance, solvent resistance, fire retardancy, insect repellency, corrosion resistance, far-curing properties, and the like. In recent years, methods for treating wooden materials used outdoors and indoors include coating the surface with various paints by brush painting, spray painting, etc., and injecting various chemicals under pressure, reduced pressure, or a combination of both. It has been. However, it has water resistance, weather resistance, rust resistance, water resistance, solvent resistance, long-distance curing, fire resistance with little afterflame, insect resistance, corrosion resistance, and also ease of application and economy. A method for processing wood materials with excellent quality has not yet been established. According to the present invention, it is possible to impart these performances to wooden materials. All of the condensation polymer compounds and/or compounds capable of forming condensation polymers referred to in the present invention are either water-soluble, water-dispersible, organic solvent-soluble, or non-water-dispersible before being treated with wood. It must be selected depending on the embodiment and purpose. and,
Specific examples of these compounds include those described in (A) to (I) below, and these may be used alone or in combination of two or more. (A) Triazine compounds such as melamine, benzoguanamine, acetoguanamine, melon, melam, etc.
Preferably, adducts or condensates of melamine or a mixture of two or more thereof and formaldehyde, and alkyl ethers thereof, preferably alkyl ethers having 1 to 4 carbon atoms. (B) A mixed amino compound consisting of a triazine compound as defined in (A) above, preferably melamine and another amino compound such as urea, thiourea, biuret, dicyandiamide, guanidine phosphate, etc., with a weight content of the triazine compound of at least 10%. Adducts, condensates, and alkyl ethers thereof similar to (A) in the above cases. (C) Triazine compounds, preferably mixtures of melamine and phenolic compounds, cocondensates with formaldehyde in which the weight ratio of melamine is at least 5%, preferably 10% or more. (D) A condensate of phenols such as phenol, resorcinol, and cresol with formaldehyde. (E) Condensate of xylenes and formaldehyde. (F) Condensate of furfural and formaldehyde. (G) Condensate of aniline and formaldehyde. (H) One or more compounds of epoxy resin, polyamide resin, polyamine or phenolic resin. (I) Alkyd resin, preferably having an oil length of 40 or less, which is hardened by baking when used in combination with an amino resin such as (A) or (B) above. Among those classified into the above nine systems, especially (A)
and (B) are superior to the above (C ), (D), (E), (F), (G),
It is more effective than (H) and (I) and can achieve the purpose of the present invention. In addition, (C), (D), (E), (F), (G) and (H) above
In the case of (A) and (B), the range of reaction targets is more limited than in the cases of (A) and (B), although there are conditions that give a good effect. Furthermore, in the case of (I), although there is a wide range of composition and performance, in order to effectively achieve the purpose of the present invention, these polymer compounds must not soften, liquefy, or even liquefy even under high-temperature heating. It is desirable that the material has as little fluidity as possible. The phosphonic acid compounds used in the present invention are exemplified by (a) to (d) below. (a) 3-(dimethylphosphono)propionamide,
3-(diethylphosphono)propionamide,
3-(dibutylphosphono)propionamide,
3-(diisopropylphosphono)propionamide, 3-[bis(2-chloroethyl)phosphono]propionamide, 3-(diphenylphosphono)propionamide, 3-[bis(2,3
-dichloropropyl)phosphono]propionamide, 3-(diethylphosphono)-2-methylpropionamide, 3-[2,2-dimethyltrimethylenephosphono]propionamide, 3-
(1-methyltrimethylenephosphono)propionamide,

【formula】

【formula】

[ka]

【formula】

An amide group-containing phosphonic acid compound such as [Formula]. (b) N-hydroxymethyl-3-(dimethylphosphono)propionamide, N-hydroxymethyl-3-(diethylphosphono)propionamide, N-hydroxymethyl-3-(dibutylphosphono)propionamide, N- Hydroxymethyl-3-(diisopropylphosphono)propionamide, N-hydroxymethyl-3-[bis(2-chloroethyl)phosphono]propionamide, N-hydroxymethyl-3-(diphenylphosphono)propionamide, N- Hydroxymethyl-3-[bis(2,3-dichloropropyl)phosphono]propionamide, N-hydroxymethyl-3-(diethylphosphono)-2
-Methylpropionamide, N-hydroxymethyl-3-[2,2-dimethyltrimethylenephosphono)propionamide, N-hydroxymethyl-3-(1-methyltrimethylenephosphono)
propionamide,

【formula】

【formula】

[ka]

[ka]

[Formula] etc., and a series of methylol compounds of amide group-containing phosphonic acids obtained by reacting the phosphonic acid amide described in (b) with formaldehyde or/or a formaldehyde generating substance. (c) bis(2-hydroxyethyl)aminomethylphosphonic acid diethyl ester, 3-(dimethylphosphono)propionic acid (2-hydroxyethyl) ester, 3-(dimethylphosphono)propionic acid (2-hydroxyethyl) ester,
3-(diisopropylphosphono)propionic acid (2-hydroxyethyl) ester, 3-(diphenylphosphono)propionic acid (2-hydroxyethyl) ester, 3-(diethylphosphono)
-2-methylpropionic acid (2-hydroxyethyl) ester, 3-(1-methyltrimethylenephosphone)propionic acid (2-hydroxyethyl) ester, 2,3-dihydroxypropylphosphonic acid diethyl ester, 1-hydroxyethane -1,1-diphosphonic acid,

【formula】

【formula】

[Formula] Hydroxyl group-containing phosphonic acid compounds. (d) 3-(dimethylphosphono)propionate glycidyl ester, 3-(diethylphosphono)propionate glycidyl ester, 3-[bis-
(2-chloroethyl)phosphono]propionic acid glycidyl ester, 3-(diethylphosphono)
-2-Methylpropionate glycidyl ester, 3-(1-methyltrimethylenephosphono)
Propionate glycidyl ester, epoxypropylphosphonic acid-bis-(2-chloroethyl)
ester, epoxypropylphosphonic acid diethyl ester, and formula

【formula】

[Formula] Epoxy group-containing phosphonic acid compounds. Examples of water-insoluble silicon-containing inorganic compounds other than oxides include aluminum aluminosilicate,
Potassium aluminosilicate, calcium aluminum disilicate, zirconium silicate, silicon carbide, calcium silicate, beryllium aluminum silicate, barium (meta)silicate, beryllium (meta)silicate, magnesium (meta)silicate,
(Meta)magnesium calcium silicate, (Meta)
Examples include silicic acid, calcium (meta)silicate, dimagnesium monosilicide, and the like, and these can be used alone or in combination with two or more or other inorganic compounds. The main uses of wooden materials treated by the method of the present invention are wall materials, ceiling materials, used indoors and outdoors,
Building materials and furniture such as roofing materials, flooring materials, pillar materials, shelf materials, other interior materials, exterior materials, etc., in the case of wooden materials that require the above-mentioned performance in vehicles, ships, and various public facilities. It can also be applied to In the present invention, a condensed polymer compound exemplified by (A) to (I) above and/or a compound having condensed polymer type performance and phosphonic acids exemplified by (a) to (d) above are combined. The mixing ratio or the weight ratio when reacting is such that the former is at least 0.1 parts by weight, preferably 1 to 50 parts by weight, in terms of phosphorus content, to 100 parts by weight of the former in terms of solid content, and 1 to 100 parts by weight, preferably 5 to 50 parts by weight of a silicon atom-containing inorganic compound or/and a magnesium atom-containing inorganic compound or/and a calcium atom-containing inorganic compound based on 100 parts by weight of the solid content of the acid-containing composition. It is best to do so. Moreover, it is preferable to use the above-mentioned inorganic compound in the form of fine powder. The composition of the present invention is applied in the form of an aqueous solution, an aqueous dispersion, or a non-aqueous dispersion, but depending on the type of polymer compound, it can also be applied without dilution. Methods for applying the composition of the present invention to wooden materials include, for example, applying the composition by dipping, spraying, brushing, flow coating, press-fitting under pressure or reduced pressure, and then curing by leaving at room temperature. A method of curing by curing and a method of curing by heating can be adopted. The polymer compound and/or polymer-forming compound used in the present invention itself, or the polymer compound and/or polymer-forming compound composition containing a silicon atom-containing inorganic compound (excluding oxides) itself has a high degree of fire protection. However, as shown in the examples, none of the wood materials treated with these compositions have high fire retardant properties, and once heated and ignited, the wood materials burn down completely. reach. In addition, wood materials treated with a phosphonic acid-containing polymer compound and/or a polymer-forming compound composition ignite even when heated, and have high fire retardant properties without burning down. However, there is a phenomenon in which a self-extinguishing afterflame remains for a long time even after the fire source is removed. On the other hand, according to the present invention, a wooden material treated with a condensed polymer compound containing a phosphonic acid and a silicon atom-containing inorganic compound or/and a compound having the ability to form a condensed polymer shape is heated. It has a high degree of fireproofing properties, and shows surprising performance in that the afterflame time is significantly shortened or no afterflame occurs at all.In addition, it also has the excellent performance described above. The advantage of using phosphonic acids and condensation resins as their fixing agents for wood materials is that a film with higher hardness can be obtained compared to the case of polymer resins, and as shown in the examples below. If an appropriate combination of the two is selected, the phosphonic acid will be fixed by the chemical bond between the two, and water resistance will be obtained. However, in order to completely cure both components on the surface of the wood material, conditions that cause deterioration of the wood material, such as heating at 100° C. or higher, are required. here,
When the above-mentioned inorganic compound is preferably added in the form of fine powder, the reaction between the condensation resin and the fine powder on the surface not only improves fireproofing properties, but also significantly accelerates curing at low temperatures and cures at high temperatures. Prevention of cracks due to the difference in expansion coefficient between the wood material and the fireproof coating film can be achieved. Example 1 PH of 252 parts of melamine and 486 parts of 37.2% formalin
After reacting at 10.3, the pH was lowered to 4.0, 384 parts of methanol was added for etherification, and approximately 700 parts of water-soluble methylated methylolmelamine resin with a solid concentration of 70% was obtained by concentration under reduced pressure. (yield approx. 95
%). 500 parts of this melamine resin, 250 parts of 70% 3-(dimethylphosphono)propionamide aqueous solution,
1000 parts of a treatment liquid was prepared by adding 192 parts of water to 50 parts of fine magnesium silicate powder, 10 parts of ammonium chloride as a curing catalyst, and 3 parts of sodium salt of succinic acid ethylene oxide sulfate as a penetrant. This treatment solution was applied with a brush to the surface of a 15 cm x 30 cm x 1 cm rice cedar board at a rate of 250 parts/m ² in terms of solid content, and then left to dry and harden at 25° C. for 48 hours.
The properties obtained are shown in Table 1. Example 2 In Example 1, instead of 250 parts of 70% 3-(dimethylphosphono)pyropionamide aqueous solution,
Exactly the same test was conducted except that 230 parts of 3-(dimethylphosphono)propionic acid glycidyl ester was used, and the properties are shown in Table 1. Example 3 In Example 1, instead of 250 parts of 70% 3-(dimethylphosphono)propionamide aqueous solution, 3
Exactly the same test was carried out except that 140 parts of 2-hydroxyethyl ester -(dimethylphosphono)propionate and 50 parts of aluminum silicate fine powder were used instead of 50 parts of silica magnesium fine powder. The properties are shown in Table 1. Example 4 In Example 1, 210 parts of dimethylphosphonosuccinic acid dimethyl ester was used instead of 250 parts of 70% glue 3-(dimethylphosphono)propionamide aqueous solution.
The same test was carried out except that 100 parts of calcium sulfate/magnesium metasilicate mixed powder (weight ratio 20/80) was used in place of 50 parts of magnesium silicate powder, and the properties were evaluated. It is shown in Table 1. Example 5 In Example 1, magnesium silicate fine powder 50
Exactly the same test was conducted except that 50 parts of calcium silicate/aluminum hydroxide mixed powder (weight ratio 60/40) was used instead of 1 part, and the properties are shown in Table 1. Example 6 63 parts of melamine, 180 parts of urea and 629 parts of 37.2% formalin were reacted at pH 10.3 and then dehydrated under reduced pressure to produce a melamine-urea co-condensed resin with a non-volatile content of 70%.
(yield approximately 96%). 400 parts of this co-condensed resin,
70% N-methylol 3-(dimethylphosphono)
250 parts of propionamide aqueous solution, calcium sulfate/aluminum silicate mixed fine powder (weight ratio 50/
50) 80 parts, 25 parts of ammonium chloride and 3 parts of sodium salt of succinic acid ethylene oxide sulfate
was added to 272 parts of water to prepare 1000 parts of a treatment liquid. Exactly the same test was conducted using this product, and its characteristics are shown in Table 1. Comparative Example 1 A test was conducted in exactly the same manner as in Example 1, except that 250 parts of a 70% aqueous 3-(dimethylphosphono)propionamide solution and 50 parts of fine magnesium silicate powder were removed, and the characteristics are shown in Table 1. Ta. Comparative Example 2 In Example 1, magnesium silicate fine powder 50
Exactly the same test was conducted except that the part was removed, and the characteristics are shown in Table 1. Comparative Example 3 A test was conducted in exactly the same manner as in Example 1, except that 250 parts of a 70% 3-(dimethylphosphono)propionamide aqueous solution was removed, and the characteristics were compared to those of the first example.
Shown in the table. Comparative Example 4 In Example 1, 40 parts of 70% 3-(dimethylphosphono)propionamide aqueous solution was replaced with 250 parts of 3-(dimethylphosphono)propionamide aqueous solution.
Exactly the same test was conducted except that 525 parts of an aqueous solution of % ammonium phosphate was used, and the properties are shown in Table 1.

[Table] Example 7 Obtained by heating and reacting 220 parts of resorcin, 80.6 parts of 37.2% formalin, and 110 parts of water at 80°C for 3 hours.
For 100 parts of 60% aqueous resorcinol resin, 3 parts of curing catalyst mainly composed of paraformaldehyde.
- Add 10 parts of (dimethylphosphono)propionate glycidyl ether and 80 parts of fine aluminum calcium silicate powder and apply with a brush to a 2 cm thick board of hard beech wood for high quality furniture at a solid content of 200 g/m ² . , dried at room temperature in an atmosphere of 30°C and 70% RH. After about 100 minutes, the surface will no longer be sticky.
After about 12 hours, curing was completely completed. This coated plate showed a beautiful reddish-brown color, and the coated film showed strong resistance to scratching and impact. In addition, this coated plate did not ignite until 10 times of flame contact in the fire protection test according to the method shown in Table 1 (Note 3), and showed an afterflame resistance of A. Even after drying, the appearance did not change at all, and even when exposed to flame, it exhibited fire protection and afterflame properties equivalent to those before immersion in water. Example 8 Bis(2-chloroethylphosphono)succinic acid dimethyl ester 12 with Betsukosol M-7652 70, an acid-curing aminoalkyd resin for wood coatings manufactured by Dainippon Ink and Chemicals Co., Ltd. with a non-volatile content of 55%.
1 part, 10 parts of 2 magnesium silicide fine powder, 2 parts of toluene, 2 parts of butanol, and 4 parts of para-toluene sulfonic acid catalyst, and applied this to the surface of a 4 mm thick interior plywood board, in terms of solid content, 250 g. /m ² by brushing. At a room temperature of 20℃, the curing time is 2 minutes to the touch, and the curing time is
25 minutes, pencil curing was B after 2 hours, F after 6 hours, and H after 24 hours. In addition, this coating film is transparent, has a high gloss, shows little change in appearance even after being immersed in water for 3 hours, and has excellent alkali resistance and solvent resistance.
It also showed good results in staining tests with magic ink, lipstick, etc. Furthermore, 60℃ and
Even when it was left in saturated steam at 80°C for 48 hours, the decrease in hardness and gloss was extremely low. When this painted plywood was subjected to a fire protection test using the method of Example 1, it did not catch fire until the second time. In addition, the afterflammability was ranked A. Example 9 60 parts of furfural resin with 100% non-active content, 8 parts of diphenylphosphonosuccinic diamide, magnesium silicate/aluminum oxide mixed fine powder (weight ratio
40/60), 1 part of resin curing catalyst paratoluenesulfonic acid, and 21 parts of water were used as a treatment liquid, and a solid content of 180 g/
It was applied at a ratio of m ² and left to cure at room temperature for 3 days. This treated plate formed a tough film with impact resistance and a pencil hardness of H on the surface. This processed board exhibited water-resistant and fire-retardant properties, and did not catch fire even when exposed to the flame of a gas burner at 950°C for 4 minutes. Example 10 Epoxy resin [Epiclon 153-60T, Dainippon Ink & Chemicals Co., Ltd. product, epoxy equivalent 390-410
(per solid content), bromine content 46% (per solid content),
solid content 60%] 300 parts, epoxy curing agent mainly composed of aliphatic polyamide [Epicron B-3150,
Company product, amine value 150 (per solid content), acid value 3 or less, solid content 70%] 140 parts, reactive 3-(dimethylphosphono)propionic acid glycidyl ester 50
100 parts of non-reactive bis(2-chloroethylphosphono)succinic acid dimethyl ester, 15 parts of potassium aluminum silicate fine powder, and 380 parts of toluene were applied to the plate of Example 1 with a solid content of 200 parts.
It was brushed on both sides at a ratio of g/m ² and cured at room temperature for 3 days. The properties of this coated plate are shown in Table 2. Comparative example 5 Epicuron 153-60T 486 parts, Epicuron B-
A processing liquid consisting of 195 parts of 3150 and 320 parts of toluene,
was applied to a homogeneous plate in the same manner as in Example 10, and its properties are shown in Table 2.

【table】

Claims (1)

[Scope of Claims] 1 (1) A condensed polymer compound or/and a compound having the ability to form a condensed polymer; (2) a phosphonic acid having an amide group, methylolamide group, epoxide group, or hydroxyl group; and (3) A method for treating wood materials using a reaction product or mixture consisting of a silicon atom-containing inorganic compound (excluding oxides). 2. A method for treating a wooden material according to claim 1, wherein the condensation polymer compound and/or the compound (1) having the ability to form a condensation polymer is a triazine thermosetting resin. .