JP2005194319A - Flame retardant treatment liquid and flame retardant material treated with the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a flame retardant treatment liquid which solves the problem that the use of a boron compound in a flame retardant treatment liquid brings about the lowering of flame retardance at a low concentration of the boron compound due to its low solubility and causes the problem of leaching due to its solubility in water. <P>SOLUTION: The flame retardant treatment liquid is obtained by adding phosphoric acid and a silane coupling agent to a weak acidic or a weak alkaline metal salt aqueous solution containing a boron compound to obtain a mixture solution and adding a plant extract containing polyphenolic compounds as the main ingredient and antimony tartrate to the mixture solution. The flame retardant treatment liquid is applicable to the materials the major component of which is cellulose such as wood, paper and natural fibers. The flame retardant treatment liquid improves the fixation of the chemicals, exhibits a high flame retardance and minimizes leaching to occur. The addition of antimony tartrate strengthens the preventive effect to leaching. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to an incombustible treatment liquid, and more particularly, mainly an incombustible treatment mainly composed of a boron compound for use in a combustible member, that is, a member mainly composed of cellulose such as wood, paper and natural fiber. Regarding liquids.

Conventionally, it is said that natural organic materials such as wood, paper, and natural fibers are flammable.
In particular, from the viewpoint of the construction field, because it is flammable, legal restrictions are imposed and the range of use is extremely limited. It is the result.
On the other hand, this disadvantage is an advantage from the aspect of recycling that can be incinerated and is non-polluting.
For this reason, various techniques, that is, a flame retardant treatment technique, have been developed as fire prevention measures for natural organic materials (see Patent Document 1).

At present, there are two types of combustion suppression action by the flame retardant treatment: physical action and chemical action, and the latter action is expected in the flame retardant treatment liquid.
There are various types of flame retardant treatment solutions such as phosphorus compounds, nitrogen compounds, boron compounds, and halogen compounds.

  However, phosphorous compounds, nitrogen compounds, and halogen compounds have a large amount of smoke containing harmful gases during combustion, and phosphoric acid is a strong acid, and there is a problem that the material is damaged and discolored.

On the other hand, the boron compound does not generate harmful gas from the thermal decomposition product during combustion, and the material is hardly damaged or discolored.
In addition, there is an antiseptic ant effect, and the target material can be made high in added value.

A drug containing a boron compound as a main component has a remarkable effect of suppressing heat generation by dehydration carbonization.
The dehydration carbonization is a process in which a chemical is heated to produce an acid or a base, and cellulose is dehydrated in a short time at a low temperature to form water and carbon.
That is, this combustion suppression effect is composed of two actions: an endothermic action due to water evaporation and a reduction in the heat generation rate due to the generation of carbon residue having a slow combustion speed.
Japanese Patent Publication No. 7-14801

However, when a boron compound is used as a flame retardant solution,
1) Solubility is low, and at low concentrations, the combustion suppression effect decreases.
2) Leaching occurs due to water solubility.
There were two disadvantages, and it was necessary to overcome these problems.
The present invention provides an incombustible treatment liquid that has a high combustion suppression effect and that suppresses the occurrence of leaching as much as possible to solve such problems.

  As a result of intensive studies under these circumstances, the present inventors have found that the solubility is improved under the catalytic action of metal salts, and that the silane coupling agent produces film-forming properties. It has been found that the leaching can be suppressed by the system material, and that the fixability of the polyphenol material is improved by the antimony tartrate salt, and this finding has led to the achievement of the present invention.

  That is, the present invention provides (1) a mixed aqueous solution by adding phosphoric acid and a silane coupling agent to a weak acid or weak alkali metal salt aqueous solution containing a boron compound, and the mixed aqueous solution contains a polyphenol compound and an antimony tartrate salt. It exists in the incombustible processing liquid which added the plant extract as a component.

  And (2) exists in the nonflammable processing liquid whose content of the plant extract which has a polyphenol type compound as a main component is 0.5 to 40% of a total component weight.

  And (3) exists in the incombustible processing liquid whose content of an antimony tartrate salt is 30 to 50% of the plant extract which has a polyphenol type compound as a main component.

  And (4) exists in the fire prevention material which impregnated the above-mentioned incombustible processing liquid to the wood.

  The present invention can employ a combination of two or more selected from the above 1 to 4 as long as it meets this purpose.

According to the non-flammable treatment liquid of the present invention, the fixability of the drug is improved, the combustion suppressing effect is enhanced, and the occurrence of leaching can be suppressed as much as possible.
Therefore, it is possible to provide non-combustible wood.
Moreover, although the leaching inhibitory effect can be exhibited by adding the plant extract which has a polyphenol type compound as a main component to a process liquid, the leaching inhibitory effect becomes more excellent by adding antimony tartrate further.
This incombustible treatment liquid can be widely applied to members mainly composed of cellulose, such as wood, paper, and natural fibers.

An incombustible treatment liquid of the present invention is a mixed aqueous solution obtained by adding phosphoric acid and a silane coupling agent to a weak acid or weak alkali metal salt aqueous solution containing a boron compound, and a plant extract containing a polyphenol compound as a main component in the mixed aqueous solution, And antimony tartrate.
Therefore, by impregnating the raw material, the combustion suppressing effect and the leaching suppressing effect, particularly the leaching suppressing effect are greatly improved.
The material to be impregnated or imparted is mainly a member mainly composed of cellulose such as wood, paper and natural fibers.

[Combustion suppression effect]
As is well known, since the solubility of a boron compound alone is low, it is necessary to make the boron compound into a high-concentration solution in order to efficiently penetrate the material.
Therefore, in the present invention, the solubility is improved by the catalytic action of a weak acid or weak alkali metal salt.
As the weak acid or weak alkali metal salt, sodium fluoride, sodium phosphite, sodium sulfite, sodium borofluoride or the like was used.
The content of the weak acid or weak alkali metal salt is 1 to 10% of the total component weight.
If its content is less than 1%, it is difficult to dissolve the boron compound, and if it exceeds 10%, it is inefficient in terms of productivity.
Here, the total component weight is the total weight of each component excluding water from the incombustible treatment liquid.

Further, since the boron compound alone is powdered after drying, it is necessary to further change the crystallinity thereof, and by adding phosphoric acid and a silane coupling agent, it is possible to impart film-forming properties of the material after drying. it can.
Thereby, the fixed amount of the chemical | medical agent to a raw material increases, adhesiveness improves, and the combustion suppression effect improves.

A silane coupling agent has a functional group chemically bonded to an inorganic compound and an organic compound.
Representative examples include amino silane, ethoxy silane, methoxy silane, etc. In this experiment, Shin-Etsu Chemical Co., Ltd., for example, product names KBM-602, KBM-603, KBE-603, KBM-903 , KBE-903, KBE-04, KBM-13, KBM-22, KBE-22, KBE-103, KPN-3504, KBM-3063, KBM-3103C and the like.
The content of the silane coupling agent is 0.1 to 5% of the total component weight.
If the content is less than 0.1%, it is difficult to impart film-forming properties, and if it exceeds 5%, the viscosity of the liquid increases and it is difficult to process the material.

[Leaching suppression effect]
Next, it is necessary to suppress leaching of the chemical (noncombustible treatment liquid) in a wet state.
In this invention, the amount of drug leaching is reduced by using a polyphenol-based material as a bark extract component.

The use of the polyphenol compound aims at a chemical change that makes the boron compound difficult to dissolve in water after the material is dried by the adsorption of the boron compound by the polyphenol compound.
This chemical change is supported by Example 3 described later.
For the polyphenol compound, purified tannin is mainly used.
The content of the polyphenol compound is 0.5 to 40% of the total component weight.
If the content is less than 0.5%, the effect is small, and if it exceeds 40%, the fixing amount of the boron compound may be reduced.

However, the blending of the polyphenol compound tends to increase the temperature of the solid analysis of the drug.
There are two processing methods for applying this medicine to a material.
One is to infiltrate the polyphenol compound and then to dry it, and to infiltrate the boron compound into the material.
The second is a method in which a boron compound and a polyphenol compound are mixed to maintain the temperature up to a temperature range where no precipitation occurs and fix the material inside.
In the present invention, the latter method is adopted from the viewpoint of fixing efficiency.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated, this invention is not limited to an Example, A various modification is possible.

(I) Appropriateness of the drug fixing rate at the time of member drying First, phosphoric acid and a silane coupling agent [methoxysilane (KBM-22)] were added to a metal salt aqueous solution containing a boron compound to obtain a mixed aqueous solution.
The mixed aqueous solution was adjusted by adding tannin, which is a plant extract containing a polyphenol compound as a main component, to obtain a treatment liquid 1 (corresponding to an incombustible treatment liquid).
On the other hand, a treatment liquid 2 was prepared in the same manner as the treatment liquid 1 except that tannin was not included.
The blending ratio (wt%) of the components in the treatment liquid 1 and the treatment liquid 2 is as shown in Table 1 below.

A specimen (A, B, C, D, E) made of wood was immersed in the treatment liquid 1 of Table 1 for 3 hours, and the temperature was maintained and impregnated.
After impregnation, it was dried and its weight (weight before leaching) and water content were measured.
Here, the specimen is a piece of wood of 20 cm × 12 cm × 5 cm.
Thereafter, the specimens (A, B, C, D, E) were left for 3 days under high humidity conditions of a dry bulb temperature of 65 ° C. and a relative humidity of 90%.
This is a condition where positive leaching is likely to occur.
Furthermore, it was completely dried at 105 ° C. by constant temperature drying, and its weight (weight after drying after leaching) was measured.
The leaching amounts of the chemicals of the five specimens (A, B, C, D, E) are as shown in Table 2 below.

Next, a specimen (F, G, H, I, J) of wood pieces of 20 cm × 12 cm × 5 cm is prepared, and using the treatment liquid 2, the specimens (A, B, C, D, E) described above are used. The same treatment as in Example 1, and the weight and moisture content were measured.
The amount of drug leaching of the five specimens (F, G, H, I, J) was as shown in Table 3 below.

From Tables 2 and 3, it can be seen that the amount using the treatment liquid 1 clearly decreases the amount of leaching as compared with the case using the treatment liquid 2.
From this, it can be understood that a sufficient drug leaching suppression effect can be exhibited by using a polyphenol compound.
In addition, although the quantity of the polyphenol compound in the process liquid 1 is about 1% of the whole process liquid, it is thought that the chemical | medical agent leaching suppression effect improves by increasing the quantity.

[Improvement of anti-depression effect by antimony tartrate salt]
By the way, in the present invention, antimony tartrate is extremely effective in improving the fixability of a polyphenol compound to a boron compound in a treatment solution containing a boron compound.
Antimony tartrate salts include antimony potassium tartrate (so-called “tartar”).
In order to obtain confirmation of this point, a treatment solution 5 containing potassium antimonyl tartrate, a treatment solution 6 containing potassium antimonyl tartrate, and a treatment solution 7 were prepared.
Table 5 below shows the blending ratio (% by weight) of components in the treatment liquid 5, the treatment liquid 6, and the treatment liquid 7.

The specimen (M) made of wood was immersed in the treatment liquid 5 (980 ml) of Table 5 at 30 ° C. for 20 minutes.
Similarly, the specimen (N) made of wood was immersed in the treatment liquid 6 (980 ml) of Table 5 and the specimen (R) made of wood was soaked in the treatment liquid 7 (980 ml) at 30 ° C. for 20 minutes.
Here, the size of the specimen is a 2 cm × 2 cm × 1 cm piece of wood.
Thereafter, water was added to make 1000 ml, and the boron leaching amount was measured by ICP.
The boron leaching amount for each specimen was as shown in Table 6.
That is, in the test body (M) treated with the treatment liquid 5 not using antimonyl potassium tartrate, the boron leaching amount was 122 ppm, but the test body (N) treated with the treatment liquid 6 using antimonyl potassium tartrate was The specimen (R) treated with the treatment liquid 7 using potassium antimonyl tartrate in the same manner was 65.2 ppm.
Thus, it is clear that the amount of boron leaching is reduced in the treatment solution using potassium antimonyl tartrate.

(II) Validity of Combustion Inhibiting Effect First, phosphoric acid and a silane coupling agent [methoxysilane (KBM-22)] were added to a metal salt aqueous solution containing a boron compound to obtain a mixed aqueous solution.
To this mixed aqueous solution, tannin, which is a plant extract containing a polyphenol compound as a main component, was added to prepare a treatment liquid 3.
On the other hand, the treatment liquid 4 was prepared in the same manner as the treatment liquid 3 except that the silane coupling agent (KBM-22) was not included.
The mixing ratio (% by weight) of the components in the treatment liquid 3 and the treatment liquid 4 is as shown in Table 4 below.
In this example, a specimen made of wood was impregnated with the treatment liquid 3 in Table 4, and the specimen (K) was tested with an ISO corn calorimeter.
Similarly, the treatment liquid 4 was impregnated, and the same test was performed on the specimen (L).

FIG. 1 shows a graph of the combustion test result of the specimen (K).
This result shows that it exceeds the standard performance as a noncombustible material in the Building Standard Law.
FIG. 2 shows a graph of the combustion test result of the specimen (L).

From this result, it can be seen that it corresponds to the standard performance as a quasi-incombustible material in the Building Standard Law, but has not reached the standard performance as a non-combustible material.
In this way, by including a predetermined amount of the silane coupling agent, it is possible to realize a non-combustible material according to the Building Standard Law.

The same treatment liquid was prepared except that catechin was used instead of tannin in the treatment liquid 1 shown in Table 1.
A ¹³ C-NMR spectrum analysis was performed on this treatment liquid.
In this case, the reason why the parent catechin (polyphenol compound) is used instead of tannin is that ¹³ C-NMR spectrum analysis is easy.

FIG. 3 shows the results of ¹³ C-NMR spectrum analysis.
In this figure, since the peak derived from catechin is reduced, it can be understood that catechin and other components interact in the treatment solution, and that catechin undergoes a chemical change.

The present invention relates to an incombustible treatment liquid, and more specifically, is mainly used for a flammable member, that is, a member mainly composed of cellulose such as wood, paper, and natural fiber. It can be applied to indoor wall materials, furniture, and clothing materials, and the same effect can be expected.

FIG. 1 is a diagram illustrating a graph of a combustion test result of the test body (K). FIG. 2 is a graph showing a combustion test result graph of the specimen (L). FIG. 3 is a diagram showing the results of ¹³ C-NMR spectrum analysis.

Claims (4)

  Phosphoric acid and a silane coupling agent are added to a weak acid or weak alkali metal salt aqueous solution containing a boron compound to obtain a mixed aqueous solution, and a plant extract mainly composed of a polyphenol compound and an antimony tartrate salt are added to the mixed aqueous solution. Non-combustible treatment liquid characterized by   The incombustible treatment liquid according to claim 1, wherein the content of the plant extract containing a polyphenol-based compound as a main component is 0.5 to 40% of the total component weight.   The incombustible treatment liquid according to claim 2, wherein the content of the antimony tartrate salt is 30 to 50% of the plant extract mainly composed of a polyphenol compound. A fireproofing material, wherein wood is impregnated with the incombustible treatment liquid according to claim 1.

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