JPWO2017094517A1 - Ant-proof flame-retardant treatment liquid and method for producing flame-retardant base material using the same - Google Patents

Abstract

Problems with conventional flame retardants and flame retardants containing boron (or boron compounds) (possibility of health hazards / environmental impacts, whitening phenomenon when used on wood, and irritating feeling when used on cloth and paper, It is an object of the present invention to provide a flame retardant treatment solution that can solve the difficulty of penetrating and impregnating wood due to low water solubility and high viscosity. It does not contain any of boron and boron compounds, and contains the above problems by an ant-proofing flame-retardant treatment solution characterized by containing water, ammonium dihydrogen phosphate, ammonium sulfate, ammonia, an impregnation accelerator and an ant-proofing agent. Settled.

Description

The present invention relates to an ant-proofing flame retardant solution, and more particularly to an ant-proof flame-retardant solution that does not contain boron (or boron compounds) harmful to the human body.
Moreover, this invention relates to the manufacturing method of this ant-proofing flame-retardant processing liquid, and the manufacturing method of the flame-retardant base material which uses this ant-proofing flame-retardant processing liquid.

  The ant-proofing flame retardant treatment liquid of the present invention can add ant-proofing property and flame-retardant / flame-proofing properties to wood and bamboo by impregnating wood and bamboo, and cloth other than wood and bamboo It is a highly water-soluble treatment liquid that can add flame retardancy and flame resistance to paper.

  As a chemical | medical agent for providing a flame retardance and flameproofness to base materials, such as wood, cloth, paper, what added the boron compound etc. are known (patent documents 1-5).

Boron compounds are excellent in flame retardancy, flameproofing and antproofing properties, but boron compounds are known to have various adverse effects on the human body.
For example, it has been pointed out that boric acid, which is a boron compound, causes symptoms such as cough, sore throat, eye redness and pain, nausea, vomiting, diarrhea, abdominal pain, skin rash, headache, convulsions (Non-patent Document 1). ).

  According to the new European toy directive that has been applied since July 20, 2013, boron (boron compounds) is newly targeted for harmful substances, and boron (a harmful substance for toys from toy materials and toy paints) Transition limit values such as boron compounds) were set.

  Boron (boron compounds) also causes environmental impacts such as soil contamination and groundwater contamination in accordance with the national soil pollution control law standards when wood, cloth and paper impregnated with them are discarded in the soil. It is defined as a possible substance.

  Boron (boron compound) is mainly used as a raw material for glass fibers. For this reason, when it is impregnated with wood, a whitening phenomenon occurs on the surface of the wood, and when it is impregnated with cloth or paper, a feeling of tingling occurs.

  Boron (boron compound) is a harmful substance with low solubility in water, and when impregnating wood, most of the forced impregnation methods such as vacuum and pressure impregnation are used. Pressure regulation technology and high cost are required.

  Boron (boron compound) is known to have flame retardant and flame proof properties as well as ant proof properties (for example, Patent Document 6), but it is sufficiently penetrated and impregnated into wood. If not, the ant protection may not be exhibited.

  For this reason, development of the processing liquid excellent in the flame retardance and flameproofness using the component which substitutes for boron (boron compound) is desired.

JP 2004-050828 A JP 2014-139269 A JP 2002-348574 A JP 2010-248110 A JP-T-2001-527093 JP 2007-196420 A

National Institute of Health Sciences “International Chemical Safety Card” Boric ACID

  This invention is made | formed in view of the said background, The subject is providing the flame-retardant treatment liquid which can solve the trouble of the conventional flame retardant and flame retardant containing boron (boron compound). There is to do.

Specifically, the treatment liquid of the present invention does not use components that cause health problems and environmental loads such as boron (boron compounds), but uses only safe components.
Moreover, the conventional flame retardant / flameproofing agent containing boron (boron compound) causes a whitening phenomenon caused by boron (boron compound) to wood and a feeling of tingling to cloth or paper. In such a processing solution, such a problem hardly occurs.
Furthermore, the treatment liquid of the present invention is highly soluble in water, has a low viscosity, and uses a high-performance impregnation accelerator, so that it easily penetrates and impregnates wood and bamboo materials. For this reason, it is possible to sufficiently infiltrate and impregnate wood and bamboo, easily exhibiting ant-proofing properties, and contribute to the reduction of infiltration and impregnation costs.

  As a result of intensive studies to solve the above problems, the present inventor dissolved and dispersed water-soluble ammonium dihydrogen phosphate and ammonium sulfate, ammonia, an impregnation accelerator, and an anti-anticide in water. Found that it is not inferior to boron (boron compound) in flame retardancy and flame retardancy, and can be easily impregnated and impregnated into wood, and can produce a highly ant-proof flame retardant treatment solution, The present invention has been completed.

  That is, the present invention does not contain any of boron and boron compounds, and contains water, ammonium dihydrogen phosphate, ammonium sulfate, ammonia, an impregnation accelerator and an anti-anticide, A treatment liquid is provided.

  The present invention also provides the above-mentioned ant-proofing flame retardant solution, wherein the ant-proofing agent is a neonicotinoid compound, particularly dinotefuran.

  Further, the present invention provides a method for producing the above-mentioned ant-proofing flame retardant treatment liquid, and impregnating and impregnating a flammable base material (particularly wood / bamboo material) with the ant-proofing flame-retardant treatment liquid. A feature of the present invention is to provide a flame retardant substrate production method.

  Since the ant-proofing flame retardant treatment liquid according to the present invention can contribute to flame retardancy of wood, bamboo, cloth, paper, etc., and does not contain harmful substances such as boron (boron compound) and heavy metals, There is no risk of health problems or environmental impact.

  In addition, since the ant-proofing flame retardant treatment liquid of the present invention does not contain boron (boron compound), the whitening phenomenon of wood caused by boron (boron compound), and the irritating feeling of cloth products and paper products Hardly occurs.

  The ant-proofing flame retardant treatment liquid of the present invention, when used on wood, can be flame-retardant and at the same time, can be ant-proofed and preserved, so that application of flame retardant and application of ant-proofing agent These two processes become one process, and the efficiency of flame retardant and ant-proof construction in wooden houses is improved.

  The ant-proofing flame retardant treatment liquid of the present invention has higher water solubility and lower viscosity than conventional flame retardant / flame retardants containing boron (boron compound). For this reason, the ant-proof flame retardant treatment liquid of the present invention is easy to penetrate and impregnate wood, and can be easily infiltrated and impregnated without advanced technology, thereby reducing costs. In addition to being connected, the flame retardant substrate can exhibit sufficient flame retardancy and ant protection.

  In recent years, bamboo has attracted attention as a substitute for wood. In China, bamboo is often used as flooring, wall materials, ceiling materials, furniture materials, etc., and fire resistance is required as a fire countermeasure. In Southeast Asia and the like, there is a current situation where bamboo is overgrown and is treated as waste, and there is a demand for effective use of such bamboo.

  The ant-proofing flame retardant treatment liquid of the present invention does not penetrate (impregnate) from the surface of bamboo because of its water repellency, but easily penetrates in the direction of the conduit, making it flame retardant for building materials made of bamboo. Can be used for.

  Hereinafter, the present invention will be described. However, the present invention is not limited to the following embodiments, and can be arbitrarily modified and implemented.

The ant proof flame retardant treatment liquid of the present invention is to make the flammable base material flame retardant (or flameproof) by permeating and impregnating the flammable base material.
Specifically, the “flammable substrate” is a substance such as wood, bamboo, paper, cloth, etc. that continues to burn when ignited in a normal environment. The ant-proofing flame retardant treatment liquid of the present invention penetrates and impregnates these substrates by a method such as immersion, coating, spraying, perforation injection, impregnation with an impregnation apparatus, etc. Adds flammability and flameproofness.
“Flame retardant” means that flammable base materials such as wood, bamboo, cloth and paper are difficult to burn, and “flameproof” means that the flammable base material burns violently. Although it is difficult to do, there is no clear difference between the two. Hereinafter, in this specification, both are referred to as “flame retardant”. Further, imparting flame retardancy to a substrate is referred to as “to make it flame retardant”.

Moreover, the ant-proof flame-retardant treatment liquid of the present invention imparts “ant-proof” properties to wood and bamboo when used on wood and bamboo.
The term “ant-proof” refers to the property of preventing insects such as termites from coming close to wood or bamboo, or the property of killing close termites.

  Boron (boron compound) is killed by eating termites and the like (it is a food poison), while dinotefuran used in the present invention is killed by touching it (it is a contact poison).

The ant-proofing flame retardant treatment liquid of the present invention contains neither boron nor boron compounds.
As described above, boron (or a boron compound such as boric acid) has both flame retardancy and ant protection, so its performance as a flame retardant treatment for wood was excellent. In order to improve this problem, the ant-proofing flame retardant solution of the present invention contains neither boron nor boron compounds.

  The ant-proofing flame retardant treatment liquid of the present invention contains water, ammonium dihydrogen phosphate, ammonium sulfate, ammonia, an impregnation accelerator and an ant-proofing agent.

<Ammonium dihydrogen phosphate>
Ammonium dihydrogen phosphate (NH ₄ H ₂ PO ₄ ) is used in water-soluble fertilizers, flameproofing agents, fermentation aids, auxiliaries, metal surface treatment agents, etc., and has high water solubility and high safety to the human body. It is a substance.
Ammonium dihydrogen phosphate is a component that has been examined for toxicity by the Japan Flame Retardant Association, and its safety has been confirmed.

<Ammonium sulfate>
Ammonium sulfate ((NH ₄ ) ₂ SO ₄ ) is a substance that is used in water-soluble fertilizers, flameproofing agents, snow-curing agents, and the like, and is highly water-soluble and highly safe for the human body.
Ammonium sulfate is a component that has been tested for toxicity by the Japan Flame Protection Association, and its safety has been confirmed.

Both ammonium dihydrogen phosphate and ammonium sulfate are flame retardant / flame retardant substances, but the ant-proof flame retardant treatment liquid of the present invention contains ammonium dihydrogen phosphate and ammonium sulfate in a specific ratio. By being mixed, flame retardancy is remarkably improved.
Specifically, with respect to 1 part by mass of ammonium dihydrogen phosphate, the content ratio of ammonium sulfate is preferably 1 to 1.5 parts by mass, more preferably 1.1 to 1.4 parts by mass, and 1.2 to 1.3 parts by mass is particularly preferable.

<Ammonia>
Ammonia (NH ₃ ) is a substance that exhibits weak alkalinity. Ammonium dihydrogen phosphate and ammonium sulfate are weakly acidic, and when disinfecting and impregnating flame retardant solution using these are infiltrated / impregnated into cloth or paper, the discoloration (yellowing) of the cloth or paper is caused. In order to prevent this, it is contained in the ant-proof flame-retardant treatment liquid for the purpose of making the pH neutral or weakly alkaline and for the purpose of improving flame retardancy.
Ammonia can be appropriately used after diluting commercially available aqueous ammonia (for example, 25% aqueous ammonia).

The ratio of ammonia is preferably 0.07 to 0.12 parts by mass, more preferably 0.08 to 0.11 parts by mass, and 0.09 to 0.10 parts by mass with respect to 1 part by mass of ammonium dihydrogen phosphate. Part is particularly preferred.
When the lower limit of the ammonia ratio is not less than the above, yellowing can be sufficiently prevented. When the upper limit is not more than the above, it is difficult to adversely affect the flame retardancy.

  The ant-proofing flame retardant treatment liquid of the present invention is preferably alkaline (that is, the pH exceeds 7) in order to prevent yellowing of cloth and paper.

In addition, when the ant-proofing flame retardant treatment liquid of the present invention is used for bamboo, the pH is more preferably 7.5 or more and 9.0 or less, and the pH is 7.8 or more and 8.3 or less. It is particularly preferred that
When the pH is within the above range, the flame-retardant component and the ant-proof component easily penetrate into the bamboo material, and the flame-retardant property and the ant-proof property are easily improved.

In addition, when the ant-proofing flame retardant treatment liquid of the present invention is used for wood, the pH is more preferably 5.5 or more and 7.0 or less, and the pH is 6.0 or more and 6.5 or less. It is particularly preferred that
When the pH is within the above range, the flame-retardant component and the ant-proof component easily penetrate into the wood, and the flame-retardant property and the ant-proof property are easily improved.

  By adjusting the content ratio of ammonia to ammonium dihydrogen phosphate or ammonium sulfate, the pH of the ant-proofing flame retardant treatment liquid of the present invention can be set within the above range.

<Impregnation accelerator>
The impregnation accelerator is used to help the flame-retardant component and the ant-proof component of the ant-proofing flame-retardant treatment liquid penetrate into the base material. By using an impregnation accelerator, flame retardant components and ant repellant components can be spread evenly inside the base material, and flame retardancy and ant repellency are improved.

Examples of the impregnation accelerator include higher fatty acids, higher alcohol sulfates, fatty acid sulfates, alkylallylsulfonates, phosphates, polyoxyalkylene alkylphenyl ethers, polyacrylate resins, and polymethacrylate resins. Etc.
Also, commercially available products include Jonkrill (registered trademark, manufactured by BASF Japan), Solsperse (registered trademark, manufactured by Nihon Lubrizol Co., Ltd.), and Sunsepara (registered trademark, manufactured by Sanyo Chemical Co., Ltd.). And Disparon (registered trademark, manufactured by Enomoto Kasei Co., Ltd.).
An impregnation promoter may be used individually by 1 type, and may mix and use 2 or more types.

  In the ant-proofing flame retardant treatment liquid of the present invention, the content ratio of the impregnation accelerator is preferably 0.1% by mass or more and 5% by mass or less, and preferably 0.3% by mass or more and 2% by mass or less. More preferred. When the content ratio of the impregnation accelerator is within the above range, the flame retardant component and the ant-proof component sufficiently permeate the inside of the substrate, and the flame retardant property and the ant-proof property can be sufficiently exhibited.

Moreover, 0.01-0.5 mass part is preferable with respect to 1 mass part of ammonium dihydrogen phosphate, 0.01-0.5 mass part is more preferable, 0.03-0.2 mass part is more preferable, 0.05- 0.1 parts by mass is particularly preferable.
Within the above range, the flame retardant component easily penetrates into the substrate, and the flame retardancy and ant repellency can be sufficiently exhibited.

<Anti-anticide>
The termite-preventing agent contained in the ant-proofing flame-retardant treatment solution of the present invention is excellent in compatibility with other components and does not inhibit the flame-retarding action by the flame-retardant components (ammonium dihydrogen phosphate, ammonium sulfate). If it is a thing, arbitrary ant preventive agents can be used.

  Specifically, for example, neonicotinoid compounds such as dinotefuran, clothianidin, imidacloprid, thiamethoxam, and acetamiprid; pyrethroid compounds such as cyfluthrin and pyrethrin; carbamate compounds such as carbaryl, fenocarb and propoxur;

  Among these, neonicotinoid compounds are preferable as the termite-proofing agent in the present invention because they have low toxicity to the human body.

  Among the neonicotinoid compounds, the compound represented by the following general formula (1) is excellent in compatibility with the flame retardant component (ammonium dihydrogen phosphate / ammonium sulfate), so that the ant-proof flame retardant of the present invention is achieved. It can be suitably used for a treatment liquid.

In the general formula (1), X is a nitro group or a cyano group. R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ is an optionally substituted heterocyclic group having 3 to 8 carbon atoms.

  In addition, among the compounds represented by the general formula (1), particularly preferable conditions are as follows.

More preferably, X is a nitro group.
R ¹ is preferably a hydrogen atom or a methyl group.
R ² is preferably a hydrogen atom, a methyl group or an ethyl group.
R ³ is preferably a hydrogen atom or a methyl group.
In particular, both R ¹ and R ³ are preferably hydrogen atoms.

R ⁴ is preferably any one of the “heterocyclic groups optionally having substituents” represented by the following formulas (A1) to (A3), and the complex represented by the following formula (A1): A ring group (furan ring) is particularly preferable.

Among the compounds represented by the general formula (1), compounds satisfying the above conditions (all or a part thereof) are excellent in compatibility and fine dispersion with other components in the present invention.
In addition, in order to fully exhibit the ant-proofing property, it is necessary to contain a certain amount of the ant-proofing agent in the ant-proofing flame-retardant treatment liquid. However, among the compounds represented by the general formula (1), a compound satisfying the above condition is difficult to inhibit the flame retardancy, and is sufficient to exhibit the ant-proof property. Can be contained.

Examples of compounds satisfying the above conditions include dinotefuran (X: nitro group, R ¹ : hydrogen atom, R ² : methyl group, R ³ : hydrogen atom, R ⁴ : group represented by (A1) above), clothianidin (X: nitro group, R ¹ : hydrogen atom, R ² : methyl group, R ³ : hydrogen atom, R ⁴ : group represented by the above (A3)). From the viewpoint of safety, dinotefuran containing no chlorine is particularly preferable.

  In the ant-proofing flame retardant treatment solution of the present invention, the ant-proofing agent may be used alone or in combination of two or more.

In the ant-proofing flame retardant treatment liquid of the present invention, the content ratio of the ant-proofing agent is preferably 0.01% by mass or more and 3% by mass or less, and preferably 0.05% by mass or more and 2% by mass or less. More preferably, the content is 0.1% by mass or more and 1% by mass or less.
When the lower limit of the content ratio of the termite-proofing agent is not less than the above, the flame-retardant treated wood sufficiently exhibits the termite-proofing property, and when the upper limit is not more than the above, the compatibility with other components is excellent.

  Moreover, 0.001-0.02 mass part is preferable with respect to 1 mass part of ammonium dihydrogenphosphate, 0.001-0.02 mass part is preferable, 0.003-0.15 mass part is more preferable, 0.005- 0.10 parts by mass is particularly preferable.

<Other ingredients>
In addition, the ant-proofing flame retardant treatment liquid of the present invention may contain a preservative, an algae-proofing agent, a fungicide, and the like.

The following composition is mentioned as an example of a composition of the ant-proof flame-retardant treatment liquid of the present invention.
Ammonium sulfate 7.0 to 30.0 parts by mass Ammonium dihydrogen phosphate 5.0 to 20.0 parts by mass Ammonia water 1.5 to 8.0 parts by mass Insecticide / preservative / antifungal agent 1.5 to 2 0.0 part by weight Impregnation accelerator 0.15-3.0 parts by weight Water 37.0-84.85 parts by weight

Moreover, the following compositions are also mentioned as an example of the composition of the ant-proof flame-retardant treatment liquid of the present invention.
Ammonium sulfate 7.0 to 30.0 parts by weight Ammonium dihydrogen phosphate 5.0 to 20.0 parts by weight Ammonia water 1.5 to 8.0 parts by weight Insecticide / preservative / antifungal agent Suitable amount Impregnation accelerator 0 35-2.0 parts by weight Water 40.0-86.15 parts by weight

  The ant-proofing flame retardant treatment liquid of the present invention uses a high concentration of flame-retardant component and ant-proofing agent when used on wood or bamboo, and when used on cloth or paper. It is preferable to use a low-concentration component with a low content of flame-retardant components and anti-fungal agents.

Specifically, the water content in the ant-proofing flame retardant treatment liquid of the present invention is preferably 30% by mass or more and 80% by mass or less when the target combustible base material is wood or bamboo. The mass% is more preferably 75% by mass or less, and particularly preferably 50% by mass or more and 70% by mass or less.
Within the above range, the flame retardant component penetrates into the wood or bamboo material evenly, and the flame retardancy can be made sufficient.

In addition, the moisture content in the ant-proofing flame retardant treatment liquid of the present invention is preferably 60% by mass or more and 99% by mass or less, and more preferably 70% by mass or more when the target combustible substrate is cloth or paper. 95 mass% or less is more preferable, and 80 mass% or more and 90 mass% or less are especially preferable.
In the case of cloth and paper, the flame retardant component penetrates more easily than wood and bamboo. Therefore, the moisture content in the above range is preferable from the viewpoint of cost (even if components other than moisture are included beyond the above range). The flame retardancy and ant protection are not improved and may be wasted).

  This invention is also a manufacturing method of the said ant-proof flame-retardant treatment liquid. The production method is carried out by adding each of the above-described components to water, mixing and stirring according to a conventional method. Although it is not particularly limited, first, the impregnation accelerator is added to water and mixed and stirred, then mixed and stirred to dissolve ammonium dihydrogen phosphate, ammonium sulfate and ammonia, and finally an antifungal agent, preservative, It is preferable to produce by the procedure of adding an anti-algae agent, mixing, stirring and dissolving.

  The present invention is also a method for producing a flame retardant base material by impregnating and impregnating the flammable base material with an ant proof flame retardant treatment solution.

  Examples of the impregnation / impregnation method include dipping, coating, spraying, perforation injection, impregnation with an impregnation apparatus, etc., but the effect of the present invention is exhibited by sufficiently impregnating and impregnating the components to the inside of the combustible substrate. Therefore, impregnation or perforation injection with an impregnation apparatus or the like is preferable.

In the case of immersion, the immersion time is preferably from 30 minutes to 1 week, more preferably from 1 hour to 2 days, and particularly preferably from 2 hours to 1 day.
When the lower limit of the immersion time is not less than the above, the component sufficiently penetrates into the flammable base material, and the obtained flame retardant base material has excellent flame retardancy and ant repellency. Further, if the lower limit of the immersion time is less than or equal to the above, the productivity is sufficient (even if the upper limit of the immersion time is more than the above, the performance of the flame retardant substrate is not excellent, meaningless is there).

  In addition, it is preferable not to perform the immersion once, but to take out the substrate once in the middle and dry it, and then perform the immersion in a plurality of times. When dipping, there may be a site where flame retardant components and ant protection components are difficult to penetrate locally due to the generation of bubbles, etc., but this can be prevented by dipping in multiple times. Can do.

The drying after immersion is preferably natural drying, but may be forced drying with a hot air dryer or the like.
In the case of natural drying, the drying time is preferably from 30 minutes to 1 week, more preferably from 1 hour to 2 days, and particularly preferably from 2 hours to 1 day.
In the case of forced drying, the drying time is preferably from 1 minute to 8 hours, more preferably from 2 minutes to 3 hours, and particularly preferably from 3 minutes to 1 hour.

  Examples of flammable substrates include wood, bamboo, paper, cloth, etc., but wood used in wooden houses and the like requires not only flame retardancy but also ant-proofing properties. It is easy to produce an effect and is preferable as an application target of the present invention.

  Table 1 shows the test results on 19 items of 17 harmful elements conducted at the Japan Cultural Goods Safety Laboratory for an example of the ant-proofing flame retardant treatment liquid of the present invention. The ant-proofing flame retardant treatment liquid of the present invention is below all the standard values of EN71-3 (standard newly started for toy safety by EU on July 20, 2013). Since the ant-proofing flame retardant treatment liquid of the present invention does not contain boron (boron compound), the soluble boron was also a numerical value far below the standard value.

  Moreover, an example of the ant-proofing flame retardant treatment liquid of the present invention shown in Table 1 includes 13 substances (formaldehyde, acetaldehyde, toluene, xylene, ethylbenzene, styrene, paradichlorobenzene, tetradecane, It does not contain chlorpyrifos, fenobucarb, diazinon, di-n-butyl phthalate, di-2-ethylhexyl phthalate), and is certified as a health hazard by the Japan Shiroari Countermeasures Association and the Japan Wood Preservation Association. It is a processing solution that does not cause environmental impact.

<Action and principle>
The action / principle of the excellent flame retardancy and ant repellency of the ant-proof flame-retardant treatment liquid of the present invention is not clear, but the following may be considered. However, the present invention is not limited to the range of the following effects.

The ant-proofing flame retardant treatment liquid of the present invention significantly accelerates the carbonization of organic matter during combustion, reduces the generation of flammable carbon-containing gas, and increases the amount of carbon generated at a low combustion rate, It is thought that combustion of a combustible base material is suppressed.
Specifically, flame retardant components (ammonium dihydrogen phosphate, ammonium sulfate) generate nitrogen gas by thermal decomposition when the base material burns, and this nitrogen gas blocks oxygen and suppresses combustion it is conceivable that. Further, it is considered that the flame retardant component forms a mixture film with carbon on the surface of the combustible material and suppresses combustion.
In addition, the negative catalytic effect by ammonium ions (NH ₄ ⁺ ), hydrogen phosphate ions (HPO ₄ ²⁻ ), dihydrogen phosphate ions (H ₂ PO ₄ ⁻ ), etc. produced by decomposition of the flame retardant component, This is thought to contribute to the suppression of combustion.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples and comparative examples. However, the present invention is not limited to these examples and comparative examples unless it exceeds the gist.

<Preparation Example 1>
Solution A having the following composition was prepared.

[Solution A composition]
-Water 67.6 parts by mass-Ammonium dihydrogen phosphate 12.0 parts by mass (manufactured by Taihei Chemical Industrial Co., Ltd.)
・ Ammonium sulfate 15.0 parts by mass (made by Yoneyama Pharmaceutical Co., Ltd.)
・ 4.5 parts by mass of 25% ammonia water (manufactured by Kobayashi Co., Ltd.)
・ 0.9 part by mass of impregnation accelerator (manufactured by Nippon Lubrizol Corporation, Solsperse 20000)
・ Zinotefuran 0.1 mass part ・ Preservative small amount (Osaka Gas Chemical Co., Ltd., Suraoff 72N)
-Small amount of anti-algae agent (manufactured by Nippon Soda Co., Ltd., Biocut-AF40)

  Each component was sufficiently compatible, and a transparent and uniform solution was obtained.

<Preparation Example 2>
Solution P was prepared in the same manner as in Preparation Example 1, except that dinotefuran was changed to imidacloprid in Preparation Example 1.
The obtained solution P had white turbidity.

<Preparation Example 3>
Solution Q was prepared in the same manner as in Preparation Example 1, except that dinotefuran was changed to thiamethoxam in Preparation Example 1.
The obtained solution Q had white turbidity and was separated into two layers, an oil layer and an aqueous layer.

<Preparation Example 4>
Preparation Example 1 except that the amount of dinotefuran added in Preparation Example 1 was 0.5% by mass, 2.0% by mass, 4.0% by mass, and 6.0% by mass with respect to the entire solution. A solution was prepared as in 1.
The solution obtained had a clear and uniform appearance regardless of the amount of dinotefuran added.

<Preparation Example 5>
Solution B having the following composition was prepared.

[Solution B composition]
-Water 113.1 parts by mass-Ammonium dihydrogen phosphate 12.0 parts by mass (manufactured by Taihei Chemical Industrial Co., Ltd.)
・ Ammonium sulfate 15.0 parts by mass (made by Yoneyama Pharmaceutical Co., Ltd.)
・ 6.5 parts by mass of 25% aqueous ammonia (manufactured by Kobayashi Co., Ltd.)
・ 0.9 part by mass of impregnation accelerator (manufactured by Nippon Lubrizol Corporation, Solsperse 20000)
・ Zinotefuran 0.1 mass part ・ Preservative small amount (Osaka Gas Chemical Co., Ltd., Suraoff 72N)
-Small amount of anti-algae agent (manufactured by Nippon Soda Co., Ltd., Biocut-AF40)

  The water content of the solution B is 80% by mass. Each component was sufficiently compatible, and a transparent and uniform solution was obtained.

<Preparation Example 6>
In Preparation Example 5, the addition amount of 25% aqueous ammonia was changed so that the pH of the resulting solution was 6.0, 7.0, 7.5, 8.0. A solution was prepared as in the case.
At any value of pH, the resulting solution had a clear and uniform appearance.

<Preparation Example 7>
In Preparation Example 5, the amount of water added and the amount of 25% ammonia water were changed to provide a solution having a water content of 85% by mass and a pH of 7.0, a water content of 85% by mass and a pH of 7 A solution having a water content of 85% by mass and a pH of 8.0, a solution having a water content of 90% by mass and a pH of 7.0, a water content of 90% by mass and a pH of A solution having a water content of 90% by mass and a pH of 8.0 was prepared.
All solutions had a clear and uniform appearance.

<Preparation Example 8>
Solution C having the following composition was prepared.

[Solution C composition]
-Water 67.6 parts by mass-Ammonium dihydrogen phosphate 4.0 parts by mass (manufactured by Taihei Chemical Industrial Co., Ltd.)
・ Ammonium sulfate 5.0 parts by mass (made by Yoneyama Pharmaceutical Co., Ltd.)
・ 1.5% by weight of 25% ammonia water (manufactured by Kobayashi Co., Ltd.)
-Impregnation accelerator 0.3 part by mass (Nippon Lubrizol Corporation, Solsperse 20000)
・ Dinotefuran Small amount ・ Preservative Small amount (Osaka Gas Chemical Co., Ltd., Suraoff 72N)
-Small amount of anti-algae agent (manufactured by Nippon Soda Co., Ltd., Biocut-AF40)

  Each component was sufficiently compatible, and a transparent and uniform solution was obtained.

<Example 1>
Using the Ryukyu pine plate as a sample, the flame retardancy performance of the ant-proof flame retardant treatment liquid of the present invention was tested. Ryukyu pine is said to have a higher density than other woods, and it is difficult for the components of the liquid agent to penetrate and impregnate.

  Solution A was filled into a vat and a 10 cm × 10 cm × 1.5 cm Ryukyu pine plate was immersed for 12 hours. Then, after taking out a board and air-drying, it was immersed in the solution A for 12 hours again. Thereafter, the plate was taken out again and allowed to air dry.

  The mass of the plate before the treatment was 110.1 g, whereas the mass of the plate after the treatment was 118.6 g, and the components of the ant-proof flame-retardant treatment liquid were impregnated, The mass increased by 8.5 g.

  A gas (B) immersed in an ant-proofing flame retardant treatment solution and an untreated 10 cm × 10 cm × 1.5 cm Ryukyu pine plate (A) as test specimens, respectively, under the same conditions. Flame was irradiated with a burner. The gas used was propane, the distance between the flame tip and the test specimen was 5 cm, and the flame tip temperature was around 1000 ° C. A thermometer was installed on the back surface of each plate, and the temperature was measured at intervals of 50 seconds.

  In the plate (A), the flame penetrated the back surface 8 minutes after the flame irradiation, but in the plate (B), the temperature of the back surface 8 minutes after the flame irradiation was 75 ° C., and the temperature of the back surface increased greatly thereafter. There was no sign that the flame penetrated the back.

<Example 2>
Using the cedar board as a sample, the flame retardant performance of the ant-proofing flame retardant treatment liquid of the present invention was tested.

The solution A was filled in an impregnation apparatus (manufactured by Yasima Co., Ltd., vacuum / pressure impregnation apparatus) and impregnated with a 10 cm × 10 cm × 1.5 cm cedar board. In this state, it was allowed to stand for 4 hours at a pressure of 7 kg.
Thereafter, the plate was taken out and naturally dried for 24 hours.

When the dried cedar board was tested with a corn calorimeter tester (manufactured by Toyo Seiki Seisakusho Co., Ltd., exothermic test device), the heat generation rate was 15 kW / m ² at the maximum, and the total calorific value for a heating time of 10 minutes. Was 5.9 MJ / m ² . Also, no holes or cracks were found on the back of the cedar board after the test.
That is, the standard of “quasi-incombustible material” stipulated by the Ministry of Land, Infrastructure, Transport and Tourism (when heating for 10 minutes, (i) the total calorific value is 8 MJ / m ² or less, (ii) No hole was provided, and (iii) the maximum heat generation rate continued for 10 seconds or longer and did not exceed 200 kW / m ² .

<Example 3>
Each solution prepared in Preparation Example 4 was filled in a vat, and a 10 cm × 10 cm × 1.5 cm cedar board was immersed in each solution for 12 hours. Then, after taking out a board and air-drying, it was immersed in the solution again for 12 hours. Thereafter, the plate was taken out again and allowed to air dry.
The naturally dried cedar board was irradiated with a flame with a gas burner for 3 minutes. The gas used was propane, the distance between the flame tip and the test specimen was 5 cm, and the flame tip temperature was around 1000 ° C.

  Table 2 shows the result of calculating the area of the black-colored (carbonized) portion of the cedar board after the flame irradiation.

  As described above, it has been found that when the amount of dinotefuran exceeds 2.0% by mass, the flame retardancy is deteriorated.

<Example 4>
A bamboo cylinder having an inner radius of 3 cm, a wall thickness of 0.4 cm, and a length of 24 cm was cut in the vertical direction (conduit direction) and divided into four parts to obtain bamboo samples.
Solution B was filled in a vat and bamboo was immersed for 12 hours. Thereafter, the bamboo material was taken out and naturally dried for 12 hours, and then immersed again in the solution for 12 hours. Thereafter, the bamboo material was taken out again and naturally dried for 24 hours.
Bamboo material that has been naturally dried is propane, the distance between the flame tip and the test piece is 5 cm, the flame tip temperature is around 1000 ° C., and the flame is irradiated from the inner surface side (from the opposite side of the skin) Although the inner surface of the bamboo material turned black, no holes or cracks occurred in the bamboo material even after 8 minutes.

<Comparative Example 1>
Except for using bamboo material that was not immersed in Solution B, flame irradiation was performed in the same manner as in Example 4. After 3 minutes, a hole was confirmed in the flame irradiation portion of the bamboo material.

<Example 5>
Each solution prepared in Preparation Example 6 was filled in a vat, and the same bamboo material used in Example 4 was immersed in each solution for 12 hours. Then, after taking out bamboo material and air-drying, it was immersed in the solution again for 12 hours. Thereafter, the bamboo material was taken out again and naturally dried for 24 hours.
The bamboo material that had been naturally dried was irradiated with a flame with a gas burner for 5 minutes. The gas used was propane, the distance between the flame tip and the test specimen was 5 cm, and the flame tip temperature was around 1000 ° C.

  Table 3 shows the results of calculating the area of the blackened (carbonized) portion of the bamboo material after the flame irradiation.

  As described above, it has been found that when the ant-proofing flame retardant treatment liquid of the present invention is used for bamboo, the flame retardancy is improved when it is alkaline.

<Example 6>
Except for changing “each solution prepared in Preparation Example 6” to “each solution prepared in Preparation Example 7”, the bamboo material was irradiated with flame in the same manner as in Example 5, and the bamboo material after the flame irradiation was blackened. The area of the discolored (carbonized) part was calculated. The results are shown in Table 4.

<Example 7>
Using a thin cotton cloth (Kanakin No. 3) as a sample, the fire-proof performance test specified in Article 4-3 of the Fire Service Act Enforcement Regulations for the fire-proof performance after treatment with the ant-proof flame-retardant treatment liquid of the present invention At the Japan Flame Protection Association.

The thin cloth was immersed in the solution C (temperature 17 ° C., pH 6.3) for 4 minutes, and the drawing ratio was 116%.
The thin cloth was dried and the amount of adhered drug was measured, and it was 19.8% by mass.

  As shown in Table 5, the thin cloth after the treatment with the ant-proofing flame retardant treatment liquid of the present invention is a standard defined in Article 4-3 of the Fire Service Law Enforcement Regulations regarding the afterflame time, the residual dust time, and the carbonized area. It was registered as a flame retardant by the Japan Flame Protection Association.

  The ant-proofing flame-retardant treatment liquid of the present invention is excellent in flame-retardant and ant-proofing properties and has high safety to the human body. Paper products such as curtains, wrapping paper, cardboard, securities and documents; fabric products such as curtains, carpets, cloth blinds, sheets, cushions and stuffed animals; wooden products such as plywood, wooden fittings and wooden furniture; bamboo fittings and bamboo It is widely used for making fire-resistant and ant-proofing bamboo products such as furniture.

Claims (8)

  An ant-proof flame-retardant treatment solution containing neither boron nor a boron compound but containing water, ammonium dihydrogen phosphate, ammonium sulfate, ammonia, an impregnation accelerator and an ant-proofing agent.   The ant-proofing flame-retardant treatment solution according to claim 1, wherein the ant-proofing agent is a neonicotinoid compound. The ant-proof flame retardant treatment solution according to claim 2, wherein the neonicotinoid compound is a compound represented by the following general formula (1).

[In General Formula (1), X is a nitro group or a cyano group. R ¹ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ² is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ³ is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. R ⁴ is an optionally substituted heterocyclic group having 3 to 8 carbon atoms. ]   4. The ant-proof flame retardant treatment solution according to claim 3, wherein the neonicotinoid compound is dinotefuran.   The manufacturing method of the ant-proof flame-retardant treatment liquid according to any one of claims 1 to 4.   A method for producing a flame retardant base material, comprising impregnating and impregnating a flammable base material with the ant-proofing flame retardant treatment solution according to any one of claims 1 to 4.   The method for producing a flame-retardant substrate according to claim 6, wherein the combustible substrate is wood.   The method for producing a flame-retardant substrate according to claim 6, wherein the combustible substrate is bamboo.