JP2011162743A - Flame-retardant composition, method for flame-retarding treatment using the same, and flame-retardant material - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a liquid or powdery flame-retardant composition capable of imparting high flame-retardant performance to wood, paper, fabrics, nonwoven fabrics and resins, to provide a low-cost and simple method for frame-retarding treatment using the same, and to provide a flame-retardant material obtained by the method. <P>SOLUTION: The flame-retardant composition is provided, being characterized by comprising: a boron compound selected from boric acid, borate and mixture thereof; and a saccharide; in such a proportion as to present synergistic effect. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a flame retardant composition containing a boron compound and a saccharide, a flame retardant treatment method using the same, and a flame retardant material obtained thereby. The flame retardant composition of the present invention is suitably used for flame retarding of wood, paper, woven fabric, nonwoven fabric and resin,

Boron compounds such as boric acid (H ₃ BO ₃ ) and borax (sodium tetraborate decahydrate, Na ₂ B ₄ O ₇ · 10H ₂ O) have long been used as fire retardants (flame retardants) for wood. I came.
Boron compounds have already been studied from the first half of the 19th century as a combustion inhibitor for cellulosic materials such as wood. Among them, they have the effect of suppressing flaming combustion and red heat combustion of wood and wood materials, and are obtained at a relatively low cost. Easy boric acid and borax have been considered as fire retardants.
However, boric acid and borax have low solubility in water (amount g dissolved in 100 g of water), and in order to obtain high flame retardancy, impregnate or apply the material to be flame retardant as a high concentration boron compound solution. There was a problem that could not.

Accordingly, the present inventor has proposed that an aqueous solution of a boron compound stable at room temperature and a liquid form of boron compound containing boric acid and borate in amounts exceeding the solubility of each single compound at a temperature heated above room temperature. A composition has been proposed (see JP 2005-112700 A: Patent Document 1 and JP 2006-219329 A: Patent Document 2).
These prior art aqueous solutions and liquid compositions exhibit a high flame retardant effect for some organic polymers such as polyvinyl alcohol and ethylene-vinyl alcohol copolymers, but have low adhesion to other organic polymers, There was a problem that the flame retardant effect was low.

In addition, a flame retardant or incombustible treatment member is proposed in which a polymer coating layer having a hydroxyl group such as polyvinyl alcohol is applied to the surface of a material to be flame retardant, and a sodium borate polymer is adhered on the layer. (See JP 2009-29103 A: Patent Document 3).
This prior art is considered to be an application of a known technique in which a gel-like composition called slime is obtained by reaction when a polymer having a hydroxyl group and a borate are mixed in an aqueous solution to crosslink hydrogen bonds. .
However, in this prior art, two steps of forming a coating layer and attaching a sodium borate polymer are necessary, and it is required to simplify the flame-retarding step and to further improve the flame-retardant performance.

On the other hand, the flame retardant effect is confirmed also about the saccharide which is another active ingredient of this invention. For example, in Japanese Patent Application Laid-Open No. 2006-233006 (Patent Document 4), when a saccharide compound is present in a resin, the saccharide compound dehydrates hydroxyl groups at high temperatures during combustion, releases water, and exhibits a cooling effect. In addition, it is described that a char (carbonized layer) is generated to form a heat insulating film.
However, the above prior art does not describe the combined use of a boron compound and a saccharide and the effect of improving (providing) the high flame retardancy.

JP 2005-112700 A JP 2006-219329 A JP 2009-29103 A JP 2006-233006 A

  The present invention relates to a liquid or powder flame retardant composition capable of imparting high flame retardant performance to wood, paper, woven fabric, nonwoven fabric and resin, a low-cost and simple flame retardant treatment method using the same, and It is an object to provide a flame retardant material obtained by the above.

  As a result of intensive studies in order to solve the above-mentioned problems, the present inventor has dramatically increased the effect of imparting flame retardancy by using a boron compound and a saccharide in combination. The present invention was completed by finding that the present invention can be applied to an organic polymer that was low.

  Thus, according to the present invention, there is provided a flame retardant composition comprising a boron compound selected from boric acid, a borate salt or a mixture thereof and a saccharide in a ratio that exhibits a synergistic effect. .

Moreover, according to this invention, the flame-retardant processing method characterized by obtaining a flame-retardant material by processing a flame-retardant target material with said flame-retardant composition is provided.
Furthermore, according to this invention, the flame-retardant material obtained by said flame-retarding processing method is provided.

According to the present invention, a liquid or powdery flame retardant composition capable of imparting high flame retardant performance to wood, paper, woven fabric, nonwoven fabric and resin, and a low-cost and simple flame retardant treatment method using the same And providing a flame retardant material obtained thereby.
In the present invention, by using a saccharide which is the same carbohydrate as cellulose, a dense carbonized layer is formed on the surface of the organic polymer which is difficult to generate a carbonized layer on the surface at the time of flame contact. Is considered to be expressed.

According to the present invention, the boron compound is boric acid (H ₃ BO ₃ ), borax (Na ₂ B ₄ O ₇ .10H ₂ O), sodium pentaborate (NaB ₅ O ₈ ), or a mixture thereof. And the saccharide is selected from monosaccharides selected from glucose and fructose, sucrose (sucrose), trehalose, cellobiose and α-cyclodextrin or oligosaccharides or starches, glucomannan and hydroxypropyl methylcellulose By being a polysaccharide, the above-described excellent effects are particularly exhibited.

  Moreover, according to the present invention, the synergistic ratio is 100 parts by weight of the boron compound, 5 to 2000 parts of saccharide when the saccharide is monosaccharide or oligosaccharide, or 1 to 2000 parts of saccharide when the saccharide is polysaccharide. By the ratio, the above-described excellent effect is particularly exhibited.

Also, according to the present invention, the flame retardant composition is
A part of boric acid and part b of borax (provided that a <35, b <40, 0 <a <b + 5) are added to 100 parts of water, heated to 70-90 ° C. to dissolve, and then at room temperature. An aqueous solution containing 2.5 mol / kg or more in terms of boron without containing a chelating agent or surfactant,
To 100 parts of water, add c part of boric acid and d part of borax (provided c ≧ 35, d ≧ 40) and heat to 40 to 100 ° C. to dissolve and 100 parts of water Boron selected from aqueous solutions in which 2-28 parts of boric acid, 2-98 parts of borax or 6-50 parts of sodium pentaborate (NaB ₅ O ₈ ) are added and heated to 40-100 ° C. In an aqueous solution of the compound,
When the saccharide is a monosaccharide or oligosaccharide, 1 to 80 parts of the saccharide is added to 100 parts of water, or when the saccharide is a polysaccharide, 1 to 30 parts of the saccharide is added to 100 parts of water and dissolved. The above-described excellent effect is particularly exhibited by the flame retardant composition.
Since the liquid flame retardant composition of the present invention is a one-component composition, according to the present invention, flame retardancy can be imparted to the material to be flame retardant in one step.

According to the present invention, the flame retardant composition is a mixture of a boron compound selected from boric acid, borate or a mixture thereof and a saccharide, or the liquid flame retardant composition is evaporated to dryness. By being a powdery flame retardant composition obtained by solidifying, the above-described excellent effects are particularly exhibited.
The powdery flame retardant composition of the present invention can provide a resin material having excellent flame retardancy by blending it into a resin or the like.

Further, according to the present invention, there is provided a flame retardant treatment method comprising obtaining a flame retardant material by treating a flame retardant target material with the flame retardant composition, and a flame retardant material obtained thereby. The
When the flame retardant target material is a material selected from wood, paper, woven fabric, nonwoven fabric, and resin, the flame retardant material can be easily obtained at low cost.

Furthermore, the above process
The flame retardant composition is a liquid flame retardant composition selected from aqueous solutions, aqueous suspensions and colloidal solutions, and the material to be flame retardant is a material selected from wood, paper, woven fabric, non-woven fabric and resin. When applying or impregnating the material with a liquid flame retardant composition,
When the flame retardant composition is a powdered flame retardant composition and the flame retardant material is a resin, the powder flame retardant composition is added to the resin and melt-kneaded, or the flame retardant material is When it is a resin, the above-described excellent effects are particularly exhibited by comprising adding the powdery constituents of the flame retardant composition individually to the resin and melt-kneading them.

Moreover, said application | coating is performed so that it may become 5 to 400% by the weight increase rate of the flame retardant material, or 0.004 to 1.5 g / cm < ² > by the adhesion amount, and said impregnation is said flame retardant material. The above-mentioned excellent effect is particularly exhibited when the amount of impregnation is 50 g or more per kg of the resin, and the amount of addition is 5 to 30 parts with respect to 100 parts of the resin. Is done.

It is a figure which shows the temperature change of the test body surface at the time of flame contact of the test body which apply | coated the liquid flame-retardant composition of this invention (Test Example 1). It is a figure which shows the temperature change of the test body surface at the time of flame contact of the test body which apply | coated the liquid flame-retardant composition of this invention (Test Example 2). It is a figure which shows the temperature change of the test body surface at the time of flame contact of the test body which apply | coated the liquid flame retardant composition of this invention (Test Example 5).

The flame retardant composition of the present invention is characterized by containing a boron compound selected from boric acid, borate, or a mixture thereof, and a saccharide in a ratio that exhibits a synergistic effect.
In the present invention, “flame retardant” means that it is difficult to burn, “flame retardant” means that it is difficult to burn, and “flame retardant composition (also referred to as“ flame retardant ”) means an additive for making material difficult to burn. Means.
Depending on the material and its application, laws and regulations have been established, and detailed standards and evaluation methods for "flame retardants" have been standardized.
Among them, terms such as “non-combustible”, which means that combustion with flames cannot be performed, “flame-proof” which means that fire does not burn and spread, and “fireproof” and “fireproof” are used. However, in the present invention, all these terms are included and defined as “flame retardant”.

The boron compound selected from boric acid, borate or a mixture thereof is not particularly limited as long as it is industrially available. For example, borate may be borax (Na ₂ B ₄ O ₇ · 10H ₂ O), and the like, sodium pentaborate (NaB ₅ O _8).
Among these boron compounds, boric acid (H ₃ BO ₃ ), borax, sodium pentaborate or a mixture thereof is particularly preferable.
When the boron compound is a mixture of boric acid and sodium salt of boric acid, the molar ratio Na / B of boron (B) to sodium (Na) is preferably more than 0 and 0.5 or less.

The boric acid used in the present invention is H ₃ BO ₃ (orthoboric acid) and / or HBO ₂ (metaboric acid), and borax is sodium tetraborate decahydrate Na ₂ B ₄ O ₇ .10H ₂ O. Preferably there is. Although the weight of borax is in terms of the weight of decahydrate, borax is not necessarily a hydrate and may be an anhydride.

The saccharide is a saccharide that can exhibit the effects of the present invention when used in combination with a boron compound, and is not particularly limited as long as it is industrially available, and those that are easily available at low cost are particularly preferable.
Such saccharides are classified into monosaccharides, oligosaccharides (oligosaccharides) and polysaccharides.

As monosaccharides,
Triose (tricarbon sugar) such as glyceraldehyde, Tetrose (tetracarbon sugar) such as erythrose and threose, Pentose (pentose sugar) such as ribose, lyxose, xylose, arabinose, apiose, allose, talose, growth, glucose (Dextrose), aldoses such as hexose (hexose) such as altrose, mannose, galactose, idose;
Hexoses such as triose such as dihydroxyacetone, tetrose such as erythrulose, pentose such as ribulose and xylulose, psicose, fructose, fructose, sorbose and tagatose (Carbon sugar), ketose such as heptose (seven carbon sugar) such as sedoheptulose and coliose.

As oligosaccharides,
Disaccharides such as trehalose, isotrehalose, cordobiose, sophorose, nigerose, laminaribiose, maltose (maltose), cellobiose, isomaltose, gentiobiose, lactose (lactose), sucrose (sucrose);
Fructooligosaccharide, galactooligosaccharide, dairy oligosaccharide, deoxyribose, fucose, rhamnose, glucuronic acid, galacturonic acid, glucosamine, galactosamine, glycerin, xylitol, sorbitol, ascorbic acid (vitamin C), glucuronolactone, gluconolactone, α -Oligosaccharides such as cyclodextrins.

  Examples of the polysaccharide include starch, amylose, amylopectin, glycogen, cellulose, hydroxypropylmethylcellulose, pectin, glucomannan, polydextrose and the like.

  Among these saccharides, monosaccharides selected from glucose and fructose, sucrose (sucrose), trehalose, cellobiose and oligosaccharides selected from α-cyclodextrin or starch, glucomannan and hydroxypropyl methylcellulose Saccharides are particularly preferred.

When the saccharide is a monosaccharide or oligosaccharide, the proportion of the synergistic effect between the boron compound and the saccharide is 5 to 2000 parts, preferably 30 to 150 parts, or the saccharide is a polysaccharide. Sometimes the ratio is 1 to 2000 parts, preferably 1 to 15 parts of sugars.
When the blending ratio is within the above range, the excellent effect of the present invention can be obtained.

The flame retardant composition of the present invention comprises:
A part of boric acid and part b of borax (provided that a <35, b <40, 0 <a <b + 5) are added to 100 parts of water, heated to 70-90 ° C. to dissolve, and then at room temperature. An aqueous solution (aqueous solution 1) containing 2.5 mol / kg or more in terms of boron without containing a chelating agent or surfactant obtained by cooling to
An aqueous solution (aqueous solution 2) prepared by adding boric acid c part and borax d part (provided c ≧ 35, d ≧ 40) to 100 parts of water and heating to 40 to 100 ° C. 2 to 28 parts of boric acid, 2 to 98 parts of borax or 6 to 50 parts of sodium pentaborate (NaB ₅ O ₈ ) are added to the aqueous solution, and heated to 40 to 100 ° C. to dissolve the solution ( Aqueous solution 3)
In an aqueous solution of a boron compound selected from
When the saccharide is a monosaccharide or oligosaccharide, 1 to 80 parts of saccharide with respect to 100 parts of water, more preferably 15 to 25 parts, or 1 to 30 parts of saccharide with respect to 100 parts of water when the saccharide is a polysaccharide, More preferably, it is a liquid flame retardant composition in which 2 to 6 parts are added and dissolved.
When the blending ratio is within the above range, the excellent effect of the present invention can be obtained.
The liquid flame retardant composition of the present invention may be an aqueous solution, an aqueous suspension, or a colloidal solution.

  The aqueous solution 1 can be prepared, for example, by the method described in paragraphs 0019 to 0022 and 0030 to 0031 of JP-A-2005-112700 (Patent Document 1). Specifically, it will be described in detail in Examples.

In the present invention, “parts” means parts by weight.
“Concentration unit: mol / kg” is the molar concentration by weight, and is expressed by the mass (mol) of boron dissolved per 1 kg of water as a solvent.
“Room temperature” means a temperature range of 15 ° C. to 25 ° C.
“Stable at room temperature” means that it does not precipitate at room temperature.

Among the aqueous solutions 1, powders having a peak at 880 ± 150 cm ⁻¹ in the Raman spectrum and evaporated to dryness are 2θ = 27.8 ± 1.2 and 45.5 in powder X-ray diffraction (CuKα ray 1.5418４). Those having a peak at 7 ± 1.2 are particularly preferable because they are stable at room temperature.

  The aqueous solution 2 can be prepared, for example, by the method described in paragraphs 0020 to 0024 of JP-A-2006-219329 (Patent Document 2). Specifically, it will be described in detail in Examples.

The aqueous solution 3 can be prepared according to the method of the aqueous solution 2 described above.
The amount of boric acid (H ₃ BO ₃ ) is preferably 2 to 28 parts, more preferably 15 to 25 parts per 100 parts of water.
The amount of borax (Na ₂ B ₄ O ₇ .10H ₂ O) is preferably 2 to 98 parts, more preferably 25 to 50 parts, per 100 parts of water.
The amount of sodium pentaborate (NaB ₅ O ₈ ) is preferably 6 to 50 parts, more preferably 25 to 45 parts, per 100 parts of water.
If each compounding amount is within the above range, the excellent effect of the present invention can be obtained.

The flame retardant composition of the present invention may contain an additive exhibiting an additional effect as long as the effects of the present invention are not impaired.
In the case of a liquid flame retardant composition, examples of such additives include a film-forming agent and a penetrating agent.
The penetrant has an effect of allowing the flame retardant component to penetrate into the material to be flame retardant, particularly into the resin.
Examples of such a film-forming agent include an aqueous polyurethane emulsion, an ethylene-vinyl acetate copolymer (EVA) emulsion, and an ethylene-acrylic acid copolymer (EEA) emulsion.
When the flame retardant composition is an aqueous solution, the amount of the film forming agent added is about 2 to 15% by weight, preferably 2 to 5% by weight.

The penetrant has an effect of promoting the impregnation of the boron compound into the flame retardant material.
Examples of such penetrants include alcohols such as methanol, ethanol, propanol, butanol, pentanol, and hexanol; diols such as ethylene glycol and propylene glycol; triols such as glycerin; alditols having 3 to 11 carbon atoms (also called glycitol). Polyol), polyphenols, and surfactants having an action of reducing interfacial tension.
When the flame retardant composition is an aqueous solution, the amount of penetrant added is about 1 to 10% by weight, preferably 1 to 3% by weight.

Moreover, the flame retardant composition of the present invention is a mixture of a boron compound selected from boric acid, borate or a mixture thereof and a saccharide, or the above liquid flame retardant composition is evaporated to dryness. It is preferable that it is a powdery flame-retardant composition obtained by this.
Evaporation to dryness can be performed by a known method, but spray drying (spray drying) is particularly preferred. The “spray drying method” is a method in which a liquid is made into a fine mist, sprayed in hot air, and instantaneously dried to obtain a powder. Specifically, it will be described in detail in Examples.

  According to the present invention, there is provided a flame retardant treatment method comprising treating a flame retardant material with the flame retardant composition to obtain a flame retardant material, and a flame retardant material obtained thereby. .

The flame retardant material is preferably a material selected from wood, paper, woven fabric, non-woven fabric and resin. As such a material, for example,
Wood such as cedar, Japanese pine, Japanese cypress, Japanese cypress, veneer, Japanese zelkova, SPF laminated timber (a mixture of spruce, pine, pine, fir) and bamboo;
Japanese paper, bran paper, western paper, etc .;
Woven fabrics such as cotton fabric, polyester woven fabric, polypropylene woven fabric, nylon woven fabric, acrylic woven fabric, vinylon woven fabric, aramid woven fabric, polyethylene terephthalate (PET) woven fabric;
Nonwoven fabrics such as polyester nonwoven fabric, polypropylene nonwoven fabric, nylon nonwoven fabric, acrylic nonwoven fabric, vinylon nonwoven fabric, and aramid nonwoven fabric;

Polypropylene, polyethylene, polyurethane (hard, soft), polystyrene, vinyl chloride, polycarbonate, phenol resin, urea resin, melamine resin, vinyl acetate resin, methacrylic resin, epoxy resin, acrylic resin, polyurethane (hard, soft), vinyl chloride resin , Polyvinylidene chloride, Teflon resin, ABS (acrylonitrile butadiene styrene) resin, AS (acrylonitrile styrene) resin, polyacetal, modified polyphenylene ether resin, polybutylene terephthalate resin, butadiene rubber, neoprene (chloroprene) rubber, styrene butadiene rubber (SBR) ), Butadiene acrylonitrile rubber (NBR), isobutene isoprene rubber, polyvinyl acetate, polyethylene terephthalate (PET), and composites thereof. Molding of the material and film.

The treatment with the flame retardant composition of the present invention comprises:
The flame retardant composition is a liquid flame retardant composition selected from aqueous solutions, aqueous suspensions and colloidal solutions, and the material to be flame retardant is a material selected from wood, paper, woven fabric, non-woven fabric and resin. When applying or impregnating the material with a liquid flame retardant composition,
When the flame retardant composition is a powdered flame retardant composition and the flame retardant material is a resin, the powder flame retardant composition is added to the resin and melt-kneaded, or the flame retardant material is When it is a resin, it is preferable that the powdery constituents of the flame retardant composition are individually added to the resin and melt kneaded.

In order to impregnate or apply the liquid flame retardant composition to the flame retardant material, a known method can be applied.
The impregnation is preferably performed under heating and / or pressure. The conditions may be set as appropriate depending on the type and shape of the flame retardant material. For example, a heating temperature or higher at the time of preparing the liquid flame retardant composition is preferable, and a pressure of about 2 to 20 atm is usually preferable.
Although the amount of impregnation depends on the concentration of the liquid flame retardant composition, it is 50 g or more, preferably 500 to 2000 g per kg of the flame retardant material.
If the amount of impregnation is within the above range, the excellent effect of the present invention can be obtained.

The application method and its conditions may be set as appropriate depending on the type and shape of the material to be flame retardant, the properties of the liquid flame retardant composition, etc., and include known methods such as application using a brush, a blade, and spraying. It is done. When the liquid flame retardant composition has a high viscosity, a method using a butter knife-like blade is preferable.
The coating amount (after drying) depends on the type and shape of the material to be flame retardant, but the weight increase rate of the material to be flame retardant is about 5 to 400%, preferably 60 to 80%, and the amount of adhesion is 0.004. to 1.5 g / cm ² or so, preferably from 0.01 to 0.1 g / cm ^2.
When the coating amount is within the above range, the excellent effect of the present invention can be obtained.
In addition, in order to obtain a desired flame retardancy, when the application is insufficient in one application, the application / drying process may be repeated.

After impregnating or applying the liquid flame retardant composition to the flame retardant material, the material may be dried to remove water which is a solvent of the liquid flame retardant composition.
The drying method and the conditions thereof are not particularly limited as long as water as a solvent of the liquid flame retardant composition is removed, and the flame retardant component and the flame retardant material are not altered or deformed, and may be set as appropriate.

Known methods can be applied to the method of melt-kneading the powdered flame-retardant composition and the resin, and the method of individually adding the components of the flame-retardant composition to the resin and melt-kneading. The melt-kneaded resin can be usually formed into a desired shape by a known method.
For example, a twin-screw kneader can be used for the melt kneading, and an extrusion molding machine or an injection molding machine can be used for the molding.

What is necessary is just to set suitably the compounding quantity of the powdery flame retardant composition or the total amount of the structural component of a flame retardant composition by the kind of resin material, the flame retardance requested | required, etc. Usually, it is 5 with respect to 100 parts of resin. About 30 parts, preferably 15-20 parts.
When the blending amount is within the above range, the excellent effect of the present invention can be obtained.

The present invention will be described in more detail with reference to test examples including the following examples and comparative examples, but the present invention is not limited to these examples.
In the following description, “parts” means “parts by weight” unless otherwise specified.

(Test Example 1)
To 100 parts of water, 20 parts of boric acid (manufactured by US Borax, the same applies hereinafter) and 25 parts of borax (manufactured by US Borax, the same applies hereinafter) are added and heated to 60 ° C. or higher to dissolve the additives. An aqueous solution was obtained by further adding and dissolving 25 parts of sucrose (manufactured by HIRANO, super white sugar, the same shall apply hereinafter) to an aqueous solution of boron compound (solid content 22.9%, hereinafter referred to as “2025 solution”).
An aqueous solution was obtained in the same manner as above except that 10 parts, 5 parts, 2.5 parts, 1.6 parts and 1.3 parts of sucrose were added to the 2025 solution.
The flame retardant performance of the obtained 2025 solution containing sucrose was compared with a 2025 solution not containing sucrose and an aqueous sucrose solution (an aqueous solution in which 17 parts of sucrose was added to and dissolved in 100 parts of water).

The 45 ° Meckel burner method of flameproof performance test standards (corresponding to JIS standard A1322) of flameproof articles defined in Article 4-3, Paragraphs 3 to 7 of the Fire Service Act Enforcement Regulations. Based on.
Specifically, the specimen (approx. 300 mm x 200 mm) is tilted 45 ° from the horizontal plane, and if the specimen does not ignite and does not penetrate for 2 minutes from the bottom of the specimen with a 65 mm flame length, it will continue to be the longest. Flame contact (heating) was performed for 12 to 14 minutes, and carbonization length, carbonization area, penetration time, and temperature change of the upper surface of the test specimen during heating were examined.

Using a brush for bran and shoji paste (hair foot 30 mm x width 73 mm) on the surface of a test specimen made of a polyester nonwoven fabric (thickness 10 mm, density 0.1 g / cm ³ ) used for nursing mats, Each aqueous solution was applied and dried.
The weight of the specimen was measured in advance, and the weight increase rate (WPG:%) and the amount of flame retardant component adhered (g / cm ² ) were determined from the weight after coating and drying.
The test body in which the 2025 solution was applied and dried once had a WPG of 7% and an adhesion amount of 0.007 g / cm ² . In the same manner, the test piece repeatedly applied and dried seven times had a WPG of 50% and an adhesion amount of 0.050 g / cm ² .

The 2025 solution WPG 7% and 50% specimens penetrated and flamed 10 and 47 seconds after flame contact, respectively.
These results indicate that sufficient flame retardancy cannot be obtained by applying and drying the 2025 solution. On the other hand, in the previous tests of the present inventor, in the impregnation / drying treatment of the 2025 solution, a result that the test specimen does not penetrate in the same evaluation of the flame retardant performance is obtained because the flame retardant spreads over the entire test specimen. ing. This is thought to be because the flame retardant is present in the vicinity of the specimen surface in the coating / drying process, so that the surface where the flame retardant does not exist (lower part of the specimen) is ignited and flames are generated. That is, the above results indicate that protection with a polymer layer coated and dried with a 2025 solution is insufficient to protect a polymer that has not been flame-retardant from flame.
In addition, the test specimens of WPG 56%, adhesion amount 0.056 g / cm ² and WPG 66% and adhesion amount 0.066 g / cm ² of the aqueous sucrose solution penetrated 40 seconds and 60 seconds, respectively, after the flame contact. These showed a slight flame retardant effect but did not reach a practical flame retardant level as compared with the 2025 solution specimen.

Specimens coated and dried with a 2025 solution containing 25 parts, 10 parts and 5 parts of sucrose were WPG 69%, 52% and 49%, adhesion amounts 0.069 g / cm ² , 0.052 g / cm ² and At 0.049 g / cm ² , no ignition / non-penetration.
In addition, test specimens coated and dried with a 2025 solution containing 2.5 parts, 1.6 parts, and 1.3 parts of sucrose were WPG 40%, 32%, and 27%, respectively, and the adhesion amount was 0.040 g / cm ^2. in 0.032 g / cm ² and 0.027 g / cm ^2, 130 seconds after flame contact, penetrating in 110 seconds and 110 seconds.
From these results, it can be seen that the greater the amount of sucrose added to the boron compound, the higher the flame retardancy.

As a result of continuously monitoring the temperature of the back surface (surface opposite to the flame contact surface) for 14 minutes in the flame contact state, the back surface temperature was in a temperature range of 60 to 80 ° C. (see FIG. 1). ).
In addition, the flame contact surface of the unpenetrated specimen was carbonized black to produce a uniform and dense carbide, and the back surface was white and remained unchanged.
From these results, it can be seen that these specimens are excellent not only in flame retardancy but also in fire resistance and heat insulation.
The obtained results are summarized in Tables 1 and 2.

(Test Example 2)
An aqueous solution was prepared in the same manner as in Test Example 1 except that trehalose (manufactured by Hayashibara Co., Ltd., Treha) was used instead of sucrose, and the flame retardant performance was evaluated by applying and drying them on a polyester nonwoven fabric.
The test body coated and dried with 2025 solution containing 25 parts and 10 parts of trehalose was unignited / non-penetrated, and the back surface temperature after 12 minutes of the test body was constant at 80 to 90 ° C.
Moreover, the test body which apply | coated and dried the 2025 solution containing 5 parts of trehalose penetrated 180 seconds after flame contact, and the back surface temperature of the test body rose rapidly from 50 degreeC before penetration.
Furthermore, the test specimens coated and dried with 2025 solutions containing 2.5 parts, 1.6 parts and 1.3 parts of trehalose penetrated at 140 seconds, 140 seconds and 70 seconds, respectively, after the flame contact. The back surface temperature rose rapidly from around 40 ° C. before penetration (see FIG. 2).
The obtained results are summarized in Tables 1 and 2.

(Test Example 3)
Except that glucose (glucose, manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of sucrose, an aqueous solution was prepared in the same manner as in Test Example 1, and applied to a polyester nonwoven fabric and dried to evaluate flame retardancy. did.
Specimens coated and dried with 2025 solutions containing 25 parts, 10 parts, 5 parts and 2.5 parts of glucose were non-ignited and non-penetrated, and the back surface temperature after 12 minutes of the specimen was constant at about 80 ° C. Met.
Specimens coated and dried with a 2025 solution containing 1.6 parts and 1.3 parts of glucose penetrated at 170 seconds and 140 seconds, respectively, after the flame contact, and the back surface temperature of the specimens was around 45 ° C. before penetration. Soared.
The obtained results are summarized in Tables 1 and 2.

(Test Example 4)
Except that fructose (fructose, manufactured by Wako Pure Chemical Industries, Ltd.) was used instead of sucrose, an aqueous solution was prepared in the same manner as in Test Example 1, and these were applied to polyester nonwoven fabric and dried to evaluate flame retardant performance. did.
Specimens coated and dried with 2025 solutions containing 25 parts, 10 parts, 5 parts and 2.5 parts of fructose were not ignited and not penetrated, and the back surface temperature after 12 minutes of the specimen was constant at about 80 ° C. Met.
In addition, the test specimens coated and dried with 2025 solutions containing 1.6 parts and 1.3 parts of fructose penetrated 180 seconds and 170 seconds, respectively, after flame contact, and the back surface temperature of the specimens was 45 ° C. before penetration. It soared from the front and back.
The obtained results are summarized in Tables 1 and 2.

(Test Example 5)
An aqueous solution was prepared in the same manner as in Test Example 1 except that starch (made by Koda Shoten, potato potato starch, hereinafter the same) was used instead of sucrose, and the addition amount was 6 parts, 3 parts and 1 part, They were applied to polyester nonwoven fabric and dried to evaluate flame retardancy.
Specimens coated and dried with a 2025 solution containing 6 parts and 3 parts of starch were non-ignited and non-penetrated, and the back surface temperature after 12 minutes of the specimens was constant at 75 ° C. and 95 ° C., respectively (see FIG. 3).
Moreover, the test body which apply | coated and dried 2025 solution containing 1 part of starch penetrated 220 seconds after flame contact, and the back surface temperature of the test body rose rapidly from about 60 degreeC before penetration (refer FIG. 3).
The obtained results are summarized in Tables 1 and 2.

(Test Example 6)
An aqueous solution was prepared in the same manner as in Test Example 1, except that glucomannan (manufactured by Shimizu Chemical Co., Ltd., ROLEX LM) was used instead of sucrose, and the addition amount was 6 parts, 3 parts and 1 part. They were applied to polyester nonwoven fabric and dried to evaluate flame retardancy.
The test piece coated and dried with a 2025 solution containing 6 parts and 3 parts of glucomannan was not ignited / non-penetrated, and the back surface temperature after 12 minutes of the test piece was constant at 65 ° C. and 80 ° C., respectively.
Moreover, the test body which apply | coated and dried 2025 solution containing 1 part of glucomannan penetrated 580 seconds after flame contact, and the back surface temperature of the test body rose rapidly from about 80 degreeC before penetration).
The obtained results are summarized in Tables 1 and 2.

(Test Example 7)
An aqueous solution was prepared in the same manner as in Test Example 1, except that hydroxypropylmethylcellulose (water-soluble cellulose, manufactured by Shin-Etsu Chemical Co., Ltd., Metrose 60SH) was used instead of sucrose, and the addition amount was 6 parts, 3 parts and 1 part. They were prepared and applied to polyester nonwoven fabric and dried to evaluate flame retardancy.
The test specimens coated and dried with a 2025 solution containing 6 parts, 3 parts and 1 part of hydroxypropylmethylcellulose were not ignited / non-penetrated, and the back surface temperatures after 12 minutes of the test specimens were 62 ° C., 70 ° C. and 80 ° C., respectively. Constant at ° C.
The obtained results are summarized in Tables 1 and 2.

(Test Example 8)
Except that cellobiose (manufactured by Matsutani Chemical Co., Cellobiose 90) was used instead of sucrose, an aqueous solution was prepared in the same manner as in Test Example 1, and applied to a polyester nonwoven fabric and dried to evaluate flame retardancy. .
Specimens coated and dried with a 2025 solution containing 25 parts, 10 parts and 5 parts of cellobiose were not ignited and not penetrated, and the back surface temperatures after 12 minutes of the specimens were 70 ° C, 73 ° C and 85 ° C, respectively. It was constant.
Moreover, the test body which apply | coated and dried the 2025 solution containing each 2.5 parts of cellobiose, 1.6 parts, and 1.3 parts penetrated 450 seconds, 340 seconds, and 280 seconds after flame contact, respectively.
The obtained results are summarized in Tables 1 and 2.

(Test Example 9)
An aqueous solution was prepared in the same manner as in Test Example 1, except that 3 parts of starch (made by Koda Shoten, potato potato starch) was used instead of sucrose, and a polypropylene plate (thickness 1 mm) was used instead of the polyester nonwoven fabric. It was applied to a polypropylene plate and dried to evaluate flame retardancy.
An attempt was made to compare and evaluate the 2025 solution and an aqueous starch solution (an aqueous solution in which 3 parts of starch were added / dissolved with respect to 100 parts of water).
The test sample coated and dried with the 2025 solution containing starch was unignited / non-penetrated, and the back surface temperature after 12 minutes of the test sample was constant at 75 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape.
The results obtained are summarized in Tables 3 and 4.

(Test Example 10)
An aqueous solution was prepared in the same manner as in Test Example 9 except that a polyethylene plate (thickness 1 mm) was used instead of the polypropylene plate, and the flame retardant performance was evaluated by applying and drying the solution on a polyethylene plate.
An attempt was made to compare and evaluate the 2025 solution and an aqueous starch solution (an aqueous solution in which 3 parts of starch had been added / dissolved with respect to 100 parts of water).
The test sample coated and dried with the 2025 solution containing starch was unignited / non-penetrated, and the back surface temperature after 12 minutes of the test sample was constant at 78 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape.
The results obtained are summarized in Tables 3 and 4.

(Test Example 11)
Except that a rigid urethane foam (thickness 10 mm) was used instead of the polypropylene plate, an aqueous solution was prepared in the same manner as in Test Example 9, and applied to the rigid urethane foam and dried to evaluate the flame retardant performance. .
An attempt was made to compare and evaluate the 2025 solution and an aqueous starch solution (an aqueous solution in which 3 parts of starch were added / dissolved with respect to 100 parts of water), but the rigid urethane foam could not be applied because it repels these solutions, and thus could not be evaluated.
The test piece coated and dried with the 2025 solution containing starch was non-ignited / non-penetrated, and the back surface temperature after 12 minutes of the test piece was constant at 40 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape.
The results obtained are summarized in Tables 3 and 4.

(Test Example 12)
Except that a flexible urethane foam (thickness 10 mm) was used in place of the polypropylene plate, an aqueous solution was prepared in the same manner as in Test Example 9, and applied to the flexible urethane foam and dried to evaluate flame retardancy. .
The test piece coated and dried with the 2025 solution containing starch was non-ignited / non-penetrated, and the back surface temperature after 12 minutes of the test piece was constant at 40 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape.
On the other hand, the specimens immersed and dried (impregnation treatment) in the 2025 solution and the starch aqueous solution, respectively, were flamed 30 seconds and 27 seconds after the flame contact, respectively.
The results obtained are summarized in Tables 3 and 4.

(Test Example 13)
An aqueous solution was prepared in the same manner as in Test Example 9 except that a polypropylene nonwoven fabric (Nippon Paper Crecia, Kimtex, thickness 0.7 mm) was used instead of the polypropylene plate, and an aqueous solution was applied to the polypropylene nonwoven fabric and dried. The flame retardant performance was evaluated.
The test specimen coated and dried with the 2025 solution containing starch was unignited / non-penetrated, and the back surface temperature after heating for 12 minutes or more was constant at 78 ° C.
Further, when the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact with the test body and heated from the side, it did not ignite for 12 minutes and did not rise. The flame contact surface of the test body was blackened and carbonized.
On the other hand, the test specimens obtained by immersing and drying (impregnating) the test specimens in a 2025 solution and an aqueous starch solution, respectively, burned up at 15 seconds and 10 seconds after contact with flame.
The obtained results are summarized in Table 1.

In addition, the evaluation of flame retardancy was carried out based on FMVSS302 (American Automobile Safety Standard Flammability Test).
Specifically, a test specimen (305 mm × 305 mm) prepared in the same manner as described above was placed horizontally with a U-shaped frame, a burner port was installed at a position 18.8 mm directly below the test specimen, and a 15-second indirect flame ( The flame length was 19 mm) and the time during which the flame passed through the 38 mm and 325 mm lines from the ignition end of the specimen was measured. Moreover, when combustion did not continue to the position of 287 mm from the ignition end of the test body, the time to extinction and the length from the ignition end of the test body were measured. From these measurements, the burning time (seconds) and burning rate (mm / sec) were determined.
The untreated polypropylene non-woven fabric had a burning time of 88 seconds and a burning rate of 69 mm / sec. However, the test piece coated and dried with a 2025 solution containing starch did not ignite, and had a burning time of 0 sec and a burning rate of 0 mm / sec. It was.
Moreover, the test body which apply | coated and dried the 2025 solution and the starch aqueous solution, respectively, had a burning time of 30 seconds and 77 seconds, a burning speed of 28 mm / sec, and a burning speed of 50 mm / sec.
The results obtained are summarized in Tables 3 and 4.

(Test Example 14)
Except that a polyurethane film (thickness 0.3 mm) was used in place of the polypropylene plate, an aqueous solution was prepared in the same manner as in Test Example 9, and applied to the polyurethane film nonwoven fabric and dried to evaluate flame retardancy. did.
The test specimen coated and dried with the 2025 solution containing starch was unignited / non-penetrated, and the back surface temperature after heating for 12 minutes or more was constant at 65 ° C.
On the other hand, the test specimens obtained by immersing and drying (impregnating) the test specimens in a 2025 solution and an aqueous starch solution, respectively, burned up at 23 seconds and 15 seconds after contact with flame.
The results obtained are summarized in Tables 3 and 4.

(Test Example 15)
Except that a foamed polystyrene foam plate (thickness 10 mm) was used instead of the polypropylene plate, an aqueous solution was prepared in the same manner as in Test Example 9, and applied to the foamed polystyrene foam plate and dried to provide flame retardancy. evaluated.
An attempt was made to compare 2025 solution and aqueous starch solution (aqueous solution in which 3 parts of starch was added / dissolved with respect to 100 parts of water), but the foamed polystyrene foam board could not be applied to repel these solutions, and could not be evaluated. .
The test sample coated and dried with the 2025 solution containing starch was unignited / non-penetrated, and the back surface temperature after heating for 12 minutes or more was constant at 35 ° C.
Moreover, when the end of the flame of the gas burner (flame length 10 cm) having a stronger heating power than the 45 ° method Meckel burner test was brought into contact with the test body and heated from the side, it did not ignite for 12 minutes and did not burn. The part in contact with the flame was carbonized black, but there was no change in the shape of the back.
The results obtained are summarized in Tables 3 and 4.

(Test Example 16)
An aqueous solution was prepared in the same manner as in Test Example 9 except that α-cyclodextrin (C ₃₆ H ₆₀ O ₃₀ , molecular weight 973, manufactured by Junsei Kagaku) was used instead of starch, and this was applied to a polypropylene plate. It dried and evaluated flame retardancy.
An attempt was made to compare 2025 solution and an α-cyclodextrin aqueous solution (an aqueous solution in which 3 parts of α-cyclodextrin was added / dissolved to 100 parts of water), but the polypropylene plate could not be applied to repel these solutions, Could not be evaluated.
The test specimen coated and dried with the 2025 solution containing α-cyclodextrin was non-ignited / non-penetrated, and the back surface temperature after 12 minutes of the test specimen was constant at 63 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape.
The results obtained are summarized in Tables 3 and 4.

(Test Example 17)
Instead of the 2025 solution, an aqueous solution of a boron compound in which 60 parts of boric acid and 75 parts of borax are added to 100 parts of water and heated to 60 ° C. or more to dissolve the additive (solid content: 42.4%, (Hereinafter referred to as “6075 solution”), an aqueous solution was prepared in the same manner as in Test Example 9, and applied to a polypropylene plate and dried to evaluate flame retardancy.
The test body coated and dried with the 6075 solution containing starch was unignited / non-penetrated, and the back surface temperature after 12 minutes of the test body was constant at 71 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and white foam was seen, but almost no change was seen on the back.
The results obtained are summarized in Tables 3 and 4.

(Test Example 18)
Instead of 2025 solution, 120 parts of boric acid and 150 parts of borax are added to 100 parts of water and heated to 90 ° C. or more to dissolve the additive (solid content 53.8%, (Hereinafter referred to as “1215 solution”), an aqueous solution was prepared in the same manner as in Test Example 9, and applied to a polypropylene plate and dried to evaluate flame retardancy.
The test sample coated and dried with the 1215 solution containing starch was unignited / non-penetrated, and the back surface temperature after 12 minutes of the test sample was constant at 95 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and white foam was seen, but almost no change was seen on the back.
The results obtained are summarized in Tables 3 and 4.

(Test Example 19)
Other than using 2025 solution, an aqueous solution of boron compound (hereinafter referred to as “borax solution”) in which 38 parts of borax was added to 100 parts of water and heated to 60 ° C. or higher to dissolve the additive was used. In the same manner as in Test Example 1, an aqueous solution was prepared, and applied to a polyester nonwoven fabric and dried to evaluate flame retardancy.
Specimens were coated and dried borax solution containing 25 parts of sucrose and 10 parts respectively, WPG56% respectively and 43%, in coating weight 0.056 g / cm ² and 0.043 g / cm ^2, un-ignited and not It was a penetration.
In addition, the specimens coated and dried with the borax solution containing 5 parts, 2.5 parts, 1.6 parts and 1.3 parts of sucrose adhered to WPG 41%, 39%, 29% and 19%, respectively. The penetrations were 120 seconds, 105 seconds, 90 seconds and 70 seconds after flame contact in the amounts 0.041 g / cm ² , 0.039 g / cm ² , 0.029 g / cm ² and 0.019 g / cm ² .
On the other hand, the test body coated and dried with the borax solution penetrated 60 seconds after the flame contact.
From these results, it can be seen that the synergistic effect of flame retardancy by the combined use of sucrose is not only in the 2025 solution but also in the borax solution.
The results obtained are summarized in Tables 5 and 6.

(Test Example 20)
An aqueous solution containing 3 parts of starch was prepared in the same manner as in Test Example 9 except that a borax solution was used instead of the 2025 solution, and applied to a polypropylene plate and dried to evaluate the flame retardancy.
The test piece coated and dried with the borax solution containing starch was not ignited and not penetrated, and the back surface temperature after 12 minutes of the test piece was constant at 82 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape.
The results obtained are summarized in Tables 5 and 6.

(Test Example 21)
Instead of 2025 solution, 25 parts of boric acid was added to 100 parts of water and heated to 95 ° C. or higher to dissolve an additive (hereinafter referred to as “boric acid solution”). In the same manner as in Test Example 1, an aqueous solution was prepared, and applied to a polyester nonwoven fabric and dried to evaluate flame retardancy.
Specimens coated and dried with a boric acid solution containing 25 parts and 10 parts of sucrose respectively had WPG of 45% and 38%, and deposits of 0.450 g / cm ² and 0.380 g / cm ² , respectively. It was a penetration.
In addition, the test specimens coated and dried with boric acid solutions containing 5 parts, 2.5 parts, 1.6 parts and 1.3 parts of sucrose adhered to WPG 21%, 13%, 8% and 7%, respectively. It penetrated at 115 seconds, 95 seconds, 78 seconds and 55 seconds after flame contact in amounts of 0.210 g / cm ² , 0.130 g / cm ² , 0.080 g / cm ² and 0.070 g / cm ² .
On the other hand, the test body on which the boric acid solution was applied and dried penetrated 15 seconds after the flame contact.
From these results, it can be seen that the synergistic effect of the flame retardant performance by the combined use of sucrose is not only in the 2025 solution but also in the boric acid solution.
The results obtained are summarized in Tables 5 and 6.

(Test Example 22)
An aqueous solution containing 3 parts of starch was prepared in the same manner as in Test Example 9 except that a boric acid solution was used instead of the 2025 solution, and applied to a polypropylene plate and dried to evaluate flame retardancy.
The test specimen coated and dried with the boric acid solution containing starch was unignited / non-penetrated, and the back surface temperature after 12 minutes of the test specimen was constant at 96 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape.
The results obtained are summarized in Tables 5 and 6.

(Test Example 23)
Instead of the 2025 solution, an aqueous solution of a boron compound in which 56 parts of sodium pentaborate decahydrate (manufactured by US Borax) is added to 100 parts of water and heated to 60 ° C. or higher to dissolve the additive (hereinafter referred to as “the aqueous solution”) Except for using “borate solution”), an aqueous solution was prepared in the same manner as in Test Example 1 and applied to a polyester nonwoven fabric and dried to evaluate flame retardancy.
Specimens coated and dried with a borate solution containing 25 parts and 10 parts of sucrose, respectively, were WPG 58% and 50%, adhesion amounts 0.058 g / cm ² and 0.050 g / cm ² , respectively. It was non-penetrating.
Moreover, the test body which apply | coated and dried the borate solution which each contains 5 parts, 2.5 parts, 1.6 parts, and 1.3 parts of sucrose is WPG 41%, 25%, 21%, and 19%, coating weight ^{0.041g / cm 2, 0.025g / cm} 2, at a 0.021 g / cm ² and 0.019 g / cm ^2, 179 seconds after flame contact, 115 seconds, was pierced with 88 seconds and 62 seconds.
On the other hand, the test body on which the borate solution was applied and dried penetrated 35 seconds after the flame contact.
From these results, it can be seen that the synergistic effect of flame retardancy by the combined use of sucrose is not only in the 2025 solution but also in the borate solution.
The results obtained are summarized in Tables 5 and 6.

(Test Example 24)
Except that a borate solution was used instead of the 2025 solution, an aqueous solution containing 3 parts of starch was prepared in the same manner as in Test Example 9, and applied to a polypropylene plate and dried to evaluate flame retardancy. .
The test body coated and dried with the borate solution containing starch was unignited / non-penetrated, and the back surface temperature after 12 minutes of the test body was constant at 96 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape.
The results obtained are summarized in Tables 5 and 6.

(Test Example 25)
An aqueous solution was prepared in the same manner as in Test Example 9 except that a 2025 solution in which 6 parts of an aqueous polyurethane emulsion (solid content 45%, manufactured by DIC, Hydran APX-101H) was further added to 3 parts of starch was used. It was applied to a polypropylene plate and dried to evaluate flame retardancy.
The test body coated and dried with a 2025 solution containing starch and an aqueous polyurethane emulsion was non-ignited and non-penetrated, and the back surface temperature after 12 minutes of the test body was constant at 80 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape. The film formed on the surface of the test specimen by flame contact has flexibility, and is cracked when bent compared to the test specimen film coated and dried with the 2025 solution containing only the starch of Test Example 9. It was a film that was difficult to generate.
The results obtained are summarized in Tables 5 and 6.

(Test Example 26)
Test Example 9 except that a 2025 solution in which 6 parts of an ethylene-vinyl acetate copolymer (EVA) emulsion (solid content 55%, manufactured by Sumitomo Chemical Co., Ltd., Sumikaflex 201HQ) was further added to 3 parts of starch was used. Similarly, an aqueous solution was prepared, and applied to a polypropylene plate and dried to evaluate flame retardancy.
The test body coated and dried with the 2025 solution containing starch and EVA emulsion was non-ignited and non-penetrated, and the back surface temperature after 12 minutes of the test body was constant at 76 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape. The film formed on the surface of the test specimen by flame contact has flexibility, and is cracked when bent compared to the test specimen film coated and dried with the 2025 solution containing only the starch of Test Example 9. It was a film that was difficult to generate.
The results obtained are summarized in Tables 5 and 6.

(Test Example 27)
Except that a 2025 solution in which 12 parts of an ethylene-acrylic acid copolymer (EEA) emulsion (solid content 25%, Sumitomo Seika, Xyxen L type) was further added to 3 parts of starch was used in the same manner as in Test Example 9. Then, an aqueous solution was prepared and applied to a polypropylene plate and dried to evaluate flame retardancy.
The test body coated and dried with the 2025 solution containing starch and EEA emulsion was non-ignited and non-penetrated, and the back surface temperature after 12 minutes of the test body was constant at 69 ° C.
Further, the end of the flame of a gas burner (flame length 100 mm) having a heating power stronger than that of the 45 ° Meckel burner method was brought into contact (flame contact) from the side of the test body, but the shape was maintained for 12 minutes or more. The flame-contacting surface of the test body was blackened and carbonized, but the back surface was slightly melted and changed its shape. The film formed on the surface of the test specimen by flame contact has flexibility, and is cracked when bent compared to the test specimen film coated and dried with the 2025 solution containing only the starch of Test Example 9. It was a film that was difficult to generate.
The results obtained are summarized in Tables 5 and 6.

(Test Example 28)
482 kg of a 2025 solution prepared in the same manner as in Test Example 1 was granulated by the spray drying method under the following conditions.
Apparatus: Nippon Chemical Machinery Manufacturing Co., Ltd. Nozzle diameter: 0.84 mm
Swirl: SC
Spray pressure: about 120 kgf / cm ² (12 mPa)
Spray amount: about 120L / H
Hot air volume: 40 Nm ³ / min.
Hot air temperature: 160 ° C
Exhaust air temperature: 79.8-83.8 ° C. (cone portion)
75.8-80.2 ° C (Cyclone part)

Clean spherical particles having the following physical property values were obtained (powder recovery amount 64.2 kg).
Water content: 7.2% (105 ° C. × 2 hours loss on drying value)
Particle size: 30-50 μm (measured from electron micrograph)
Average particle size: 41.7 μm
Bulk specific gravity: 0.87 (touch specific gravity)
0.61 (apparent specific gravity)
Thus, the aqueous solution of the boron compound of the present invention could be evaporated and dried (granulated) by a known method.

A low-density polyethylene resin (manufactured by Sumitomo Chemical Co., Ltd., the same applies hereinafter) obtained by heating and melting 10 parts of the powder obtained by evaporating and drying the 2025 solution and 3 parts of starch using a spray drying apparatus (manufactured by Nippon Chemical Machinery Manufacturing Co., Ltd.) ) 100 parts, and the mixture was uniformly dispersed by melt kneading. Next, using an extrusion molding machine (manufactured by Hitz Hitachi Zosen), the obtained kneaded material was formed into a 1 mm thick plate to obtain a test piece of a polyethylene plate. Evaluated.
The test body was not ignited and not penetrated, and the back surface temperature after 12 minutes of the test body was constant at 69 ° C. The flame contact surface of the test body was blackened and white foam was observed, but the shape was almost maintained.
The results obtained are summarized in Tables 7 and 8.

(Test Example 29)
The flame retardant performance of the test specimen of the polypropylene plate was evaluated in the same manner as in Test Example 28 except that a polypropylene resin (manufactured by Sumitomo Chemical Co., Ltd., the same applies below) was used instead of the low density polyethylene resin.
The test body was not ignited and not penetrated, and the back surface temperature after 12 minutes of the test body was constant at 58 ° C. The flame contact surface of the test body was blackened and white foam was observed, but the shape was almost maintained.
The results obtained are summarized in Tables 7 and 8.

(Test Example 30)
Except that 10 parts of sucrose was used instead of 3 parts of starch, the flame retardancy performance of the polyethylene plate specimen was evaluated in the same manner as in Test Example 28.
The specimen was unignited / non-penetrated, and the back surface temperature after 12 minutes of the specimen was constant at 72 ° C. The flame contact surface of the test body was blackened and white foam was observed, but the shape was almost maintained.
The results obtained are summarized in Tables 7 and 8.

(Test Example 31)
The flame retardant performance of the test specimen of the polypropylene plate was evaluated in the same manner as in Test Example 28, except that 10 parts of sucrose was used instead of 3 parts of starch, and a polypropylene resin was used instead of the low density polyethylene resin.
The test body was not ignited and not penetrated, and the back surface temperature after 12 minutes of the test body was constant at 54 ° C. The flame contact surface of the test body was blackened and white foam was observed, but the shape was almost maintained.
The results obtained are summarized in Tables 7 and 8.

Claims (10)

  A flame retardant composition comprising a boron compound selected from boric acid, borate or a mixture thereof and a saccharide in a synergistic ratio. The boron compound is boric acid (H ₃ BO ₃ ), borax (Na ₂ B ₄ O ₇ .10H ₂ O), sodium pentaborate (NaB ₅ O ₈ ) or a mixture thereof, and the saccharide is A monosaccharide selected from glucose, fructose, sucrose (sucrose), trehalose, cellobiose and α-cyclodextrin or a polysaccharide selected from starch, glucomannan and hydroxypropylmethylcellulose The flame retardant composition according to 1.   When the saccharide is a monosaccharide or oligosaccharide, the proportion of the synergistic effect is 5 to 2000 parts of saccharide when the saccharide is a monosaccharide or oligosaccharide, or 1 to 2000 parts of saccharide when the saccharide is a polysaccharide. The flame retardant composition according to claim 1 or 2. The flame retardant composition is
A part of boric acid and part b of borax (provided that a <35, b <40, 0 <a <b + 5) are added to 100 parts of water, heated to 70-90 ° C. to dissolve, and then at room temperature. An aqueous solution containing 2.5 mol / kg or more in terms of boron without containing a chelating agent or surfactant,
To 100 parts of water, add c part of boric acid and d part of borax (provided c ≧ 35, d ≧ 40) and heat to 40 to 100 ° C. to dissolve and 100 parts of water Boron selected from aqueous solutions in which 2-28 parts of boric acid, 2-98 parts of borax or 6-50 parts of sodium pentaborate (NaB ₅ O ₈ ) are added and heated to 40-100 ° C. In an aqueous solution of the compound,
When the saccharide is a monosaccharide or oligosaccharide, 1 to 80 parts of saccharide is added to 100 parts of water, or when the saccharide is a polysaccharide, 1 to 30 parts of saccharide is added to 100 parts of water and dissolved. The flame retardant composition according to any one of claims 1 to 3, which is a liquid flame retardant composition.   The said flame-retardant composition mixes the boron compound selected from the said boric acid, borate, or those mixtures, and the said saccharides, or evaporates the liquid flame-retardant composition of Claim 4 to dryness The flame retardant composition according to any one of claims 1 to 3, wherein the flame retardant composition is a powdery flame retardant composition.   A flame retardant treatment method comprising obtaining a flame retardant material by treating a flame retardant target material with the flame retardant composition according to claim 1.   The flame retardant treatment method according to claim 6, wherein the flame retardant material is a material selected from wood, paper, woven fabric, nonwoven fabric, and resin. The process is
The flame retardant composition is a liquid flame retardant composition selected from an aqueous solution, an aqueous suspension and a colloidal solution, and the material to be flame retardant is selected from wood, paper, woven fabric, nonwoven fabric and resin. When the material is applied or impregnated with the liquid flame retardant composition,
When the flame retardant composition is a powdered flame retardant composition and the flame retardant material is a resin, the powdered flame retardant composition is added to the resin and melt-kneaded, or The flame retardant treatment method according to claim 6 or 7, wherein when the material to be combusted is a resin, powdery components of the flame retardant composition are individually added to the resin and melt-kneaded. The application is performed such that the weight increase rate of the flame retardant material is 5 to 400% or the adhesion amount is 0.004 to 1.5 g / cm ² , and the impregnation is 1 kg of the flame retardant material. The flame retardant treatment method according to claim 8, wherein the impregnation amount is 50 g or more per unit, and the addition is performed so that the addition amount is 5 to 30 parts with respect to 100 parts of the resin.   A flame retardant material obtained by the flame retardant treatment method according to claim 6.

Images