JPS61179289A - Auxiliary flame retarder for cellulose material - Google Patents

Abstract

PURPOSE:To provide an auxiliary flame retarder capable of imparting hygroscopicity and flexibility to a cellulose material, which comprises a specific quaternary ammonium salt compound. CONSTITUTION:An auxiliary flame retarder comprising a quaternary ammonium salt compound of the given formula. In the formula, R1 is an 8-24C hydrocarbon residue optionally having a hydroxyl, ether, ester, urea or amide bond in its chain; R2 is a 1-3C alkyl, hydroxyalkyl, benzyl, an 8-24C hydrocarbon residue optionally having a hydroxyl, ether, ester, urea or amide bond in its chain; R3 and R4 each are a 1-3C alkyl, hydroxyalkyl, benzyl or an 8-24 aralkyl; and X<-> is a halide ion or a methyl sulfate ion. Representative examples of a base flame retarder employed in combination with the auxiliary flame retarder include a compound containing nitrogen, phosphorus, sulfur or boron.

Description

DETAILED DESCRIPTION OF THE INVENTION "Industrial Application Field" The present invention relates to a flame retardant aid for cellulosic materials that is made of a quaternary ammonium salt compound and is capable of imparting hygroscopicity and flexibility.

"Conventional technology" Conventionally, phosphorus compounds, nitrogen compounds, sulfur compounds, boron compounds, etc. have been used as flame retardants to impart flame retardant properties to cellulose-based products whose main component is cellulose, such as cloth, wood, paperboard, and wall covering materials. is widely used.

However, for example, guanidine sulfamate has an excellent effect of imparting flexibility to cellulose products and is most commonly used, but it has poor thermal stability such as yellowing when heated at 180 to 200°C, high hygroscopicity, and In order to achieve a practically sufficient flame retardant effect, it is necessary to apply approximately 18% by weight of flame retardant to the material to be treated, and the flame retardant effect is inferior due to the amount of adhesion. have. Other organic nitrogen-based inorganic acid salts such as guanidine phosphate, guanidine sulfate, guanidine borate, guanylurea polyphosphate, and aliphatic amine phosphates have a high flame retardant effect, but
It has poor thermal stability, lacks the effect of imparting flexibility to cellulose products, and causes a significant decrease in the strength of the treated material when it is completely dry (when heated at high temperatures, when the treated material has almost no moisture). It has its drawbacks. In order to further improve the flame retardant properties of these flame retardants, borax and boric acid are often used together.
In that case, the flexibility is further reduced, and the range of applications is therefore limited. In addition, although ammonium phosphate, ammonium sulfate, ammonium hydrobromide, or their inorganic salts are used in combination with borax or boric acid, they make the treated material hard and have extremely low strength when dry. do. Also, depending on the type of flame retardant, it has strong hygroscopicity, and the degree of moisture absorption changes depending on changes in atmospheric humidity and pressure, causing various problems such as causing mold growth and impairing the dimensional stability of treated materials. This results in undesirable phenomena.

``The problem that the invention aims to solve'' It is not possible to satisfy all of the capabilities at the same time. In particular, although it has a high flame retardant effect, there are examples where its practical application is limited because it does not have sufficiently satisfactory functions in terms of hygroscopicity and flexibility imparting effect, that is, the strength of treated materials when completely dry and thermochromic properties. many. Therefore, there is a strong desire to develop a flame retardant composition that can improve the hygroscopicity and flexibility imparting effect without impairing the flame retardant effect of the flame retardant itself, and also has a favorable effect on thermochromic properties.

"Means and actions for solving problems" The inventors,
As a result of intensive research in view of these circumstances, we have found that known inorganic acid salt flame retardants of nitrogen-containing compounds, various inorganic compound flame retardants, and their compositions are used as base flame retardants. By using the quaternary ammonium salt compound having the above-mentioned long-chain hydrocarbon group, the hygroscopicity, flexibility, The present invention was completed based on new discoveries such as the fact that the strength of the treated material can be significantly improved, and that it also has a favorable effect on thermochromic properties.

That is, the present invention relates to the general formula (I) (wherein R1 is a saturated or unsaturated hydrocarbon residue having 06 to C□ carbon atoms, or a hydroxy group or an ether, ester, urea or has an amide bond, and R1 is an alkyl group having 01 to C8 carbon atoms, a hydroxyalkyl group, or a benzyl group, or a saturated or unsaturated hydrocarbon residue having C1 to C24 carbon atoms, or one of the above hydrocarbon residues. It has a hydroxy group or an ether, ester, urea or amide bond in the chain, and R3 and R1 each have a carbon number of C8 to C3.
Alkyl group of.

Hydroxyalkyl group or benzyl group or carbon number C
8~Cu aralkyl group, X is a halogen atom ion,
The present invention provides a flame retardant aid for cellulosic materials comprising a quaternary ammonium salt compound represented by a phosphate ion, a borate ion, a sulfate ion, or a methylsulfate ion.

The quaternary ammonium salt compound that is the active ingredient of the present invention basically consists of a quaternary ammonium cation □ having one or two groups having a chain length of 8 to 24 carbon atoms, a chloride ion,
Halogen atom ions such as bromine' ions, phosphate ions,
It is a compound consisting of a counter ion such as borate ion, sulfate ion, or methyl sulfate ion. The cation moiety is not particularly limited as long as one or two of the groups forming the quaternary ammonium have a chain length of 8 to 24 carbon atoms. That is, the following general formula (e/R-N-(U) in In) At least one of the groups forming the cation moiety 'R' is a saturated or unsaturated hydrocarbon residue having a carbon number of C8 to C24 or the above. It has a hydroxy group or an ether, ester, urea or amide bond in the chain of the hydrocarbon residue.The following are examples of those having an ether, ester, urea or amide bond in the chain of the hydrocarbon residue. .

(General formulas 1 to 2) R' is an alkyl group, alkenyl group or aralkyl group, and Bi is an alkylene group. The total number of carbon atoms of R/ and I is 8 to 24.

Specifically, long-chain alkenyl ammonium salts such as octyltrimethylammonium chloride, dioctyldimethylammonium phosphate, lauryldimethylhydroxyethylammonium borate, and stearyldimethylbenzylammonium chloride; Thenyltrimethylammonium chloride, dodecenyl dimethylhydroxyethylammonium sulfate. As a long chain hydroxyalkylammonium salt, 2-hydroxylauryl dimethyl hydroxyethylammonium phosphate!
, 2-hydroxystearyltrimethylammonium methyl sulfate. Also, as a compound having an ether, ester, amide or urea bond in the long alkyl chain, R-" O, H, CItH7-R'
-CffiH4m C11H6-R-011H28*
C17HfiS-R“ CfH1l+ +
011 nts-R-C8”l?s C1!”2
5- and the like are exemplified as representative compounds.

The quaternary ammonium metal chloride which is the active ingredient of the present invention is not limited to the compound having the above chemical structural formula.

A quaternary ammonium chloride having a group having 7 or less carbon atoms reduces the flexibility and absolute dry strength of the treated material, making it impossible to sufficiently improve the functionality aimed at by the present invention. If the chain length is 8 or more carbon atoms, there is no problem in terms of functionality, but if water is used alone as a solvent when impregnating or spraying cellulose products with a flame retardant composition, the chain length will be 8 or more carbon atoms. A quaternary ammonium salt compound having a long chain has reduced compatibility with water. Therefore, it is preferable to use a quaternary ammonium salt compound having a chain length of 24 or less carbon atoms. Although widely known perchlorate ions, nitrate ions, and various organic carboxyl ions are used as counterions, they are effective in improving the flexibility of the material to be treated, which is one of the purposes of the present invention, but they do not cause thermal discoloration. Therefore, the counter ions used in the present invention are halogen atom ions, phosphate ions, and borate ions.

Sulfate ion, methyl sulfate ion, etc. are preferred. Quaternary ammonium salt compounds with these counterions have many advantages as flame retardant aids for cellulosic materials, such as being flame retardant themselves and exhibiting excellent thermochromic properties. are doing.

The flame retardant auxiliary agent of the present invention contains the quaternary ammonium salt compound having the above-mentioned chemical structure in a weight ratio of 2 to 40, preferably 5 to 30, by weight based on the total amount of the flame retardant composition. If this blending ratio is less than 2% by weight, the effect of imparting flexibility is small and impractical. Moreover, if it exceeds 40% by weight, the hygroscopicity and flexibility imparting effect will not be further improved, leading to an increase in cost from an economic standpoint, and the solubility of the flame retardant composition in water will also decrease. This is also unfavorable from the viewpoint of the adhesion treatment of the flame retardant composition.

By using the quaternary ammonium salt compound, which is the active ingredient of the present invention, with known nitrogen compound, phosphorus compound, sulfur compound, and boron compound flame retardants in the above-mentioned mixing ratio, It has the effect of complementing the missing functions while maintaining the existing functions, and improving the overall function as a flame retardant for cellulosic materials.

For example, when the quaternary ammonium salt compound is used in combination with guanidine sulfamate, which has a high flexibility imparting effect,
The hygroscopicity of the sulfur amino acid guanidine can be improved, adding even more superior functionality. Further, when the quaternary ammonium salt compound is mixed with a known flame retardant such as guanidine silicate, guanidine phosphate, or guanidine borate, the hygroscopicity and flexibility of the treated material can be significantly improved. Ethylenediamine・
When the quaternary ammonium salt compound is mixed with a phosphate, a polyalkylene polyamine phosphate, or a composition containing these nitrogen/phosphorous flame retardants and boric acid/borax, the hygroscopicity and flexibility of the treated material can be improved. .

It is possible to improve the strength of treated materials when completely dry, and the range of practical applications thereof can be expanded. A composition of ammonium phosphate, ammonium polyphosphate, sodium phosphate, or an inorganic salt thereof and boric acid-borax has a high flame retardant effect by itself, but the hardness of the treated material is a major problem. By adding the quaternary ammonium salt compound to these flame retardant compositions and using them together, the flexibility and strength of the treated material when completely dry can be improved, as well as hygroscopicity, thermochromic properties, etc. The overall physical properties of are corrected in a favorable direction. As mentioned above, known flame retardants that can be used in combination with the quaternary ammonium salt compound are not particularly limited, and nitrogen,
Compounds containing phosphorus, sulfur, and boron are widely used as flame retardants.

Furthermore, alcohols (such as isopropanol) may be used as a component of a flame retardant composition containing the quaternary ammonium salt compound as an active ingredient.

The flame retardant composition can be used in the form of an aqueous solution or a powder, but a method of applying the aqueous solution to the material to be treated by impregnating or spraying it is usually widely applied.

When using the flame retardant composition in impregnation or spray treatment, the pH value (hydrogen ion concentration index in a 5 weight polyhydric solution) of the flame retardant composition is 5.0 to aO1, preferably 5.5.
It is used in the range of ~z5. When used at a pH value of 5.0 or less, the flame retardant composition exhibits corrosivity to metal materials, which is not preferred in practice. Further, use at a pT (value of aO or more) is not preferable because it lowers the thermal stability of the quaternary ammonium salt compound and causes coloration of the treated material.

The materials targeted for flame retardation in the present invention are paper and wall covering materials.

Cellulose-based products containing cellulose, such as textile products.

"Effects of the Invention" Although the quaternary ammonium salt compound, which is the active ingredient of the present invention, does not have high flame retardancy by itself, it can be used in combination with known flame retardants for cellulosic materials. It is possible to improve the hygroscopicity, flexibility, texture, and material strength when completely dry of the treated material while maintaining the high flame retardant effect of the known α-yellow flame retardant, and also to improve thermochromic properties. Demonstrates excellent effects such as being able to contribute.

〔Example〕

The present invention will be explained below with reference to Examples, but is not particularly limited thereto.

Examples 1 to 9 Table 1 shows the types and blending ratios of the flame retardant compositions used in each example.

Table 2 shows the results of impregnating paper with the flame retardant compositions listed in Table 1 and evaluating them using the test method shown below.

Acid deposition method P paper (Toyo Togami A2) is immersed in an aqueous solution in which a flame retardant composition is dissolved in water to a predetermined concentration, and then taken out.

This treated paper is sandwiched between new P papers to remove excess soaking liquid. After drying at 100° C. for 2 hours, it was left to cool and stored in a desiccator and subjected to the following tests.

Flame retardant composition adhesion rate--X 100% A: Treated paper mold after drying (100°C, 2 hours) B: Weight of paper before impregnation treatment (100°C.

2-hour dried product) 1 (Ge 11) The carbonization length was measured according to JIS A1322 (45°Metskel burner method).

Heat resistance (thermochromic) test After heating at 180°C for 10 minutes in a constant temperature hot air dryer, W
The value (whiteness) was measured and the thermochromic property was evaluated.

Flexibility evaluation test: Treated paper impregnated with the flame retardant composition shown in Table 1 and the flame retardant shown in Table 3 based on the flame retardant composition application method described above was heated at 100°C for 2 hours.
After drying for several hours, it was stored in a desiccator. Desiccator
The treated paper taken out from the filter paper was impregnated with the flame retardant composition, dried, and stored in a desiccator, and then heated to an absolutely dry state for 5 minutes at 200°C. (no weight change over time). Immediately after taking it out of the high-temperature hot air dryer, the treated paper was crushed by hand and ranked into the following four grades based on the appearance of cracks that occurred in the treated paper.

No cracks occurred in the α-force treated paper, but wrinkles did occur. ◎2 to 5 cracks occurred on the treated paper. 2-3 O-treated paper
It broke into pieces. △Hygroscopicity test The treated paper impregnated with the flame retardant composition was dried at 100°C for 12 hours and then weighed. The same dry impregnated paper was heated at a relative humidity of 80% and 30%
It was weighed immediately after being left in a constant temperature and humidity chamber at a low temperature of °C for 24 hours. The weight increase rate was defined as the moisture absorption rate.

Comparative Examples 1 to 5 Table 3 shows the flame retardants used in each comparative example and their blending ratios (weight ratios).

Table 4 shows the results of evaluating the flame retardants listed in Table 3 using the same method as in the examples.

Table 2 Evaluation results Table 3 Flame retardant (according to several terms) Table 4 Evaluation results Patent applicant Toyo Soda Kogyo Co., Ltd. Procedural amendment August 27, 1985

Claims (1)

[Claims] (1) General formula (I) ▲ Numerical formulas, chemical formulas, tables, etc. group or has an ether, ester, urea or amide bond, and R_2 is the number of carbon atoms C_
1 to C_3 alkyl group, hydroxyalkyl group, or benzyl group or saturated or unsaturated carbon number C_8
A hydrocarbon residue of ~C_2_4 or a chain of the above hydrocarbon residue has a hydroxy group or an ether, ester, urea or amide bond, and R_3 and R_4
are an alkyl group, hydroxyalkyl group, or benzyl group having a carbon number of C_1 to C_3, or a carbon number of C_8 to
A flame retardant auxiliary agent for cellulosic materials comprising a quaternary ammonium salt compound represented by an aralkyl group of C_2_4 and X^■ is a halogen atom ion, phosphate ion, borate ion, sulfate ion, or methyl sulfate ion.