JPH0730327B2 - Flame retardant composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a flame retardant composition.

[Prior Art] Conventionally, as a flame retardant composition, guanidine sulfamate,
Guanidine salt compounds such as guanidine phosphate are widely used. They are not fully satisfactory at the same time in both flame retardant and anti-coloring functions. As an improvement, there is an aqueous solution flame retardant obtained by adding boric acid or borax to condensed guanidine phosphate (for example, JP-A-61-2).
No. 43889 publication).

[Problems to be Solved by the Invention] However, when this is applied to paper and heated, the tear strength decreases.

[Means for Solving Problems] The present inventors have arrived at the present invention as a result of studying to obtain a flame retardant composition having a high tear strength even when applied to paper and heated.

That is, the present invention comprises a polyhydric alcohol borate ester-containing flame retardant composition (first invention), (1) polyhydric alcohol borate ester, and (2) guanidine salt-based compound, 20% ammonium salt of strong acid, 0-20% dicyandiamide compound and 0%
Flame retardant composition for paper, textile materials or building materials (second invention), characterized in that it contains ˜50% of phosphate (where% is% by weight of the composition).

In the boric acid ester of the polyhydric alcohol used in the present invention, the polyhydric alcohol is a dihydric to dihydric alcohol such as a trihydric to trihydric alcohol (glycerin, trimethylolpropane, pentaerythritol, sorbitol,
Sucrose, etc.) dihydric alcohol (ethylene glycol,
Propylene glycol, 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.) and alkylene oxides (ethylene oxide, propylene oxide) of these polyhydric alcohols (eg block, random) adducts (molecular weight) Is usually 100
~ 5000). 3 of these are preferred
.About.8-valent polyhydric alcohols, particularly preferred are glycerin, pentaerythritol and sorbitol.

The molar ratio of polyhydric alcohol and boric acid can be appropriately selected depending on the purpose of use and varies depending on the type of polyhydric alcohol, but boric acid is usually 0.3 to 3 per mol of polyhydric alcohol.
The molar amount is preferably 0.5 to 2.5 mol. If the amount of boric acid is less than 0.3 mol, the anti-coloring property is insufficient, and if it exceeds 3 mol, the tear strength is likely to decrease.

Specific examples of boric acid esters of polyhydric alcohols include glycerin (1) boric acid (1) ester [() indicates the number of moles. The same applies hereinafter. ], Pentaerythritol (1) boric acid (1.2) ester, sorbitol (1)
Boric acid (2.1) ester, sucrose (1) boric acid (2.6) ester and polyethylene glycol (molecular weight 600)
(1) A boric acid (0.7) ester is mentioned.

The borate ester of polyhydric alcohol can be produced by a usual dehydration condensation reaction. For example, it can be produced by adding boric acid to a polyhydric alcohol with stirring, gradually raising the temperature under nitrogen flow, and conducting a dehydration condensation reaction (esterification) at 100 to 150 ° C. After esterification, adjust the pH to 6 with an alkali such as caustic soda.
Adjusting to ~ 8.5 is preferable.

The composition of the present invention comprises, in addition to boric acid esters of polyhydric alcohols, known flame retardant components such as guanidine salt compounds (guanidine sulfamate, ridinganidine, guanidine sulfate, guanidine polyphosphate, etc .; methylolated guanidine sulfamate). , Hydroxyalkyl-substituted guanidine salts such as methylolated guanidine phosphate; cyano-substituted guanidine salts such as guanylurea phosphate; amino group-substituted or amino group-containing substituted guanidine salts such as aminoguanidine phosphate; Japanese Patent Application No. 62-67603 Guanidine Sulfamate ethylene oxide 2 moles adducts such as alkylene oxide adducts of guanidine salts, etc.), ammonium salts of strong acids (ammonium sulfamate, ammonium phosphate, ammonium sulfate, etc.), dicia Diamide compound (dicyandiamide, such as methylolated dicyandiamide), phosphate (sodium phosphate, disodium hydrogen phosphate, such as hydrogen ammonium phosphate) may contain such. Of these, guanidine salt compounds are preferred.

In the composition of the present invention, the content of each component is as follows based on the weight of the composition. The boric acid ester of polyhydric alcohol is usually 5 to 100%, preferably 10 to 100%. If it is less than 5%, sufficient performance may not be obtained.

When the composition of the present invention contains a known flame retardant component, for example, if it is a guanidine salt-based compound, the content is usually 0 to 95.
%, Preferably 5 to 90%. In the case of ammonium salt of strong acid, it is usually 0 to 20%, preferably 0 to 10%. In the case of a dicyandiamide compound, it is usually 0 to 20%, preferably 0 to 10%. In the case of phosphate, it is usually 0 to 50%, preferably 0 to 30%.

The composition of the present invention is preferably used as an aqueous solution.
When dissolved, the concentration can be variously changed depending on the purpose of use, and the concentration used is usually 0 in terms of solid content of the composition.
It is 5 to 60%, preferably 1 to 50%.

The composition of the present invention has a pH of 7.
It can be obtained by adjusting to 0 and usually mixing a guanidine salt-based compound and other components and water if necessary.

If necessary, a guanidine salt-based compound and other components may be allowed to coexist during production of the borate ester.

Examples of the substrate to be used for the composition of the present invention include cellulosic materials such as paper (shoji paper, bran paper, wallpaper, paperboard, synthetic paper, etc.). Further, it can be used as a fiber material such as cloth and a building material such as wood, plywood, and synthetic wood.

The amount of the composition of the present invention adhered to the substrate is usually 2 to 40%, preferably 3 to 35% in terms of solid content.

The method of applying the composition of the present invention to a substrate may be a conventionally used method, for example, a method of immersing paper in the composition of the present invention or a water-diluted solution thereof and then drying, with a size press. A method of spraying, a method of applying with a brush, and the like.

Further, the composition of the present invention can be used in combination with a sizing agent, a surface treating agent such as starch, and other paper treating agents.

[Examples] Hereinafter, the present invention will be further described with reference to Examples, but the present invention is not limited thereto. Parts in the examples indicate parts by weight.

Example 1 Boric acid 231 was prepared by stirring 1099 parts of a 70% aqueous solution of sorbitol.
And the temperature is gradually raised under nitrogen flow to carry out the dehydration condensation reaction.
The process was carried out until the temperature reached 140 ° C. to produce a light brown viscous boric acid ester. After cooling to a temperature of 180 ° C., the pH was adjusted to 7.0 and the solid content concentration was adjusted to 60% aqueous solution with a caustic soda aqueous solution.

45 parts of this borate aqueous solution, 73 parts of methylol guanidine sulfamate, and 382 parts of water were heated to a temperature of 50 to 70 ° C.
And mixed for 60 minutes to obtain a transparent and uniform flame retardant composition.

Example 2 1053 70% aqueous solution of sorbitol was used as polyhydric alcohol.
Parts and boric acid were changed to 263 parts to produce boric acid ester in the same manner as in Example 1 with a pH of 7.0 and a solid content of 6
Adjusted to 0%.

20 parts of this borate ester aqueous solution, 88 parts of guanidine sulfamate, and 392 parts of water were mixed at a temperature of 50 to 70 ° C. for 60 minutes to obtain a transparent and uniform flame retardant composition.

Example 3 Sorbitol borate aqueous solution prepared in Example 2
30 parts, 77 parts of methylolated guanidine sulfamate, 4 parts of ammonium sulfamate, 1 part of dicyandiamide and 388 parts of water were mixed at a temperature of 50 to 70 ° C. for 60 minutes to obtain a transparent and uniform flame retardant composition.

Example 4 629 parts of pentaerythritol as a polyhydric alcohol,
A boric acid ester was produced in the same manner as in Example 1 except that boric acid was changed to 371 parts, and the pH was 7.0 and the solid content concentration was 60%.
Adjusted to.

22 parts of this borate ester aqueous solution, 85 parts of guanidine sulfamate, 1.8 parts of dicyandiamide and 391.2 parts of water were mixed at a temperature of 50 to 70 ° C. for 60 minutes to obtain a transparent and uniform flame retardant composition.

Example 5 599 parts of glycerin and 401 of boric acid as polyhydric alcohol
A borate ester was produced in the same manner as in Example 1 except that parts were changed to adjust pH to 7.0 and solid content concentration to 60%.

25 parts of this borate aqueous solution, 82 parts of methylolated guanidine sulfamate, 3 parts of dicyandiamide and water
390 parts were mixed at a temperature of 50 to 70 ° C. for 60 minutes to obtain a transparent and uniform flame retardant composition.

Comparative Example 1 100 parts of guanidine sulfamate and 400 parts of water were mixed and dissolved at 50 to 70 ° C. to obtain a transparent composition.

Comparative Example 2 100 parts of guanidine phosphate and 400 parts of water were mixed and mixed at 50-70 ° C.
And dissolved to obtain a transparent composition.

Comparative Example 3 Guanidine sulfamate 95 parts, boric acid 5 parts and water 40
0 parts were mixed and melted at 50 to 70 ° C. to obtain a transparent composition.

Comparative Example 4 88 parts of condensed guanidine phosphate, 6 parts of boric acid, 6 parts of borax and 400 parts of water were mixed and dissolved at 50 to 70 ° C. to obtain a transparent composition.

Test Example 1 Using the flame retardant compositions of Examples 1 to 5 and Comparative Examples 1 to 4, the treatment liquid was treated on paper by a size press method to give 100 to 105
The performance was evaluated by the following method after drying with an auto dryer adjusted to a temperature of ℃. The results are shown in Table-1.

Anti-coloring property: heated in an oven at 180 ° C for 5 minutes to compare the degree of coloring.

Tear strength: The sample was heat treated in an oven at 180 ° C. for 5 minutes, and immediately thereafter, measured according to JIS-P-8116 “Test method for tear strength of paper”.

Flame retardance: The carbonization length was measured according to JIS-Z-2150 "Flame resistance test for thin materials" (45 ° Meckel burner method).

Example 6 Sorbitol borate aqueous solution prepared in Example 1
333 parts and 167 parts of water were added and dissolved to obtain a transparent and uniform flame retardant composition.

Example 7 450 parts of the aqueous solution of pentaerythritol borate ester prepared in Example 4 and 50 parts of water were added and dissolved to obtain a transparent and uniform flame retardant composition.

Comparative Example 5 Methylolated guanidine sulfamate 180 parts, boric acid 2
0 parts and 300 parts of water were mixed and stirred at 50 to 70 ° C. for 60 minutes to obtain a transparent and uniform flame retardant composition.

Test Example 2 Using the flame retardant compositions of Examples 6 and 7 and Comparative Example 5, the performance was evaluated in the same manner as in Test Example 1. The results are shown in Table-2.
Shown in.

[Effects of the Invention] The composition of the present invention has the following effects.

Tear strength is strong even when applied to paper and heated. When boron is simply added to the condensed guanidine phosphate, the effect of anti-coloring property is recognized, the paper becomes hard and the tear strength is lowered, but the composition of the present invention does not have such a phenomenon.

In addition, the anti-coloring property is further improved as compared with the conventional ones such as guanidine phosphate and guanidine sulfamate.

Further, the flame retardancy is further improved as compared with, for example, guanidine sulfamate.

Further, when it is used as an aqueous solution, it is easily dissolved and has good compatibility with other treating agents such as sizing agents and binders (starch, polyvinyl alcohol, etc.) and good workability.

It has high penetrability into the base material and can quickly and highly adhere to thick paper products such as kraft paper and paperboard.

Since it has the above effects, the composition of the present invention can be used for paper, cloth,
It is effective in many applications for various products such as wood and building materials.

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Claims (2)

[Claims] 1. A flame retardant composition for paper, fiber material or building material, which comprises boric acid ester of polyhydric alcohol. 2. A boric acid ester of a polyhydric alcohol and (2) a guanidine salt compound, an ammonium salt of a strong acid of 0 to 20%, a dicyandiamide compound of 0 to 20% and a phosphate of 0 to 50%. A flame retardant composition for paper, fiber material or building material, characterized in that (% is based on the weight of the composition).