JPH0450398A - Combustion-proof agent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition having excellent coloringinhibiting property, tear strength and combustion-proof property in the case of applying on paper and heating containing a reaction product derived from reaction of a mixture of ammonium salt of an inorganic acid and dicyandiamides with alkylene oxide in the presence of water as an active ingredient. CONSTITUTION:The aimed composition contains a reaction product derived from reaction of a mixture of (A) ammonium salt of an inorganic acid (preferably ammonium sulfamate) and (B) dicyandiamides (preferably dicyandiamide) preferably in a molar ratio of 0.5:1-1.8:1 with (C) alkylene oxide (preferably ethylene oxide or propylene oxide) in an amount of preferably 1-50wt.% in the presence of water as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to flame retardant compositions. More specifically, it relates to flame retardant compositions for paper and the like.

[Prior Art] Conventionally, flame retardants for paper and the like include guanidine sulfamate, methylolated guanidine sulfamate, and the like (for example, Japanese Patent Application Laid-Open No. 1990-1994).

[Problems to be Solved by the Invention] However, this product had problems in that when it was applied to paper and heated, the paper was likely to become colored, and the tear strength after heating was significantly reduced. Furthermore, when a flame retardant is applied to paper or the like, it may be required to have a soft stiffness, but there is a problem that the softness is insufficient.

C. Means for Solving the Problems] As a result of intensive studies by the present inventors in order to obtain a flame retardant composition that has the same or higher flame retardant performance as conventional paper, etc. and does not have these problems, the present inventors have found that: We have arrived at the present invention.

That is, the present invention provides a product (4) obtained by reacting an alkylene oxide (3) with a mixture of an inorganic acid ammonium salt (1) and a dicyandiamide (2) in the presence of water.
This is a flame retardant composition characterized by containing as an active ingredient.

In the present invention, examples of the inorganic acid ammonium salt (1) include ammonium sulfamate, ammonium phosphate, ammonium borate, ammonium sulfate, ammonium polyphosphate, ammonium chloride, and mixtures of two or more thereof. Among these, preferred is ammonium sulfamate.

In the present invention, as the dicyandiamide (2),
Examples include 1, dicyandiamide, monomethylol dicyandiamide, dimethylol dicyandiamide, and mixtures of two or more thereof. Among these, preferred is dicyandiamide.

In the present invention, the molar ratio of the inorganic acid ammonium salt (1) and the dicyandiamide (2) is usually 0.4:I to 2.
:11 Preferably 0.5:I-1,8:1. If the ammonium salt of an inorganic acid (1) is less than 0.4, the flame retardant property itself may deteriorate, and if it exceeds 2, the paper becomes more likely to be colored.

In the present invention, alkylene oxide (3) (hereinafter referred to as
For example, ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as EO),
AO having 2 to 4 carbon atoms such as 1,2-butylene oxide; hydroxyl-substituted products (e.g., glycidol), phenyl-substituted products (e.g., styrene oxide), and halo-substituted products (e.g., epichlorohydrin) of these Examples include. Furthermore, two or more of these may be used in combination. Among these, preferred is E.

and PO. In the case of an adduct of two or more types of AO, the addition format may be block, random, or a mixture thereof.

The amount of AO added in the product (4) is usually 0.5 to 60%, preferably 1 to 60%, based on the weight of the mixture of inorganic acid ammonium salt (1) and dicyandiamide (2).
It is 50%. If the amount added is less than 0.5%, coloring of paper, etc. is likely to occur, and if it exceeds 60%, the flame retardant property itself may deteriorate. Further, the amount of AO added is usually 0.00% based on the weight of the product (4) in terms of solid content.
It is 5 to 50%, preferably 1 to 4%.

If the AO content is less than 0.5%, coloring of the paper is likely to occur, and if it exceeds 50%, the flame retardant property itself may deteriorate.

The product (4) of the present invention may contain unreacted ammonium salts of inorganic acids (1) and/or dicyandiamides (2) of AO.

An example of the product (4) according to the invention is E of a mixture of ammonium sulfamate and dicyandiamide.
O reactant, EO reactant of a mixture of ammonium sulfate and dicyandiamide, PO reactant of a mixture of ammonium phosphate and dicyandiamide, EO/PO reactant of a mixture of ammonium sulfamate and dicyandiamide, EO reactant of a mixture of ammonium sulfate and dicyandiamide, Examples of the reactants include EO-PO reactants. (In the above description, the EO/PO reactant refers to a random reaction product of EO and PO, and the EO@PO reactant refers to a block reaction in the order of EOlPO. The same description will be used hereinafter.) In the present invention, The amount of water when reacting AO in the presence of water (in the case of using an aqueous formaldehyde solution, the amount including water in this aqueous solution) is usually 5 to 50%, based on the weight of the product (4) in terms of solid content. 35%, preferably 20-80
%. If the amount of water is less than 5%, the components of the raw materials may not be dissolved or dispersed, and if it exceeds 95%, the reaction will be slow.

To exemplify the method for producing the reaction product (4), AO is used without a catalyst or with a base catalyst (caustic potash, trimethylamine, etc.) or an acid catalyst (boron trifluoride, etc.) using an inorganic compound as a solvent or dispersion medium. The reaction product (4) can be produced by carrying out the reaction in the presence of pressure or normal pressure. This reaction temperature is usually 40 to 130
C1 Preferably carried out at 60-120°C. (40
If the temperature is below 130°C, the reaction progresses slowly, and if it exceeds 130°C, side reactions may occur and water-insoluble substances may be produced. ) The content of the product (4) in the composition of the invention is usually at least 10%, preferably at least 20%, based on the weight of the composition. If it is less than 10%, sufficient performance may not be obtained.

In addition to the product (4), the composition of the present invention can also contain other components such as other known flame retardants, if necessary.

Examples of this include guanidine salt-based compounds (hydroxyalkyl-substituted guanidine (methylolated guanidine sulfamate, etc.), guanidine salts (guanidine sulfamate, guanidine phosphate, guanidine hypophosphite, guanidine polyphosphate, guanidine borate, etc.) ), cyano-substituted guanidine (guanylurea sulfamate, guanylurea phosphate, guanylurea polyphosphate, etc.), amino-substituted or substituted guanidine salt containing an amine group (aminoguanidine sulfamate, amininganidine phosphate, etc.)
); Sulfamate compounds (magnesium sulfamate, etc.); Melamines (melamine, ammeline, etc.).

When these known components such as flame retardants are included in the composition of the present invention, the reaction product (4) and these known components are mixed, or these known components are mixed during the production of the reaction product (4). Components may be present together.

In the composition of the present invention, the content of components such as these known flame retardants can be selected without particular limitation within a range that satisfies the performance as a flame retardant. And/or in the case of sulfamate compounds, it is usually 90% or less, and in the case of melamines, it is usually 70% or less.

Preferably, the composition of the invention is used as an aqueous solution.

When dissolved, the concentration can be varied depending on the purpose of use. The concentration used is usually 0.5 to 60%, preferably 1 to 50%, based on the solid weight of the composition.
It is.

Substrates to which the composition of the present invention can be used include cellulosic materials such as paper (shoji paper, fusuma paper, wallpaper, paperboard,
synthetic paper, etc.). In addition, fiber materials such as cloth,
It can also be used for construction materials such as wood, plywood, and synthetic wood.

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

The composition of the present invention may be applied to the substrate by any conventional method, such as by dipping paper in the composition of the present invention or its water diluted solution and then drying it, or by applying it using a size press. There are two methods: applying with a brush, and applying with a brush.

The composition of the present invention can also be used in combination with a sizing agent, starch, a surface treatment agent such as polyvinyl alcohol, or other paper treatment agent.

[Example] The present invention will be further explained below with reference to Production Examples and Examples, but the present invention is not limited thereto. Parts in Production Examples and Comparative Production Examples indicate parts by weight.

Production Example 1 103 parts of ammonium sulfamate, 84 parts of dicyandiamide, and 154 parts of water were mixed. EO44 on this one
was gradually added under pressure and reacted at 80 to 100°C for 5 hours to obtain a liquid flame retardant composition. Solid content is GO, 1%
(EO content 19.0%).

Production Example 2 103 parts of ammonium sulfamate, 84 parts of dicyandiamide, and 163 parts of water were mixed. PO58 to this thing
was gradually added under pressure and reacted at 80 to 100°C for 5 hours to obtain a liquid flame retardant composition. The solids content was 60.0% (PO content 23.7%).

Production Example 3 80 parts of ammonium sulfamate, 84 parts of dicyandiamide, and 133 parts of water were mixed. 8035 parts of the mixture was gradually added under pressure and reacted at 80 to 100°C for 5 hours to obtain a liquid flame retardant composition. Solid content was 60.2%. (EO content 17.6%).

Production Example 4 148 parts of ammonium sulfamate, 84 parts of dicyandiamide, and 178 parts of water were mixed. EO35 for this thing
was gradually added under pressure and reacted at 80 to 100°C for 5 hours to obtain a liquid flame retardant composition. The solids content was 60.0% (EO content 13.194).

Comparative Production Example 1 194 parts of ammonium sulfamate and 84 parts of dicyafdiamide were mixed and reacted at 140 to 170°C for 3 hours. 417 parts of water was added to this to obtain a liquid guanidine sulfamate flame retardant composition. Solid content was 40.2%.

Comparative Production Example 2 194 parts of ammonium sulfamate and 84 parts of dicyandiamide were mixed and reacted at 140 to 170°C for 3 hours. Next, the above reactant was added to a system of 154 parts of water and 81 parts of formalin, and reacted at 70° C. for 2 hours to obtain a liquid methylolated guanidine sulfamate flame retardant composition. Solid content was 59.7%.

Comparative Production Example 3 In Comparative Production Example 1, ammonium sulfamate 1
A liquid guanidine sulfamate flame retardant composition was obtained in the same manner except that 94 parts were changed to 180 parts and 417 parts of water was changed to 366 parts.

The solid content was 40.3%.

Examples 1 to 4 and Comparative Examples 1 to 3 After treatment with the flame retardants of Production Examples 1 to 4 and Comparative Production Examples 1 to 3 and drying in an auto dryer with a temperature control of 100 to 105°C, performance was evaluated using the following method. evaluated.

The results are shown in Table-1. Here, "Production Examples 1 to 4 and Comparative Production Examples 1 to 3" and "Examples 1 to 4 and Comparative Examples 1 to 3"
3" are displayed in correspondence.

Coloration prevention property: Heated in an oven at 180°C for 10 minutes and compared the degree of coloration.

Tear strength: Immediately after heating the sample in an oven at 180°C for 10 minutes, it was measured according to JIS-P-811 Gr paper tear strength test method.

Flame retardancy: The carbonized layer was measured according to JIS-Z-215Or "Flame retardant test for thin materials" (45° Mezkel burner method).

In Examples 1 to 4, each flame retardant composition maintained the softness of the paper after treatment. On the other hand, in Comparative Examples 1 to 3, the paper lost its softness and had lower flexibility than the paper before treatment.

Table 1 (Note) Coloring prevention property: O light yellow, △ yellow, × light brown Flame retardancy: Carbonized layer (mm) Coating amount (2) Coating amount (%) in terms of solid content on paper [Effect of the invention The flame retardant composition of the present invention has the same or higher flame retardant performance on paper and the like as conventional compositions (guanidine sulfamate, methylolated guanidine sulfamate, etc.), and is particularly easier to apply to paper than conventional compositions. It has further improved coloration prevention properties and tear strength when heated.

In addition, when applying flame retardants to paper, etc., stiffness
Although conventional flame retardants have not been sufficient, the composition of the present invention is also excellent in this respect.

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

Since it has the above effects, the flame retardant composition of the present invention is useful as a flame retardant for paper, cloth, wood, building materials, and the like.

Procedural Amendment Statement March B, 1990 Patent Application No. 152172, 1990 Name of Invention Flame Retardant Composition Person Who Amends Relationship to the Case Patent Applicant Address 11 Hashino Honmachi, Higashiyama Ward, Kyoto City Date: August 28, 1990 (shipment date) Number of inventions increased by the amendment 0 Contents of the amendment on page 12 of the seed box of the “Detailed Description of the Invention” of the specification subject to the amendment

Claims (1)

[Claims] 1. It is characterized by containing as an active ingredient a product (4) obtained by reacting an alkylene oxide (3) with a mixture of an ammonium salt of an inorganic acid (1) and a dicyandiamide (2) in the presence of water. flame retardant composition.