JPH0450397A - Combustion-proof agent composition - Google Patents

Abstract

PURPOSE:To obtain the subject composition useful for paper, etc., having excellent combustion-proof property, improved coloringinhibiting property and tear strength and soft rigidity comprising ammonium salt of an inorganic acid, dicyandiamides, alkylene oxide and formaldehyde. CONSTITUTION:(A) a mixture of (i) ammonium salt of an inorganic acid and (ii) dicyandiamides is reacted with (iii) alkylene oxide in the presence of water and resultant compound is reacted with (iv) formaldehyde to obtain a reaction product. The aimed composition contains at a least one species selected from the group consisting of a reaction product A, (B) a product derived from reaction of a mixture comprising the component 'i', the component 'ii' and the component 'iv' in the presence of water and further reaction of the resultant compound with the component 'iii' and (C) a product derived from reaction of a mixture comprising the component 'i', the component 'ii' and the component 'iv' is reacted with the component 'iii' in the presence of water as an active ingredient.

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial 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, JP-A-199094).

[Problems to be solved by the invention] However, when this product is applied to paper or the like and heated,
There were problems in that the paper was likely to be 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.

[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 (formed (referred to as craftsmanship):
Ammonium salts of inorganic acids (1), dicyandiamides (
A product obtained by reacting a mixture of 2) and formaldehyde (4) in the presence of water and then reacting with alkylene oxide (3) (referred to as product 2): and an ammonium salt of an inorganic acid (1), dicyandiamide (2) and formaldehyde (4) in the presence of water with alkylene oxide (3) (referred to as product 3) as an active ingredient. This is a characteristic flame retardant composition.

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.

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

In the present invention, the mixing molar ratio of the ammonium salt of an inorganic acid (]) and the dicyandiamide (2) is usually 0.4:I to 2:11, preferably 0.5 in any case of products 1 to 3. :I~1.8:1. If the ammonium salt of an inorganic acid (1) is less than 0.4, the flame retardant property itself may be lowered, and if it exceeds 2, paper etc. are likely to be colored.

In the present invention, alkylene oxide (hereinafter abbreviated as AO) includes 1, for example, ethylene oxide (hereinafter E
AO having 2 to 4 carbon atoms, such as propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide; ), halo-substituted products (eg, epichlorohydrin), and the like. Furthermore, two or more of these may be used in combination. Among these, preferred are EO and PO. In any case of products 1 to 3, when an adduct of two or more types of AO is used, the addition form may be block, random, or a mixture thereof.

In any case of Products 1 to 3, the amount of AO added is usually 0.1 to 70%, preferably 0.1 to 70%, based on the total weight of the inorganic acid ammonium salt (1) and the dicyandiamide (2). It is 0.5-50%. If the amount added is less than 0.1%, paper or the like is likely to be colored, and if it exceeds 70%, the flame retardant property itself may deteriorate.

Further, the amount of AO added is usually 0.1 to 50%, preferably 0.5 to 40%, based on the weight of each of the products 1 to 3 in terms of solid content. If it is less than 0.1%, paper, etc., is likely to be colored, and if it exceeds 50%, the flame retardant property itself may deteriorate.

In the present invention, as the formaldehyde (4), formalin (for example, a 37% aqueous solution of formaldehyde) or a formaldehyde generating substance (for example, rose formaldehyde), preferably formalin, may be used.

In each of the products 1 to 3, the amount of formaldehyde (4) constituting the product is equal to the amount of ammonium of the inorganic acid! (
Based on the total weight of 1) and dicyandiamide (2), it is usually 0.1 to 60% in terms of solid content, preferably 0.5%.
~50%. If this amount is less than 0.1%, paper or the like is likely to be colored, and if it exceeds 60%, the flame retardant property itself may deteriorate. Also, formaldehyde (
The amount of 4) is usually 0.1 to 50%, preferably 0.5%, based on the solid content weight of each of the products 1 to 3.
~45%. If this amount is less than 0.1%, paper or the like is likely to be colored, and if it exceeds 50%, the flame retardant property itself may deteriorate.

In any case of Products 1 to 3, the amount of water when reacting in the presence of water (However, in the case of Products 2 or 3, when using a formaldehyde aqueous solution,
The amount including the amount of water in this aqueous solution is the amount of the products 1 to 3.
It is usually 5 to 95%, preferably 20 to 80%, based on the weight of each solid content. If the amount of water is not 5%, each component of the raw material may not be dissolved or dispersed.
If it exceeds %, the reaction will be slow.

Examples of methods for producing the products 1 to 3 are as follows.

The method for producing the product 1 includes adding water and, if necessary, an organic solvent (ketones, alcohols, etc.) to a mixture of an inorganic acid ammonium salt (1) and a dicyandiamide (2) as a solvent or dispersion medium. AO is reacted without a catalyst or in the presence of a basic catalyst (potassium hydroxide, trimethylamine, etc.) or an acid catalyst (boron trifluoride, etc.) under elevated pressure or normal pressure.

The reaction temperature is usually 40 to 130°C, preferably 60°C.
Perform at ~120°C. (At temperatures below 40°C, the reaction progresses slowly; at temperatures above 130°C, a 1ir1 reaction occurs and water-insoluble substances may be produced.) Next, this reaction product is dissolved in an aqueous solution of formaldehyde (4). Usually 30
The product 1 can be produced by reacting at ~90°C for 1 to 5 hours.

As a method for producing the product 2, for example, an ammonium salt of an inorganic acid (1) is added to an aqueous solution of formaldehyde (4).
and dicyandiamide (2), usually at 30-90°C.
The product 2 can be produced by reacting for 1 to 5 hours and then adding AO to this reaction product in a similar manner to the production of the product 1.

Further, as a method for producing the product 3, for example, to a mixture of an aqueous solution of formaldehyde (4), an ammonium salt of an inorganic acid (1) and a dicyandiamide (2),
Using water, organic solvents (ketones, alcohols, etc.) as a solvent or dispersion medium, AO is applied without a catalyst or in the presence of a base catalyst (caustic potash, trimethylamine, etc.) or an acid catalyst (boron trifluoride, etc.) under pressure or under normal conditions. The product 3 can be produced by reacting under pressure.

The reaction temperature is usually 40 to 130°C, preferably 80°C.
Perform at ~120°C. (At temperatures below 40°C, the reaction progresses slowly; at temperatures above 130°C, side reactions may occur and water-insoluble substances may be produced.) Each of the products 1 to 3 of the present invention contains AO Ammonium salts of inorganic acids (1) and dicyandiamides (2) that have not reacted with either formaldehyde or formaldehyde (4).
), may contain these AO-only reactants and/or these formaldehyde-only reactants.

Examples of the products 1 according to the invention include the formaldehyde reactant of the EO reactant of a mixture of ammonium sulfamate and dicyandiamide, the formaldehyde reactant of the PO reactant of a mixture of ammonium sulfamate and dicyandiamide, the formaldehyde reactant of the PO reactant of a mixture of ammonium sulfamate and dicyandiamide, Examples include a formaldehyde reaction product of an EO/PO reaction product of a mixture with dicyandiamide, a formaldehyde reaction product of an EO/PO reaction product of a mixture of ammonium sulfamate and dicyandiamide, and the like. (As stated above, the EO/PO reactant refers to a random adduct of Eo, l!:PO, and the EO@PO reactant refers to a block addition of EO and PO in the order. The same description will be used hereinafter. ) Also, as examples of the products 2 and 3, the above product 1
Although the combination is the same as each component constituting the product, the manufacturing method may be one obtained based on the manufacturing method of each product.

The content of each of the products 1 to 3 in each composition of the present invention is usually 10% or more, preferably 20% or more, based on the weight of each composition. If it is less than 10%, sufficient flameproof performance may not be obtained.

In addition to each of the products 1 to 3, each composition of the present invention can also contain components such as other known flame retardants, if necessary. Examples of this include guanidine salt compounds (
Hydroxyalkyl-substituted guanidine (-methylolated guanidine sulfamate, etc.), guanidine salts (guanidine sulfamate, guanidine phosphate, guanidine hypophosphite, guanidine polyphosphate, guanidine borate, etc.), cyano-substituted guanidine (guanidine sulfamate, guanidine sulfamate, etc.) guanylurea phosphate, guanylurea polyphosphate, etc.), amino-substituted or amino group-containing substituted guanidine salts (aminoguanidine sulfamate, aminganidine phosphate, etc.); sulfamate-based compounds (magnesium sulfamate, etc.); melamines (
melamine, ammeline, etc.).

When these components such as known flame retardants are included in the composition of the present invention, these components are mixed with each of Products 1 to 3, or these components are added at the time of manufacturing each of Products 1 to 3. may coexist.

In each 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. In this case, it is usually 90% or less, based on the weight of each composition. Also,
In the case of the above-mentioned melamines, it is usually 70% or less.

Each composition of the present invention is preferably used as an aqueous solution, and its 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.

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

The amount of each 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 method of applying each composition of the present invention to a substrate may be a conventional method, such as a method of soaking paper in the composition of the present invention or a water diluted solution thereof and drying it, or using a size press. There are methods such as applying it, applying it with a brush, etc.

Furthermore, each composition of the present invention can be used in combination with a sizing agent, starch, a surface treatment agent such as polyvinyl alcohol, and other paper treatment agents.

[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, 81 parts of formalin, and 106 parts of water were mixed,
The reaction was carried out at 0°C for 3 hours. 18 parts of EO was gradually added to this under pressure and reacted at 80 to 100°C for 5 hours.
A liquid flame retardant composition was obtained. The solid content was [io, 1% (EO content 17.7%, formaldehyde content 1
2.8%).

Production Example 2 137 parts of ammonium sulfamate, 84 parts of dicyandiamide, and 112 parts of water were mixed, and 8013 parts were gradually added to the mixture under pressure, followed by reaction at 80 to 100°C for 5 hours. 114 parts of formalin was added to this mixture and reacted at 70°C for 3 hours to obtain a liquid flame retardant composition. The solids content was 80.0% (EO content 4.7%, formaldehyde content 15.2%).

Production Example 3 91 parts of ammonium sulfamate, 84 parts of dicyandiamide, and 94 parts of water were mixed, and 12 parts of P0 was gradually added to the mixture under pressure, followed by reaction at 80 to 100°C for 5 hours. 81 parts of formalin was added to this and reacted at 70°C for 3 hours to obtain a liquid flame retardant composition. Solid content is 60.
0% (PO content 5.5%, formaldehyde content 13.8%).

Production Example 4 103 parts of ammonium sulfamate, 84 parts of dicyandiamide, 41 parts of formalin, and 121 parts of water were mixed, and 18 parts of EO was gradually added to the mixture under pressure to give a mixture of 80 to 10 parts.
The mixture was reacted at 0° C. for 5 hours to obtain a liquid flame retardant composition. The solids content was 60.3% (EO content 8.2%, formaldehyde content 6.8%).

Comparative Production Example 1 194 parts of ammonium sulfamate and 84 parts of dicyandiamide 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 The flame retardant compositions of Production Examples 1 to 4 and Comparative Production Examples 1 to 3 were used to treat paper with the treatment liquid by a size press method.
After drying with an auto dryer whose temperature was controlled at 0 to 105°C, performance was evaluated using the following method.

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 correspondingly displayed.

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-8116 "Tear strength test method for paper".

Flame retardancy: Carbonization length was measured according to JIS-Z-215Or "Flame retardant test of 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 1) Discoloration prevention property: O light yellow, Δ yellow, x light brown 2) Flame retardancy: Charring length (mm) 3) Coating amount 2 Coating amount in terms of solid content (%) [Invention Effects of the present invention The flame retardant composition of the present invention has flame retardant performance on paper, etc. that is equal to or higher than that of conventional compositions (for example, those containing guanidine sulfamate or methylolated guanidine sulfamate), and is superior to conventional compositions. In particular, the coloring prevention property and tear strength when applied to paper and heated are further improved.

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 easy to dissolve and has good compatibility with other processing agents such as sizing agents and binders (starch, polyvinyl alcohol), resulting in fast dissolution and good workability.

Since the flame retardant composition of the present invention exhibits the above effects,
It is useful as a flame retardant for various products such as paper, cloth, wood, and building materials.

Procedural Amendment September 6, 1990 Patent Application No. 152171 of 1990 Name of Invention Flame Retardant Composition Amendment to the Case Patent Applicant Address 11 Hashinohonmachi, Higashiyama Ward, Kyoto City Date: August 28, 1990 (shipment date) Number of inventions increased by the amendment 0 Contents of the amendment on page 16 of the seed box of “Detailed Description of the Invention” of the specification subject to the amendment

Claims (1)

[Claims] 1. Add alkylene oxide (
3) and formaldehyde (4) (referred to as product 1); a mixture of an inorganic acid ammonium salt (1), dicyandiamides (2) and formaldehyde (4) in the presence of water. and a mixture of ammonium salts of inorganic acids (1), dicyandiamides (2) and formaldehyde (4). A flame retardant composition containing as an active ingredient at least one selected from the group consisting of products (referred to as product 3) formed by reacting alkylene oxide (3) in the presence of water.