JPH0286695A - Flameproofing agent composition - Google Patents

Abstract

PURPOSE:To provide a flameproofing agent composition which has excellent flame retardancy and, when applied to, especially, paper, can part thereto excellent discoloration resistance upon being heated and tearing strength, etc., by mixing a specified dicyandiamide derivative as an effective component. CONSTITUTION:An ammonium salt of an acid (e.g., ammonium sulfamate) is reacted with a dicyandiamide (e.g., dicyandiamide). The product is reacted with an alkylene oxide (e.g., ethylene oxide), and the product is further reacted with formaldehyde. The order of the reaction with the alkylene oxide and formaldehyde may be reversed. The obtained reaction product is used as an effective component, and a well-known flameproofing agent such as methylolated guanidine sulfamate is added to it to produce a flameproofing agent composition.

Description

[Detailed description of the invention] [Industrial application fields] FIELD OF THE INVENTION This invention relates to flame retardant compositions.

[Prior Art] Conventionally, guanidine sulfamate, methylolated guanidine sulfamate, etc. have been used as flame retardants. (For example, Japanese Patent Application Laid-open No. Sho GO-1!19094).

[Problems to be solved by the invention] However, the quality of this product is not sufficient; for example, when it is applied to paper and heated, the paper tends to become colored, and the tear strength after heating is greatly reduced. There was a point.

[Means for Solving the Problems] The present inventors have determined that the product KT is sufficient, and for example, when applied to paper and heated, the paper's ? In order to obtain a flame retardant composition that is less likely to cause discoloration and has less deterioration in tear strength after aging, the present invention has been arrived at after extensive research.

That is, the present invention provides (1) a reaction product of an ammonium salt of an acid and a dianediamide, (2) an alkylene oxide, and (
3) A flame retardant composition characterized by containing a reaction product with formaldehyde as an active ingredient.

In the present invention, the -[- reaction product may be one obtained by reacting formaldehyde with an alkylene oxide (hereinafter abbreviated as AO) adduct of a reaction product of an ammonium salt of an acid and a dicyandiamide; AO may be added to the formaldehyde reaction product of the reaction product of dicyandiamide and dicyandiamide.

In the present invention, ammonium salts of acids include ammonium sulfamate, ammonium phosphate, ammonium borate, ammonium sulfate, ammonium polyphosphate, and mixtures of two or more thereof.

Among these, ammonium sulfamate is preferred.

Examples of dicyandiamides include dicyandiamide, monomethylol dicyandiamide, dimethylol dicyandiamide, and mixtures of two or more thereof.

Preferred is dicyandiamide.

In the reaction product of dicyandiamide and ammonium salt of acid, the molar ratio of dicyandiamide and ammonium salt of acid is usually 1:1 to 1:3, preferably I:1.4 to I
: I, 8. When the number of acid ammonium salts is less than 1, the content of water-insoluble substances such as melamine and ammeline increases. Furthermore, when the number of acid ammonium salts exceeds 3, the amount of unreacted acid ammonium salts (ammonium sulfamate, etc.) and accessory ammonium (guanidine ammonium imidodisulfonate, etc.) increases, and these reactants, alkylene oxide, and formaldehyde The thermal stability of cellulose-based materials treated with the reaction products of is reduced, and the tendency of coloring increases due to high temperature treatment, giving the product fatal drawbacks.

The reaction can be carried out in a melt reaction. The reaction temperature is usually 1
The temperature is 20 to 200°C, preferably 130 to 189°C.

In addition to the guanidine salt of the acid which is the main product, this reaction product may also contain a small amount of unreacted ammonium salt of the acid, dicyandiamide, and a small amount of side reaction products such as melamine and ammeline.

In the present invention, alkylene oxide (hereinafter abbreviated as AO)
Examples include AO having 2 to 4 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide, etc., and phenyl or halo substituted products thereof such as styrene oxide, epichlorohydrin, etc. Or two or more types. Preferred are EO and PO.

When using two or more types of AO, the addition format may be block, random, or a mixture of these.

The adduct of AO is usually 0.0% based on the weight of the addition reaction starting materials.
It is 1 to 70%, preferably 1 to 50%. Addition ■ is 0
．． If it is less than 1%, the paper tends to be colored, and if it exceeds 70%, the flame retardant property itself may deteriorate. In addition, the AO content is determined by the formaldehyde reaction product of the AO adduct of the reaction product of an ammonium salt of an acid and a dicyandiamide, or the AO adduct of a formaldehyde reaction product of a reaction product of an ammonium salt of an acid and a dicyandiamide (hereinafter referred to as AO adduct of the reaction product of an ammonium salt of an acid and a dicyandiamide). (referred to as the reaction product in the invention), usually 0.
It is 1 to 50%, preferably 1 to 40%. If the AO content is less than 0.1%, coloring of lit tends to occur. 50
%, the flame retardant property itself may deteriorate.

An AO adduct of a reaction product of an ammonium salt of an acid and a dicyandiamide and an AO adduct of a formaldehyde reaction product of an ammonium salt of an acid and a dicyandiamide can be produced by a conventional method.

For example, a reaction product of an ammonium salt of an acid and a dicyandiamide, or a reaction product of an ammonium salt of an acid and a dicyandiamide, a formaldehyde reaction product, may be added in a molten state, or in water, an organic solvent (ketones, alcohols, etc.). ) as a solvent or dispersion medium, AO is added without a catalyst or in the presence of a basic catalyst (caustic potash, trimethylamine, etc.) or an acid catalyst (boron trifluoride, etc.) under pressure or normal pressure (addition temperature is usually 50-1110 'c1 preferably 100 to +80'C).

Formaldehydes include formalin (a 37% aqueous solution of formaldehyde) and formaldehyde generating substances such as paraformaldehyde. Polmarine is preferred.

The reaction amount of formaldehyde is usually 0.1 to 60%, preferably 0.5 to 50%, based on the weight of the reaction starting materials. When the amount of reaction is less than 0.1%, heat resistance decreases, and 60
%, flame retardant properties may deteriorate.

Further, the content of formaldehyde in the reaction product of the present invention is usually 0.1 to 50%, preferably 0.5 to 45% by weight. Formaldehyde content is 50
%, there is a tendency for flame retardancy to decrease. Furthermore, if the formaldehyde content is less than 0.1%, heat resistance will decrease.

A formaldehyde reaction product of a reaction product of an ammonium salt of an acid and a dicyandiamide and a formaldehyde reaction product of an AO adduct of a reaction product of an ammonium salt of an acid and a dicyandiamide can be produced by a conventional method.

For example, by adding an AO adduct of a reaction product of an ammonium salt of an acid and a dicyandiamide or a reaction product of an ammonium salt of halogen acid and a dicyandiamide to an aqueous formaldehyde solution and reacting it at 30 to 30°C for 1 to 5 hours. can be manufactured.

The reaction products of the present invention include guanidine salts of acids that have neither added AO nor reacted with formaldehyde, ammonium salts of acids, dicyandiamides, and other side effects described in the section of the reaction products of ammonium salts of acids and dicyandiamides. May contain reaction products, these AO
may contain adducts of only formaldehyde or reactants of these only with formaldehyde.

Examples of reaction products in the present invention include a formaldehyde reaction product of an EO adduct of a reaction product of ammonium sulfamate and dicyandiamide (7% EO content, 4% in f7), and a reaction product of ammonium sulfamate and dicyandiamide. Reactant E Formaldehyde reaction product of O adduct (EO content 10%, formaldehyde preposition 2%), Formaldehyde reaction product of PO adduct of reaction product of ammonium sulfamate and dicyandiamide (I゛0 content 1113%, formaldehyde (contains ff1G%), formaldehyde reaction product of the reaction product of ammonium sulfamate and dicyandiamide (EO7PO publication) (contains 1G%),
715%, PO content 3%, formaldehyde content ■4%)
, formaldehyde reaction product of EO・I'01-sized reaction product of ammonium sulfamate and diandiamide (
IEO content: 5%, PO content: 3%, formaldehyde content: 3%). In the above, EO/I'0
The adduct is a random adduct of EO and 1) 0, EO/PO
The adduct indicates a block addition in the order of EOlPO. The same description will be used below.

In addition to the reaction product (A) of the reaction product of an ammonium salt of an acid and a dicyandiamide, and the reaction product of an alkylene oxide and formaldehyde, the composition of the present invention can also contain other known components as necessary.

Examples include known guanidine salt compounds (B) [hydroxyalkyl-substituted guanidine (methylolated guanidine sulfamate, etc.), guanidine salts (guanidine sulfamate, guanidine phosphate, guanidine hypophosphite, guanidine polyphosphate, boric acid guanidine, etc.)
, cyano-substituted guanidine (guanylurea phosphate, guanylurea polyphosphate, etc.), amine-substituted or substituted guanidine salt containing an amino group (aminoguanidine phosphate, etc.)
], ammonium salts (C) of strong acids (ammonium sulfamate, ammonium sulfate, ammonium phosphate, ammonium borate, ammonium polyphosphate, etc.), dicyandiamides (D) (dicyandiamide, methylolated dicyandiamide, etc.), and the like.

The composition of the present invention can be produced by mixing (A), (B), (C), (D), etc., but at the time of producing (A), (Il) (C
) (D) etc. may be present, or (A) may remain unreacted during production.

In the composition of the present invention, the KM content of the reaction product (A) of the reaction product of acid ammonium salt and dicyandiamide and the alkylene oxide and formaldehyde is usually 10% or more, preferably 20% or more based on the weight of the composition. % or more. If IO% is less than i:l:j, sufficient performance may not be obtained.

In the composition of the present invention, the content of (II), (C), and (D) is 1.1, within a range that satisfies the performance as a flame retardant. +i can be selected without limitation, but the content of component (B) is usually 90% or less, preferably 80% or less based on the weight of the composition.

The content of components (C) and (D) is usually 70% or less, preferably 40% or less.

The composition of the present invention is preferably used as an aqueous solution. If it is dissolved, the 1 degree can be changed as needed depending on the purpose of use. It is usually 0.5 to 60%, preferably 1 to 50%.

Examples of substrates to which the composition of the present invention can be used include cellulose-based 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 the composition of the present invention adhered to the substrate is usually 2 to 40%, preferably 3 to 35% in terms of solid weight.

The composition of the present invention may be applied to a substrate by any conventional method, such as a method in which paper is immersed in the composition of the present invention or a water diluted solution thereof and then dried in 1:IZ, or a method in which paper is dried in a size press. There are two methods: applying with a brush, applying with a brush, etc.

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

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

Example 1 84 parts of dicyandiamide and 1 part of ammonium sulfamate
After mixing 94 parts and reacting at 130-170°C for 3 hours, 22 parts of E0 was added under pressure and reacting at 110-150°C for 6 hours to obtain an EO adduct.

Add 184 parts of water and 41 parts of formalin to this,
A flame retardant composition having a solid content of about 60% was obtained (EO content: k7, g%, formaldehyde content 4.8%).

Example 2 A flame retardant X compound was obtained by carrying out the same procedure as in Example 1 except that POIO parts were used instead of E022 parts (PO content 3.3%, formaldehyde content 5.0%).
Example 3 84 parts of dicyandiamide and 719 parts of ammonium sulfamate
The 4 parts were mixed and reacted for 3117 hours at 130-+70"C.

Add 184 parts of water and 41 parts of formalin to this
The reaction was stirred at 0 to 60°C for 2 hours. Later on EO22
Add the parts under pressure! The reaction was carried out at JO~+30'C for 6 hours to obtain a flame retardant composition with a solid content of about 60% (1 buff containing EO, 0%, formaldehyde content 4.8%).

Example 4 A flame retardant composition was obtained by carrying out the same procedure as in Example 1 except that 7194 parts of ammonium sulfamate was changed to 137 parts, 22 parts of E0 to 30 parts, and 41 parts of formalin to 20 parts. Contains m11.6% and formaldehyde content 2.9%).

Example 5 A flame retardant composition was obtained in the same manner as in Example 1 except that 7194 parts of ammonium sulfamate was changed to 228 parts, 22 parts of EO was changed to 30 parts, and 41 parts of formalin was changed to 60 parts (EO Content 8.2%, formaldehyde content G,
1%).

Comparative Example 1 84 parts of dicyandiamide and 719 parts of ammonium sulfamate
4 parts were mixed and reacted at 130-170°C for 311, ν.

417 parts of water was added to this to obtain a liquid flame retardant composition.

Comparative Example 2 84 parts of dicyandiamide and 719 parts of ammonium sulfamate
4 parts were mixed and reacted for 3 hours at +30-170°C.

Next, in a system of 147 parts of water and 100 parts of formalin,
Add the above reactants and react at 40-60″C for 2 hours,
A liquid flame retardant composition was obtained.

Comparative Example 3 A liquid flame retardant composition was prepared in the same manner as in Comparative Example 1, except that 7194 parts of ammonium sulfamate was changed to 137 r:+< and 417 parts of water was changed to JIEG part.

Test Example 1 Using the flame retardant compositions of Examples 1 to 5 and Comparative Examples 1 to 3, paper was treated with the treatment liquid by the size press method to
After drying with an auto dryer controlled at 105°C, performance was evaluated using the following method. The results are shown in Table-1.

Anti-coloring property: 180"CX1 was heated in the oven for 0 minutes and compared with 1.5 degrees of irt color.

Tear strength: After heating the sample in an oven at 180°C for 10 minutes, it was measured according to the JIS-1'-8116r paper tear strength test method.

Flame retardancy: The carbonization length was measured according to JIS-Z-215Or "Low Monthly Flame Retardant Test" (45° Metschel burner method).

Table-1 ○: pale yellow, Δ: yellow, ×: pale 18 colors Flame retardancy: Carbonization length (mm) This product has further improved anti-coloring properties and tear strength when applied to paper and heated.

Furthermore, when applied to paper, a material with soft stiffness is desired. Conventional flame retardants have not been sufficient, but the composition of the present invention is also superior 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.

Because it has the above effects, the composition of the present invention can be used for paper, cloth,
It is effective for many uses, including water conservancy and various construction paulownia wood products.

Claims (1)

[Claims] 1. A flame retardant composition containing as active ingredients (1) a reaction product of an ammonium salt of an acid and a dicyandiamide, (2) a reaction product of an alkylene oxide, and (3) formaldehyde.