JPH10310772A - Flame-retardant composition for paper - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a flame-retardant composition for paper excellent in heat stability in processing paper, good in flame retardant properties and capable of giving flame-retardant paper which releases a slight amount of formaldehyde. SOLUTION: This flame-retardant composition for paper comprises (A) a mixture of a guanidine salt with a condensate of the guanidine salt with an aldehyde as effective ingredients and comprises 100 pts.wt. of the ingredient A and 1-20 pts.wt. of one or more of compounds selected from (B) urea compounds, (C) hydrazine compounds and (D) compounds having a triazine skeleton, and releases a slight amount of formaldehyde.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame retardant composition for paper, and more particularly to a flame retardant composition having excellent properties such as excellent flame retardancy and heat resistance when applied to paper, and further having a very low formaldehyde emission. The present invention relates to a paper flame retardant composition from which paper can be obtained.

[0002]

2. Description of the Related Art Conventionally, a base such as ammonia, guanidine or guanylurea and a base such as sulfamic acid, sulfuric acid or phosphoric acid have been used as flame retardants for cellulosic products made of cellulosic materials for wallpaper. Salts with acids have been used. Such a flame retardant was able to impart considerable flame retardancy to the cellulosic material. However, cellulose products processed using the above flame retardants generally have the drawback of poor paper strength retention and thermal discoloration prevention.

[0003] For example, wallpaper or other similar cellulosic materials are coated with a sol coating of a resin such as a vinyl chloride resin, dried, and then dried, for example, to a thickness of about 200 to 21.
The gelation and foaming treatment is performed by heating at 5 ° C. for about 2 to 3 minutes, and the base paper (base paper) treated with the flame retardant during such heat treatment may cause thermal discoloration or decrease in paper strength. There were problems such as coming.

Therefore, in order to impart excellent thermal stability to a cellulose product while maintaining the inherent flame retardancy of the above-mentioned flame retardant, the above-mentioned guanidine salt is used as a flame retardant, and an additive is added thereto. Various blended compositions have been proposed.

For example, Japanese Patent Publication No. 52-25448 discloses (1) ammonium sulfamate, (2) guanidine sulfamate, and (3) dicyandiamide,
There has been proposed a paper flame retardant which essentially comprises three components consisting of at least one organic nitrogen-containing compound among methylolated dicyandiamide and hexamethylenetetramine. JP-A-53-125395 discloses a melamine-based reaction product selected from the group consisting of a main component amount of guanidine sulfamate, a melamine-formaldehyde-based reaction product and a melamine-formaldehyde-alcohol-based reaction product. A flame retardant for cellulosic materials containing at least one kind of thermal discoloration preventing amount as an active ingredient has been proposed. Japanese Patent Application Laid-Open No. 56-1170 discloses a guanidine sulfamate as a main component, a urea-formaldehyde-alcohol-based reaction product, and a urea-formaldehyde-based reaction product having a methylolation rate of about 20% or more. There has been proposed a flame retardant for a cellulosic material containing as an active ingredient at least one kind of thermal discoloration preventing amount of a selected urea-based reaction product. The flame retardants or flame retardants of the above-mentioned are almost satisfactory in terms of thermal stability, but all have a large amount of residual formaldehyde, for example, when coated on paper and dried by heating, the residual formaldehyde is reduced. There was a problem that the work environment deteriorated due to scattering in the atmosphere.

The following has been proposed as a method for reducing the above-mentioned residual formaldehyde. In JP-A-2-70792, a reaction product of ammonium sulfamate and dicyandiamide is reacted with formaldehyde to give a sulfite of an alkali metal, an alkaline earth metal or ammonia, or a guanidine salt of sulfurous acid and a weak acid. A method for producing a flame retardant having a low residual formaldehyde content, characterized by reacting a compound selected from the group consisting of: However, recently, formaldehyde emitted from wallpaper or the like has been taken up as a household indoor pollutant, and is becoming a social problem.
As a wallpaper standard, JIS A 6921 regulates the amount of formaldehyde emission to 1 mg / liter or less.
It is necessary to reduce the release amount as much as possible to 5/10. In order to reduce the formaldehyde emission of wallpaper processed using the flame retardant obtained by the above-mentioned production method to 1 mg / l or less, it is necessary to use a large amount of sulfite or the like, whereby the flame retardant effect is sufficiently increased. However, there remain problems such as that the paper cannot be obtained, the paper quality becomes hard, and the strength is significantly reduced.

For the purpose of improving the anti-coloring property (heat resistance) when applied to paper and heated, the following has been proposed. That is, JP-A-1-98692 discloses that guanidine sulfamate, methylolated guanidine sulfamate and a urea compound are used, and the weight ratio of the total of guanidine sulfamate and methylolated guanidine sulfamate to the urea compound is 4: 1. ~ 2.5: 1
Is proposed as a flame retardant composition for paper, fiber or building materials. However, in the above flame retardant composition, since the urea compound is used in an amount of 25 to 40 parts by weight based on a total of 100 parts by weight of guanidine sulfamate and methylolated guanidine sulfamate, the flame retardant effect is reduced. However, there is a problem that the paper quality is deteriorated. Further, the flame retardant composition is not intended to suppress the emission of formaldehyde.

Accordingly, an object of the present invention is to provide a paper flame retardant composition which can provide a flame retardant paper which is excellent in thermal stability when processed into paper, has good flame retardancy, and emits very little formaldehyde. To provide.

[0009]

As a result of various studies, the present inventors have found that a guanidine salt having flame retardancy and a mixture of a condensate of a guanidine salt and an aldehyde are used as active ingredients, and urea compounds, hydrazide It has been found that a flame retardant composition containing a specific amount of a compound or a compound having a triazine skeleton can achieve the above object.

The present invention has been made based on the above findings, and is a flame retardant composition containing (A) a guanidine salt and a mixture of a condensate of a guanidine salt and an aldehyde as an active ingredient, and (B) a urea composition. 1 to 20 parts by weight of at least one compound selected from the group consisting of a class compound, a (C) hydraside compound and a (D) compound having a triazine skeleton based on 100 parts by weight of the component (A). It is intended to provide a paper flame retardant composition having a very small amount of formaldehyde emission.

[0011]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the flame retardant composition for paper of the present invention will be described in detail. The paper flame retardant composition of the present invention contains (A) a guanidine salt and a mixture of a condensate of a guanidine salt and an aldehyde as active ingredients, (B) a urea compound, (C) a hydraside compound, and (D) One or more compounds selected from the group consisting of compounds having a triazine skeleton are added in an amount of 1 to 100 parts by weight of the component (A).
To 20 parts by weight.

The guanidine salt in the mixture as the component (A) (active ingredient) used in the composition of the present invention is used as a flame retardant (flame retardant) having flame retardancy (flame retardancy) per se. It is something that can be done. Examples of the guanidine salt include:
It is not particularly limited as long as it has a function as a flame retardant,
For example, a reaction mixture of dicyandiamide and one or more ammonium salts selected from the group consisting of ammonium sulfamate, ammonium sulfate and ammonium phosphate, guanidine sulfamate, guanidine sulfate, guanidine phosphate, and the like, among which dicyandiamide And at least one ammonium salt selected from the group consisting of ammonium sulfamate and ammonium sulfate, and one or more guanidine salts selected from the group consisting of guanidine sulfamate and guanidine sulfate. Further, among these guanidine salts, guanidine sulfamate and guanidine sulfate are preferred in terms of excellent paper strength retention when processed into paper and in that a composition as a highly concentrated aqueous solution can be prepared, and particularly sulfamic acid. Guanidine is preferred.

When the reaction mixture is used as the guanidine salt, even if a small amount of unreacted substances or reaction by-products is present, the composition of the present invention has no particularly bad influence. The concentration of the pure guanidine salt in the reaction mixture is preferably at least 90% by weight, more preferably at least 95% by weight.

Further, as the guanidine salt, an unreacted raw material (guanidine salt) for preparing a condensate of a guanidine salt and an aldehyde described later can be used as it is.

Further, (A) used in the composition of the present invention
Examples and preferred examples of the guanidine salt forming a condensate of the guanidine salt and the aldehyde in the mixture as the component (active ingredient) include the same as the above-mentioned guanidine salt, and also form the condensate. Examples of the aldehyde include, for example, formaldehyde (formalin), acetaldehyde, glyoxal and the like, and particularly preferred is formaldehyde (formalin). In the present specification, “formaldehyde release amount”, “formaldehyde scavenger component” (described below), and the like refer to all the above-mentioned aldehydes representing formaldehyde, and are not limited to formaldehyde. .

Examples of the condensate of a guanidine salt and an aldehyde include a methylolated guanidine salt which is a condensate of a guanidine salt and formaldehyde (formalin).

The condensate of the guanidine salt and the aldehyde is not particularly limited in its production method. In a conventionally known method, for example, a method of reacting a guanidine salt with formalin in an aqueous solution, the pH of the reaction system is adjusted to 7 to 10. Keep at 9 and temperature 4
It can be obtained by a method of reacting at 0 to 90 ° C. for 1 to 5 hours. In this case, a mixture of a guanidine salt and a condensate of an aldehyde and an aldehyde [(A) component) is obtained by reacting formalin, preferably in a usage ratio of 0.1 to 0.8 mol, with respect to 1 mol of the guanidine salt. ]
Can be prepared. As used herein, the term "condensate of a guanidine salt and an aldehyde" refers to a condensate of a pure guanidine salt and an aldehyde obtained by a condensation reaction of a guanidine salt and an aldehyde. Means no unreacted substances or reaction by-products.

Here, the weight ratio of the content of the guanidine salt and the condensate of the guanidine salt and the aldehyde in the mixture as the component (A) used as the active ingredient of the composition of the present invention ( The former / the latter) is preferably 9/1
To 2/8, and more preferably 8/2 to 5/5. When the proportion of the guanidine salt is increased, the heat resistance may be insufficient.On the other hand, when the proportion of the condensate of the guanidine salt and the aldehyde is increased, the flame retardancy may be reduced. It is preferable that

One or more compounds selected from the group consisting of (B) urea compounds, (C) hydraside compounds and (D) compounds having a triazine skeleton used in the composition of the present invention are the above-mentioned active ingredients. It is used as an additive component to the component (A), and has a function of trapping residual formaldehyde in the composition of the present invention and suppressing the amount of formaldehyde emission when processed into paper to be extremely small (hereinafter referred to as “formaldehyde”). , These additive components are also collectively referred to as “formaldehyde scavenger components”).

Examples of the urea compound as the component (B) include urea, thiourea, guanylurea, guanylthiourea, and dimers thereof (buret and the like). Among them, formaldehyde is preferred. Urea is preferred in that the release inhibitory effect is even greater.

Examples of the hydrazide compound as the component (C) include, for example, hydrazide compounds of straight-chain fatty acids having 0 to 6 carbon atoms, such as carbohydrazide, succinic dihydrazide and adipic dihydrazide. No. Among these, carbohydrazide and adipic dihydrazide are preferable, and carbohydrazide is particularly preferable, in that the formaldehyde release suppressing effect and the thermal stability effect are even greater.

Examples of the compound having a triazine skeleton as the component (D) include melamine and guanylmelamine. Of these, melamine is preferable because it has a greater formaldehyde emission inhibitory effect. .

These formaldehyde scavenger components include:
Of the components (B), (C) and (D), only one component may be used, or two or three components may be mixed and used. Further, each component can be used alone or in combination of two or more.

The formaldehyde scavenger component used here is not particularly limited as long as it reacts easily with formaldehyde and its product does not dissociate formaldehyde and is a harmless and stable substance. Those that are easily decomposed by heating and those that are easily decomposed are not used. Further, the properties of the flame retardant, that is, the flame retardancy and thermal stability, and the physical properties of the flame retardant treated paper must not be impaired.

The use ratio of the formaldehyde scavenger component is, as described above, the component (A) [the mixture of the guanidine salt and the condensate of the guanidine salt and the aldehyde].
It is 1 to 20 parts by weight with respect to parts by weight. Here, when the use ratio is less than 1 part by weight, the function as the formaldehyde scavenger component cannot be exhibited, and the effect of the composition of the present invention to suppress formaldehyde emission becomes insufficient. When the use ratio is more than 20 parts by weight, the composition of the present invention has an excellent formaldehyde emission suppressing effect, but the flame retardant (flame preventing) effect is reduced. Many flame retardants need to be deposited, and as a result, the quality of the obtained flame retardant paper deteriorates. Further, such an increase in the use ratio of the flame retardant is not economical. The preferred use ratio of the formaldehyde scavenger component is 5 to 100 parts by weight of the component (A).
10 parts by weight.

In the composition of the present invention, the above-mentioned active ingredient (component (A)) and the above-mentioned formaldehyde scavenger component (components (B), (C) and (D)) are essential components. Amides such as formamide and acrylamide, alkali metal salts or alkaline earth metal salts of sulfamic acid, and the like. By adding these compounds, the effect of the composition of the present invention for suppressing formaldehyde emission can be further improved. These compounds can be used in any amount that does not adversely affect the effects of the present invention.

Further, the composition of the present invention may further contain, if necessary, other additives such as a surfactant, a rust preventive, a sizing agent, a paper strength enhancer, a surface treatment agent, and other paper treatment agents. Can be added. The addition amount of these other additives can be used in any amount that does not adversely affect the effects of the present invention.

The composition of the present invention is characterized in that the formaldehyde scavenger component (a component selected from the group consisting of the components (B), (C) and (D)) is added to the component (A) as the active component. These compounds are used in the above-described proportions, and if necessary, other components are used, and these components are mixed to prepare the above compound.

The content of each component in the composition of the present invention is such that the formaldehyde scavenger component is 1 to 20 parts by weight, preferably 5 to 100 parts by weight of the component (A).
To 10 parts by weight, and other components are preferably 0 to 1 part by weight.
It is 5 parts by weight, more preferably 0 to 7 parts by weight.

The method of preparing the composition of the present invention is not particularly limited, and examples thereof include a method in which the composition is prepared in an aqueous solution. This method is performed by, for example, dissolving a mixture of the above components in water.

When the composition of the present invention is prepared by the above-mentioned method in the state of an aqueous solution, the solid content of the composition of the present invention in the aqueous solution is preferably relatively high.
It is preferably about 60% by weight.

The dosage form when the composition of the present invention is processed into paper is not particularly limited. For example, it is preferably in the form of an aqueous solution, and particularly preferably used as a diluted aqueous solution. In this case, the solid content concentration in the aqueous solution of the composition of the present invention is preferably, for example, 20 to 40% by weight.

Examples of paper processed using the composition of the present invention include various building materials such as wallpaper, shoji paper, bran paper, paperboard, synthetic paper, and roofing paper.

The method of the above-mentioned processing is not particularly limited, and usually, a method of drying using an aqueous solution of the composition of the present invention using any means such as dipping, spraying, spreading, and roll coating is used. The above-mentioned processing is performed, for example, by adding a sizing agent, a paper strength agent, other paper treating agents, and water to the composition of the present invention to form an aqueous flame retardant solution, dipping by a size press, and then drying. Will be The paper processed as described above has a basis weight of usually 60 to 80 g / m ² , good flame retardancy, and extremely low formaldehyde emission.

[0035]

The present invention will be described below in more detail with reference to Examples and Comparative Examples. However, the invention is not limited in any way by these examples. In the following examples, “parts” indicates “parts by weight” and “%” indicates “% by weight” unless otherwise specified.

Examples 1 to 7 As a flame retardant, a mixture prepared in the following Reference Example 1 (a mixture of guanidine sulfamate and methylolated guanidine sulfamate)
Using 100 parts, as an additive, a commercially available compound shown in the following [Table 1] was mixed and used in an amount shown in the following [Table 1], and water was added thereto and dissolved to obtain a solid content of about 20%. A flame retardant aqueous solution was prepared. In this flame retardant aqueous solution, immerse wallpaper base paper (mean size: about 60 g / m ² , A4 size, non-size paper) for 2-3 seconds, squeeze with a size press, and use a rotary drum dryer at a temperature of about 105 ° C. Dried to produce flameproof paper. This flameproofed paper was tested for flame retardancy (flameproofness), thermal stability and formaldehyde emission according to the following [Test Method]. The results are shown in Table 1 below.

The details of the compounds used in the examples and comparative examples are as follows. Sulfamic acid: Guanidine is obtained by heating 84 g of dicyandiamide and 194 g of sulfamic acid and reacting at 155 to 175 ° C. for 3 hours (purity: 90 to 96%).・ Urea; Nissan Chemical Co., Ltd. ・ Carbohydrazide; Otsuka Chemical Co., Ltd. ・ Melamine; Nissan Chemical Co., Ltd.

Reference Example 1 Preparation of a mixture of guanidine sulfamate and methylolated guanidine sulfamate; 15 parts of 37% formalin were added to 100 parts of guanidine sulfamate, and this was dissolved in 60 parts of water. Heat at 80 ° C. for 2 hours to obtain a reaction product having a concentration of about 60% [guanidine sulfamate / methylolated guanidine sulfamate (weight ratio)
= 2/1 mixture].

[Test Method] (1) Flame Retardancy [Limited Adhesion Rate] A plurality of flame-proofed papers are prepared in advance and JIS-Z-2150.
Tested in accordance with “Test method for flame resistance of thin materials (45 ° Meckel burner method)” and passed flame resistance class 2 (carbonization length 10 cm)
Among the processed papers, the adhesion rate (chemical adhesion rate) obtained from the following equation (Formula 1) is the minimum adhesion rate of the processed paper, and the flame retardancy (flame resistance) is determined. evaluated. It should be noted that the smaller the critical adhesion ratio, the better the flame retardancy.

[0040]

(Equation 1)

(2) Thermal stability The flameproofed paper having the critical adhesion rate determined in the above-mentioned marginal adhesion rate test was placed in a hot air circulating drier at 200 ° C. for 5 minutes and at 210 ° C. for 5 minutes. , And the whiteness was measured in accordance with JIS-P-8123 “Hunter whiteness test method for paper and pulp” to evaluate the thermal stability. The smaller the change in hunter whiteness compared to before heating, the better the thermal stability.

(3) Formaldehyde Emission A flameproofed paper having a marginal adhesion rate determined in the above marginal adhesion rate test was measured according to JIS-A-6921 "Formaldehyde emission amount test for wallpaper".

Comparative Example 1 Except that 100 parts of guanidine sulfamate was used as a flame retardant instead of 100 parts of the mixture obtained in Reference Example 1 and no additive was used,
A flameproof paper was produced in the same manner as in Example 1 and tested for flame retardancy, thermal stability and formaldehyde emission. The results are shown in Table 1 below.

Comparative Example 2 Except that no additive was used,
A flameproof paper was produced in the same manner as in Example 1 and tested for flame retardancy, thermal stability and formaldehyde emission. The results are shown in Table 1 below.

[0045]

[Table 1]

From the above results, it is possible to contain the component (A),
The paper flame retardant composition of the present invention (Examples 1 to 7) to which a specific amount of at least one compound selected from the group consisting of the components (B), (C) and (D) is added, Flame-retardant paper which is excellent in the formaldehyde emission suppressing effect of flame-treated paper, and which is processed with the paper flame retardant composition of the present invention, has good flame retardancy and extremely low formaldehyde emission. Is obtained.

[0047]

Industrial Applicability The flame retardant composition for paper of the present invention can provide a flame retardant paper which is excellent in thermal stability when processed into paper, has good flame retardancy, and emits very little formaldehyde. is there.

Claims (6)

[Claims] 1. A flame retardant composition comprising (A) a guanidine salt and a mixture of a condensate of a guanidine salt and an aldehyde as an active ingredient, wherein (B) a urea compound;
It is characterized in that 1 to 20 parts by weight of at least one compound selected from the group consisting of a hydraside compound and a compound having a triazine skeleton is added to 100 parts by weight of the component (A). A flame retardant composition for paper which emits very little formaldehyde. 2. The guanidine salt and the guanidine salt forming the condensate in the mixture as the component (A),
The flame retardant composition for paper according to claim 1, which is a reaction mixture of dicyandiamide and one or more ammonium salts selected from the group consisting of ammonium sulfamate and ammonium sulfate. 3. The guanidine salt and the guanidine salt forming the condensate in the mixture as the component (A),
2. A guanidine salt selected from the group consisting of guanidine sulfamate and guanidine sulfate.
The flame retardant composition for paper according to the above. 4. The urea compound as the component (B),
The flame retardant composition for paper according to any one of claims 1 to 3, which is urea. 5. The flame retardant composition for paper according to claim 1, wherein the hydrazide compound as the component (C) is a carbohydrazide. 6. The flame retardant composition for paper according to claim 1, wherein the compound having a triazine skeleton as the component (D) is melamine.