JPS6025475B2 - Flame retardant for cellulose materials and treatment method - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to cellulose materials, particularly cellulose containing cellulose, such as wallpaper, fusuma paper, shoji paper, wall cloth, and various other paper materials or cloths for interior decoration, furniture, and building materials. The present invention relates to a flame retardant for cellulosic materials and a treatment method that can be preferably used for flame retardant treatment of cellulosic materials.

More specifically, it is an excellent heat-resistant material useful for providing a flame-retardant cellulosic material that combines excellent thermal discoloration resistance with desirable properties such as flame retardancy, bending resistance, and resistance to scratching. Regarding flame retardants having flame retardant properties, in particular, di- to tetra-methylol melamine and mono- to di-methylol-di- to tri- A component selected from the group consisting of methoxymethylmelamine or a substantially water-soluble melamine-formaldehyde reaction product containing these as a main component, and a melamine-based reaction product selected from a melamine-formaldehyde-alcohol reaction product. It relates to a flame retardant for nitrocellulose materials, characterized in that it contains about 0.1 parts by weight or more of at least one of the following as an active ingredient, and is free of ammonium sulfamate.

Furthermore, the present invention provides a main component amount of guanidine sulfamate, di- to tetra-methylolmelamine and mono-
Components selected from the group consisting of methylol-di- or tri-toxymethylmelamine, or substantially water-soluble melamine-formaldehyde reaction products and melamine-formaldehyde-alcohol reaction products containing these as main components. Cellulose with at least one kind of melamine-based reaction product selected from the above, in an amount of about 0.1 part by weight or more of the melamine-based reaction product based on 10 parts by weight of guanidine sulfamate as the main component. The present invention relates to a flame retardant treatment method for cellulosic materials, characterized in that the materials are treated simultaneously, or either one and then the other, and the materials are not treated with ammonium sulfamate. Conventionally, guanidine sulfamate has been known as a flame retardant for cellulosic materials and has been put to practical use.

The guanidine sulfamate treated product has flame retardant properties,
Not only does it have favorable properties in terms of bending durability and tear resistance, but it also has better thermal discoloration prevention than ammonium salt-based flame retardants such as ammonium phosphate, ammonium sulfate, and ammonium sulfamate. have sex. however,
Its thermal discoloration prevention properties are not fully satisfactory, and guanidine sulfamate, which is industrially produced by the melt reaction of dicyandiamide and ammonium sulfamate, is free from unreacted ammonium sulfamate and by-product impurities that may be contained in the product. However, they often still exhibit unsatisfactory anti-thermal discoloration properties. In order to overcome these disadvantages, it is difficult to obtain satisfactory high purity guanidine sulfamate by removing these reactive products and by-products, and there are difficulties in terms of operation and cost. Improved heat discoloration prevention that avoids heat discoloration and has excellent heat discoloration prevention properties, and does not adversely affect the preferable flame retardant properties, bending durability, tear resistance, etc. of the guanidine sulfamate treated product. It is desired to provide a flame retardant for cellulosic materials that exhibits excellent flame retardant properties. In particular, wallpaper and similar cellulose-based materials are often used by coating their surfaces with a resin such as vinyl chloride resin, and this coating process involves heating at approximately 150 to 200 qC, making them an excellent material. There is an even stronger demand for a flame retardant for cellulosic materials that has thermal discoloration prevention properties as well as other properties and is suitable as a flame retardant. The present inventors have conducted research to provide a flame retardant for cellulosic materials that can satisfy such demands.

As a result, it was discovered that the thermal discoloration prevention property was significantly improved by using guanine sulfamate and the melamine-based reaction product in combination. Although these melamine-based reaction products alone do not exhibit properties that can be used as a flame retardant, when combined with a small amount of melamine-based reaction products, guanidine sulfamate has other desirable properties as a flame retardant. The reason for overcoming the disadvantages in heat discoloration prevention and exhibiting significantly improved heat discoloration prevention without causing any adverse effects is as follows:
Although unknown, this was a completely unexpected and surprising result, as will be explained later with reference to the accompanying drawings. Therefore, the object of the present invention is to provide a flame retardant for cellulosic materials that has excellent thermal discoloration prevention properties together with favorable properties such as flame retardancy, bending resistance, and tear resistance, and has excellent flame retardant suitability. To provide a flame treatment method.

The above objects and many other objects and advantages of the present invention include:
This will become clearer from the description below.

The flame retardant for cellulosic materials of the present invention contains di- to tetra-methylolmelamine and mono- to di-methylol-di- to tri-methoxymethylmelamine based on 100 parts by weight of guanidine sulfamate as the main component. at least a melamine-formaldehyde-based reaction product selected from the group consisting of a component selected from the group consisting of a substantially water-soluble melamine-formalhyde-based reaction product based on these components, and a melamine-formaldehyde-alcohol-based reaction product. Contains about 0.1 part by weight or more of one kind as an active ingredient,
It is characterized by not adding ammonium sulfamate.

The amount of the melamine-based reaction product used may be an amount that prevents thermal discoloration, and is usually at most about 3 parts by weight or less, based on 100 parts by weight of guanidine sulfamate. Usually about 0 parts by weight of guanidine sulfamate.
．． 1 part by weight or more, for example about 0.1 to about 3 parts by weight, more preferably about 0.3 to about 2.5 parts by weight,
In particular, it is a small amount of about 0.5 to 2.5 parts by weight. When a cellulosic material is treated with guanidine sulfamate alone, the physical properties of the material include, for example, the above-mentioned bending durability,
The use of melamine-based reaction products in amounts in excess of thermochromic protection levels that would substantially alter tear resistance and the like should be avoided. The use of melamine-based reaction products in excess of the amount that prevents thermal discoloration will adversely affect the fold resistance, tear resistance, and other desirable properties of guanidine sulfamate-treated cellulosic materials, as well as their excellent flame retardant properties. It is used in an amount that prevents thermal discoloration without causing such adverse effects. Therefore, as long as it does not adversely affect the bending durability and tear resistance, it is of course possible to use the resin in amounts exceeding the above-mentioned range.

The melamine-based reaction product used in the present invention can be produced by a method known per se.

The melamine-based reaction product used in the present invention is, for example, a mixture of melamine and formaldehyde under neutral to weakly alkaline conditions, preferably at a pH of about 8 to about 10, at about 50°C to about 100°C. and/or methylolated melamine derived from, for example, melamine and formaldehyde, and alcohols, preferably lower alcohols, under weakly acidic conditions, e.g. at a pH of about 4. Examples include melamine-formaldehyde-alcohol reaction products that can be easily produced by etherification reaction under conditions of 5 to about 5, for example, at the reflux temperature of the alcohol used. Further, pH adjustment can be carried out using, for example, acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and hakamaic acid; and alkalis such as sodium hydroxide, sodium carbonate, and guanidine carbonate. The above-mentioned lamin-formaldehyde-alcohol reaction product can be formed by adding alcohol at any point in the melamine-formaldehyde reaction product formation reaction and adjusting the pH. The reaction product may be obtained using any of the well-known variations. As is well known, these reaction products are usually obtained in the form of mixtures with various degrees of methylolation, etherification, and/or condensation. is common and can be used as a melamine-based reaction product in the present invention. Moreover, these levels or degrees can be changed as appropriate by selecting the pH conditions as exemplified above, or reaction conditions such as reaction temperature, reaction time, and vehicle medium. In the present invention, it is preferable to use a reaction product that does not become substantially nonflammable in water or other solvents depending on the degree of condensation or etherification, such as water-soluble methylolmelamine, melamine-formaldehyde initial condensate, etc. Commonly known melamine-formaldehyde-based reaction products that are substantially soluble in water and methylolated melamine etherified products that are substantially soluble in water can be preferably used. In particular, di- to tetra-methylolmelamine and mono- to di-methylol-di- to tri-
A component selected from the group consisting of methoxymethylmelamine or a substantially water-soluble reaction product based thereon is utilized. The use of these components not only has favorable properties in terms of flame retardancy, bending resistance, tear resistance, etc., but also exhibits good thermal discoloration prevention properties.
It has excellent stability and there is no risk of gelling, and there is no risk of deteriorating the surface condition of the treated product and losing its practicality. In addition, as the above-mentioned melamine-based reaction product-forming component used in the present invention, a part of melamine (less than mol % thereof) can be used as an amino resin-forming co-condensation component, such as urea.
It can be replaced with known cocondensation components such as ureas such as thiourea and guanylurea, guanamines such as acetoguanamine, propioguanamine, and benzoguanamine; and dicyandiamide and its functional enigmatic conductors.

It is also possible to partially replace formaldehyde (or paraformaldehyde) with acetaldehyde, propionaldehyde, or the like. The flame retardant for cellulose-based materials of the present invention contains as active ingredients the above-described main component amounts of guanidine sulfamate and an amount of a melamine-based reaction product to prevent thermal discoloration. Other additives may be included, such as anti-corrosive agents, rust inhibitors, pH regulators, anti-moisture agents, and the like.

The amount of these additives to be used is an arbitrary amount that does not substantially reduce the thermal discoloration resistance improved by the melamine-based reaction product and does not adversely affect the flame retardant properties and other desirable properties of guanine sulfamate. Available. The cellulosic material flame retardant of the present invention can be in any dosage form, for example, powder, granules, pellets, pellets, lumps, aqueous liquid, etc., or In addition, a two-drug liquid-liquid type in which each active ingredient is used together at the time of use,
It can also be in solid-liquid or solid-solid dosage form.
According to the present invention, the flameproofing of cellulosic materials is characterized in that the cellulosic materials are treated with a main component amount of guanidine sulfamate and an amount of at least one type of melamine-based reaction product for preventing thermal discoloration as described above. A processing method can be provided.

The treatment can be carried out by sufficiently applying guanidine sulfamate and a melamine-based reaction product to a cellulose-based material of any shape, and usually using an aqueous solution of these materials, it is immersed, sprinkled, sprinkled, etc. It can be applied by any means such as coating, and a treated product can be obtained by drying. In this case, the treatment may be performed using either guanidine sulfanate or the melamine-based reaction product, preferably the melamine-based reaction product, and then the other, or a mixture of the two may be used. can be processed simultaneously. The flame retardant treatment can be applied to the sum of guanidine sulfamate and melamine-based reaction products (as solids), e.g.
The treatment is preferably carried out with an aqueous liquid containing about 6% by weight, and the amount of adhesion to the cellulosic material is preferably about 15 to about 30 parts by weight (as solid content) per 100 parts by weight of the material, more preferably It is about 20 to about 25 parts by weight. If desired, a squeezing step can be added to adjust the amount of impregnation, and a treated product can be obtained by drying at a temperature of, for example, about 90 to about 150 qo. The pH of the treatment solution is preferably from weakly acidic to weakly alkaline, and is usually around 5 to 8.
It is preferable to adopt the H condition. Next, some examples of the unique thermal discoloration resistance achieved by the flameproofing treatment of the present invention will be described with reference to the accompanying drawings. Figure 1 shows an example of using industrial guanidine sulfamate (purity 933%) alone;
The results of a thermal discoloration prevention test for the combination example of the industrial guanidine sulfamate and the melamine-formaldehyde reaction product, and the combination example of the industrial guanidine sulfamate and the melamine-formaldehyde-alcohol reaction product. An example is shown.

In the figure, the axis shows the flameproofing pH, the vertical tree shows the whiteness (hunter), curve a is the result of using industrial sulfamic acid guanine alone (comparative example No.1), and curve b is the result of using the industrial sulfamic acid guanine alone. As a result of the combined use example of guanidine and a melamine-formaldehyde reaction product (a water-soluble melamine-formaldehyde-based reaction product containing dimethylolmelamine as a main component) (Example 1 of the present invention), the curve c shows the industrial guanidine sulfamate. The results of the combined use example (Example 2 of the present invention) with a melamine-formaldehyde-alcohol-based reaction product (a water-soluble melamine-formaldehyde-methanol-based reaction product whose main component is monomethylol dimethoxymethyl melamine) are shown below. It shows. The above-mentioned example of the present invention. 1
and no. The amount of the melamine-based reaction product used together in Comparative Example 2 was 2 parts by weight per 100 parts by weight of industrial guanidine sulfamate. 1
The amount used is the same as that of industrial guanidine sulfamate alone. Furnace paper (Toppan No. 2) was used as the sample paper stock. The test method is as follows. Thermal discoloration prevention test (Hunter whiteness test): - After adding and dissolving a predetermined amount of melamine-formaldehyde-based reaction product or melamine-formaldehyde-alcohol-based reaction product into an aqueous solution of guanidine sulfamate, or the aqueous solution. The pH of the solution was adjusted to a predetermined pH with an aqueous phosphoric acid solution, and about 3 capes of sand was soaked in the sample paper material, taken out, squeezed with a wringer, and then dried in a dryer at 90° C. to a constant weight.

The amount of flame retardant attached (as solid content) is 2 per 100 parts by weight of the test paper when furnace paper (Totsupan No. 2) is used as the test material.
0-21 parts by weight, and 22-2 parts by weight when wallpaper base paper was used as the sample paper material. A set of 3 pieces of paper with an area of approximately 4 x 4 skin was cut out from each treated paper, and after being kept in hot air drying at a temperature of 170q0±1°C for 1 minute, they were taken out and tested using a color difference meter as described in JISP8123. The Hunter whiteness on the front and back sides of the specimen was measured by
The average value of six measurements on the front and back sides of the sheet is calculated and rounded to the nearest whole number. Furthermore, in FIG. 2, industrial guanidine sulfamate (purity 92.1%) was used in place of the industrial guanidine sulfamate used in the example shown in FIG. The melamine-formaldehyde reaction product (
A water-soluble melamine-formaldehyde reaction product containing trimethylolmelamine as the main component) was used, and the first
Instead of the melamine-formaldehyde-alcohol reaction product used in the example shown in the figure, a melamine-formaldehyde-alcohol reaction product (a water-soluble melamine whose main component is monomethyloltrimethoxymethylmelamine) was used.
The results are shown in the same manner as shown in FIG. 1, except that a formaldehyde-tanol reaction product (formaldehyde-tanol reaction product) was used.

In the figure, curve a' is an example of the use of industrial guanidine sulfamate alone (Comparative Example 2), and curve b'' is an example of the combination of guanidine and a melamine-formadehyde reaction product (invention example M.3). and curve c' respectively show the results of an example of the combined use of the guanidine and the melamine-formaldehyde-alcohol reaction product (invention example 4). Furthermore, in the example shown in FIG. 2, wallpaper base paper was used as the test paper material in the example shown in FIG. The results obtained in the same manner as Example M.2 (curve a'') and the results obtained in the same manner as Invention Example M.3 (curve b'') are shown. From the results shown in Figures 1 to 3 above, problems with the thermal discoloration prevention properties of guanidisosulfamic acid can be significantly improved when used in combination with a very small amount of melamine-formaldehyde or melamine-formaldehyde-alcohol reaction product. It can be seen that a completely unexpected synergistic effect is achieved.

Hereinafter, several embodiments of the flame retardant and anti-inflammatory treatment method of the present invention will be further explained with reference to Examples.

Examples 1 to 16 and Comparative Examples 1 to 7 The following guanidine sulfamate, GSA-1: Industrial guanidine sulfamate (purity 9
2.1%) GSA-2: Industrial guanidine sulfamate (purity 93.3%) GSA-2: Industrial guanidine sulfamate (purity 94.6%) and the following melamine-based reaction product DMM: Dimethylolmelamine A water-soluble melamine-formaldehyde reaction product whose main component is

TMM: A water-soluble melamine-formaldehyde reaction product whose main component is trimethylmelamine.

TEMM: A water-soluble melamine-formaldehyde reaction product containing tetramethylolmelamine as a main component.

MMDM: Water-soluble melamine-formaldehyde- whose main component is monomethylol dimethoxymethyl melamine
Methanol-based reaction product.

MMTM: Water-soluble melamine-formaldehyde-based on monomethyloltrimethoxymethylmelamine
Methanol-based reaction product.

DMTM: A water-soluble melamine-formalhyde-methanol-based reaction product containing dimethyloltrimethoxymethylmelamine as a main component.

The thermochromic test was conducted under the conditions shown in Table 1 below.

The results are shown in Table 1. Table 1 shows the results of the folding durability (times) test conducted using wallpaper base paper in accordance with JIS-P8115 (17000, 10 minutes) and the JIS-P
The results of a tear strength test conducted in accordance with 8116 (20° C., 65%-RH) are also shown. Table 1: Whiteness of untreated paper after heating at 170°C for 10 minutes (Hunter) 78**
〃 〃 7 2zozakura Treated with melamine-based reaction product and then treated with guanidine sulfamate *Konafune Treated with guanidine sulfamate and then treated with melamine-based reaction Ikusaka Tanmono

[Brief explanation of the drawing]

Attached Figure 1 shows industrial guanidine sulfamate alone (
Prevention of thermal discoloration in line a), the combination of the guanidine and melamine-formalhyde reaction product of the invention (line b), and the combination of the guanidine and melamine-formaldehyde-alcohol reaction product of the invention (line c) Graph showing the whiteness-pH curve for an example of a whiteness test, second
FIG. 3 and FIG. 3 are graphs showing similar whiteness-pH curves for other examples. Figure 2 Figure 3

Claims (1)

[Scope of Claims] 1. Based on 100 parts by weight of guanidine sulfamate as the main component, a compound selected from the group consisting of di- or tetra-methylolmelamine and mono- or di-methylol-di- or tri-methoxymethylmelamine. about 0.1 weight of at least one melamine-based reaction product selected from a substantially water-soluble melamine-formaldehyde-based reaction product and a melamine-formaldehyde-alcohol-based reaction product containing these components as main components. 1. A flame retardant for nitrocellulose-based materials, characterized in that the flame retardant contains as an active ingredient at least 50% of ammonium sulfamate. 2 A main component amount of guanidine sulfamate and a component selected from the group consisting of di- to tetra-methylolmelamine and mono- to di-methylol-di- to tri-methoxymethylmelamine, or a component substantially containing these as the main component. At least one melamine-based reaction product selected from a water-soluble melamine-formaldehyde-based reaction product and a melamine-formaldehyde-alcohol-based reaction product, and the main component amount of guanidine sulfamate 1
About 0.1 parts by weight of the melamine-based reaction product
1. A method for flameproofing a cellulose-based material, characterized in that the cellulose-based material is treated simultaneously or with one and then the other under conditions of parts by weight or more, and the cellulose-based material is not treated with ammonium sulfamate.