JPS6317115B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to cellulosic materials such as wallpaper,
For cellulose-based materials that can be advantageously used for flame-retardant treatment of cellulose-based materials containing cellulose, such as fusuma paper, shoji paper, wall cloth, and other various papers and cloths for interior decoration, furniture, and building materials. This invention relates to a flame retardant and a flame retardant treatment method. More specifically, the present invention provides excellent heat discoloration resistance, as well as flame retardancy, bending resistance, tear resistance, prevention of size effect reduction, aqueous solution storage stability, excellent texture,
Regarding a flame retardant and a flame retardant treatment method useful for providing a flame retardant cellulose material having favorable properties such as low cost, in particular, the main component amount of guanidine sulfamate and a urea-formaldehyde-alcohol based It is characterized by containing as active ingredients a reaction product and an amount of at least one urea-based reaction product selected from the group consisting of urea-formaldehyde-based reaction products with a methylol conversion rate of about 20% or more to prevent thermal discoloration. A method for flameproofing a cellulosic material, comprising treating the cellulosic material with a flame retardant for a cellulosic material and an amount of the guanidine sulfamate and at least one of the urea-based reaction product to prevent thermal discoloration. Regarding. Conventionally, guanidine sulfamate has been known as a flame retardant for cellulosic materials and has been put to practical use. The guanidine sulfamate treatment product not only has favorable properties in terms of flame retardancy, bending durability, tear resistance, etc. It has better thermal discoloration prevention properties than other flame retardants. 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 difficult to prevent from unreacted ammonium sulfamate that may be contained in the product. This is thought to be due to by-product impurities, but they often still exhibit unsatisfactory anti-thermal discoloration properties. In order to overcome these disadvantages, it is difficult to remove these unreacted substances and by-products to obtain guanidine sulfamate with a satisfactory high purity, which is difficult in terms of operation and cost. Therefore, it is possible to avoid the above-mentioned difficulties, and it has excellent heat discoloration prevention properties, while also having no adverse effects on the preferable flame retardancy, bending durability, tear resistance, etc. of the guanidine sulfamate treated product. It is desired to provide a flame retardant for cellulosic materials with excellent flame retardant suitability that exhibits improved thermal discoloration resistance without adversely affecting the flame retardant. In particular, wallpaper and similar cellulose-based materials are often used with their surfaces coated with a resin such as vinyl chloride resin, and in this coating process they are heated to about 150 to 200 degrees Celsius. There is an increasing demand for a flame retardant for cellulosic materials that has excellent 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 and a flame retardant treatment method that can satisfy the above demands. As a result, by using the main component amount of guanidine sulfamate in combination with the above-mentioned urea-based reaction product, which does not exhibit properties that can be used as a flame retardant by itself, the thermal discoloration prevention property is significantly improved. I discovered that. Conventionally, urea-
Regarding attempts to use formaldehyde resin in combination,
This is reported in the upper right column of page 34 of Japanese Patent Application Laid-open No. 19808/1983. According to this report, the addition of the urea-formaldehyde resin caused cloudy solidification, and it was reported that it was impossible to improve the heat resistance of such an aqueous medium by adding the resin. Quite surprisingly, the present inventors have discovered that the main component amount of guanidine sulfamate and a urea-based reaction product that does not exhibit properties that can be used as a flame retardant by itself, especially urea-aldehyde-alcohol-based By using the reaction product in combination with a urea-based reaction product selected from the group consisting of urea-formaldehyde-based reaction products with a methylolization rate of about 20% or more, the thermal discoloration prevention property can be significantly improved. However, it was discovered that the storage stability of this combination system as an aqueous solution was extremely good. Furthermore, the cellulose-based material treated with this combination system has favorable properties such as excellent flame retardancy, bending resistance, tear resistance, ability to prevent deterioration of size effect, etc., in addition to the above-mentioned improved properties. I learned that it also shows properties. Therefore, the purpose of the present invention is to provide excellent thermal discoloration resistance, flame retardancy, bending resistance, tear resistance, prevention of size effect deterioration, aqueous solution storage stability, excellent texture, low cost, etc. It is an object of the present invention to provide a flame retardant for cellulosic materials and a flame retardant treatment method that have both advantages and excellent flame retardant suitability. The above objects and many other objects and advantages of the present invention will become more apparent from the following description. The flame retardant for cellulosic materials of the present invention is selected from the group consisting of a main component of guanidine sulfamate, and a urea-formaldehyde reaction product and a urea-formaldehyde-alcohol reaction product with a methylol conversion rate of about 20% or more. It contains as an active ingredient an amount of at least one selected urea-based reaction product to prevent thermal discoloration. The amount of the urea-based reaction product used may be an amount that prevents thermal discoloration, and is usually at most about 20 parts by weight per 100 parts by weight of guanidine sulfamate.
The amount is about parts by weight or less. Generally, the amount is preferably about 0.1 to about 20 parts by weight, more preferably about 0.5 to about 15 parts by weight, and particularly about 1 to about 10 parts by weight, based on 100 parts by weight of guanidine sulfamate.
The use of resin processing amounts of urea-based reaction products in excess of thermal discoloration prevention amounts that would substantially alter the physical properties of cellulosic materials when treated with guanidine sulfamate alone should be avoided. be. The use of urea-based reaction products in excess of the amount that prevents thermal discoloration will adversely affect the bending durability, tear resistance, and other favorable properties that guanidine sulfamate-treated cellulosic materials have, along with their excellent flame retardant properties. It is used in an amount that prevents thermal discoloration without causing such adverse effects. In the present invention, the urea-formaldehyde reaction product has a methylol conversion rate of about 20% or more, for example about 25% to about 60%, more preferably about
About 30% to about 50% of the reaction product is used. Also, in the case of a urea-formaldehyde-alcohol reaction product, it is preferable to use a product obtained by etherifying the urea-formaldehyde reaction product with the above-mentioned methylol conversion rate before etherification with alcohol. can. In the present invention, the methylol conversion rate is a value determined by the following method. Methylolation rate (%) = {[TF]−[fF]}/30
×14×2/[N]×100/4 [TF]: Total formaldehyde % by phosphoric acid decomposition/sodium sulfite method [fF]: Free formaldehyde % by sodium sulfite method [N]: Nitrogen amount % by Kieldahl method This invention The urea-based reaction product used in can be produced by means known per se. For example, it can be easily produced by reacting urea and formaldehyde under neutral to weakly alkaline conditions, preferably at a pH of about 8 to about 10, at a temperature of about 50°C to about 100°C. The resulting urea-formaldehyde reaction product and/or methylolated urea derived from, for example, urea and formaldehyde, and an alcohol, preferably a lower alcohol, under weakly acidic conditions, for example, at a pH of about 4 to about 5,
For example, a urea-formaldehyde-alcohol reaction product can be exemplified, which can be easily produced by subjecting the alcohol used to an etherification reaction under reflux temperature conditions. The pH can be adjusted using, for example, acids such as hydrochloric acid, sulfuric acid, phosphoric acid, and oxalic acid; and alkalis such as sodium hydroxide, sodium carbonate, and guanidine carbonate. In addition, the above-mentioned urea-formaldehyde-alcohol reaction product can be formed by adding an alcohol at any point in the urea-formaldehyde reaction product formation reaction to adjust the pH. It may be a reaction product obtained using any well-known modified method. As is well known, these reaction products are usually obtained in the form of mixtures having various degrees of methylolation, etherification, and/or condensation. It is common and can be used as a urea-based reaction product in the present invention. In addition, these degrees or degrees are determined by the PH conditions as exemplified above, or by the reaction temperature, reaction time,
It can be changed as appropriate by selecting the catalyst and reaction conditions. In the present invention, it is preferable to use a reaction product that does not become substantially insoluble in water or other solvents, depending on the degree of condensation or etherification, for example. In addition, a part of urea (its
less than 50 mol%, preferably less than 40 mol%), amino resin-forming cocondensation components, such as ureas such as thiourea and guanylurea; guanamines such as acetoguanamine, propioguanamine, and benzoguanamine; dicyandiamide and its It can be replaced with known co-condensation components such as functional derivatives; 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 urea-based reaction product to prevent thermal discoloration. Other additives may be included, such as anti-corrosion agents, anti-corrosion agents, pH-adjusting agents, 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 urea-based reaction product and does not adversely affect the flame retardant properties and other desirable properties of guanidine sulfamate. Available. The flame retardant for cellulosic materials of the present invention can be in any dosage form, such as powder, granules, granules, pellets, lumps, aqueous liquid, or It can also be a two-dose liquid-liquid, solid-liquid, or solid-solid dosage form in which each active ingredient is used in combination. According to the present invention, the cellulosic material is treated with a main component amount of guanidine sulfamate and an amount of at least one of the above-mentioned urea-based reaction products to prevent heat discoloration. A flame treatment method can be provided. The treatment can be carried out by sufficiently applying guanidine sulfamate and a urea-based reaction product to a cellulosic material of any shape, and is usually carried out by immersion in an aqueous solution of these materials,
It can be applied by any means such as spraying, sprinkling, or roll coating, and can be dried to obtain a treated product. In this case, after treatment with either guanidine sulfamate or a urea-based reaction product, preferably with a urea-based reaction product, the other may be used,
It is also possible to simultaneously process with a mixed solution of both. The flame retardant treatment is the sum of guanidine sulfamate and urea-based reaction products (as solids), e.g.
It is preferable to treat with an aqueous liquid containing about 10 to about 60% 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. is about 20 to approx.
It is 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°C. The pH of the treatment liquid is preferably weakly acidic to weakly alkaline, and it is generally preferable to adopt a pH condition of about 5 to about 8. Next, some examples of the unique thermal discoloration prevention properties achieved by treatment with the flame retardant of the present invention will be explained with reference to the accompanying drawings. FIG. 1 shows an example in which industrial guanidine sulfamate (purity 95.1%) is used alone, an example in which the industrial guanidine sulfamate is used in combination with a urea-formaldehyde reaction product with a methylol conversion rate of about 20% or more,
and the industrial guanidine sulfamate and urea.
An example of the results of a thermal discoloration prevention test for an example of combined use with a formaldehyde-alcohol reaction product is shown. In the figure, the horizontal axis is flameproofing treatment
The vertical axis shows the whiteness (Hunter), and the curve a
is the result of using industrial guanidine sulfamate alone (Comparative Examples 1 to 4); curve b is the result of using industrial guanidine sulfamate alone and a urea-formaldehyde-based reaction product with a methylolation rate of about 20% or more (methylolation rate 57.5% ( 2.3F) in combination with water-soluble urea-formaldehyde-based reactant) (Example 15 of the present invention)
and 18-20), curve c is the industrial guanidine sulfamate and urea-formaldehyde.
Examples of combined use with alcohol-based reaction products (water-soluble urea-formaldehyde-methanol-based reaction products (2.2F1.8M) whose main component is dimethyloldimethoxymethylurea) (present invention examples 2 and 5 to 7) ) shows the results. The amount of the urea-based reaction product used in combination in the above examples of the present invention is:
The amount is 5 parts by weight per 100 parts by weight of industrial guanidine sulfamate, and the total amount used is as follows: Comparative Examples 1-
The amount is the same as the amount of industrial guanidine sulfamate used alone in No. 4. In addition, paper (Toyo Roshi No. 2) was used as the sample material. The test method is as follows. Thermal discoloration prevention test (Hunter whiteness test):
- After adding and dissolving a guanidine sulfamate aqueous solution, or a predetermined amount of a urea-formaldehyde-based reaction product or a urea-formaldehyde-alcohol-based reaction product to the aqueous solution, the pH of the solution is adjusted to a predetermined PH with an aqueous sulfamic acid solution. The test paper material was immersed in this for about 30 seconds, taken out, squeezed with a wringer, and dried in a dryer at 90°C to a constant weight. The amount of flame retardant attached (as solid content) is 100% of the sample paper material
When paper (Toyo Roshi No. 2) was used as the test paper material, it was 20-21 parts by weight, and when wallpaper base paper was used as the test paper material, it was 22-23 parts by weight. A set of three specimens with an area of approximately 4 x 4 cm was cut from each treated paper, kept in a hot air dryer at a temperature of 200°C ± 1°C for 5 minutes, and then taken out and tested with a color difference meter as described in JIS P8123. Hunter whiteness was measured on the front and back sides of each specimen piece, and the average value of the six measurements on the front and back sides of each three sheets was calculated and rounded to the nearest whole number. Furthermore, in the example shown in FIG. 1, the results (curves) obtained in the same manner as Comparative Examples 1 to 4 in FIG.
a': Comparative Examples 5 to 8), Invention Examples 15 and 18 to
Results obtained in the same manner as in 20 (curve b′: Examples 30 to 32)
And the results obtained in the same manner as Examples 2 and 5 to 7 of the present invention (curve c': Examples 24 to 26) are shown. From the results shown in Figures 1 and 2 above, thermal discoloration of guanidine sulfamate can be prevented by combined use with a urea-formaldehyde or urea-formaldehyde-alcohol reaction product with a methylol conversion rate of about 20% or more. It can be seen that the mutual effect of significantly improving sexual problems is achieved. Hereinafter, several embodiments of the flame retardant and flame retardant treatment method of the present invention will be further explained with reference to Examples. In addition, 1FU in the urea-formaldehyde reaction product,
The label 2.3FU indicates that 1 mol and 2.3 mol of formaldehyde were reacted with 1 mol of urea, respectively. In addition, the 1F1MU and 2F1.2MU labels for urea-formaldehyde-alcohol reaction products indicate that 1 mole of urea was reacted with 1 mole of formaldehyde and 1 mole of methyl alcohol in the former, and the latter indicates that 1 mole of urea was reacted with 1 mole of formaldehyde and 1 mole of methyl alcohol. 2 moles of formaldehyde, 1.2 moles of methyl alcohol
Indicates that moles have been reacted. Examples 1 to 32 and Comparative Examples 1 to 15 The following guanidine sulfamate, GSA: Industrial guanidine sulfamate (purity
95.1%) and the following urea-based reaction product 1FU: water-soluble urea-formaldehyde-based reaction product whose main component is a methylolation rate of 25% 2.3FU: water-soluble urea-formaldehyde whose main component is a methylolation rate of 57.5% System reaction product 1F1MU: Water-soluble urea-formaldehyde-methanol system reaction product whose main component is monomethoxymethylurea 2F1.2MU: Water-soluble urea-formaldehyde-methanol system reaction whose main component is monomethylolmonomethoxymethylurea Product 2.2F1.8MU: Water-soluble urea-formaldehyde-methanol reaction product containing dimethoxymethylurea as the main component and the following amino-based reaction product S-305: Trimethylolmelamine condensate DD resin: Dimethylol dicyandiamide resin The thermochromic property, critical adhesion rate, flexibility, and storage stability of the blended solution were tested under the conditions shown in Table 1 below. The respective test methods are as follows. Critical adhesion rate: According to JIS Z-2150, measure the minimum treatment agent adhesion rate (dry pick-up on paper) that passes JIS flame retardant class 2 (charring length 10 cm or less). Flexibility: 20mm of flame-retardant paper in the vertical and horizontal directions
Collect 5 x 120mm test pieces, RH65%,
After being left in the standard condition of 20℃ for 24 hours, the degree of flexibility is measured using a textile softness tester under the same standard condition. For flexibility, fix 20cm of one end of the specimen and
100mm on the moving table, lower the moving table horizontally, read the length (mm) between the moving table and the fixed table at the point where the free end of the test piece leaves the moving table, measure it five times, and then Find the average value. Storage stability of processing agent mixture: Each example in a 100ml glass sample bottle,
Approximately 100 ml of a 20% aqueous solution of the formulation of the comparative example is poured into the container, tightly stoppered, and left in a furan vessel at 40°C, and the number of days until cloudiness or precipitate appears is measured. The results are shown in Table 1.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 is a graph showing an example of the relationship between PH and whiteness for the flame retardants of the present invention and comparative flame retardants.
FIG. 2 is a graph showing another example of the same relationship as FIG. 1.

Claims (1)

[Scope of Claims] 1. A urea-based product selected from the group consisting of a main component amount of guanidine sulfamate, a urea-formaldehyde-alcohol reaction product, and a urea-formaldehyde reaction product with a methylol conversion rate of about 20% or more. 1. A flame retardant for cellulosic materials, characterized in that it contains as an active ingredient at least one of a reaction product in an amount that prevents thermal discoloration. 2. The flame retardant according to claim 1, wherein the amount of the urea-based reaction product is about 0.1 to about 20 parts by weight based on 100 parts by weight of the guanidine sulfamate. 3. The flame retardant according to claim 1, wherein the methylolation rate is about 20% to about 60%. 4 At least one urea-based reaction product selected from the group consisting of guanidine sulfamate in the amount of the main component, a urea-formaldehyde-alcohol-based reaction product, and a urea-formaldehyde-based reaction product with a methylol conversion rate of about 20% or more. 1. A flameproofing method for cellulosic materials, characterized by treating the cellulosic materials with a thermal discoloration prevention amount. 5. The treatment method according to claim 4, wherein the amount of the urea-based reaction product is about 0.1 to about 20 parts by weight based on 100 parts by weight of the guanidine sulfamate. 6. The treatment method according to claim 4, wherein the methylolation rate is about 20% to about 60%.