JPS6332116B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention mainly relates to a flame retardant treatment agent that exhibits excellent performance on cellulosic materials. More specifically, it has excellent flame retardant properties,
The present invention provides a flame retardant treatment agent for cellulosic materials that has good thermal stability, is free from hygroscopicity and does not cause rust, and further releases extremely small amounts of formaldehyde. Conventionally, ammonium phosphate, ammonium sulfate, boric acid, ammonium bromide, or carbonate compounds have been used singly or as a mixture as flame retardant treatment agents for cellulosic materials such as paper. However, when treated with these flame retardants,
The thermal stability, weather resistance, coloration over time, hygroscopicity, texture, strength, etc. of the processed material deteriorate, making it difficult to maintain the quality of the processed material, and the flame retardance is also unsatisfactory. It wasn't something I could do. In recent years, various proposals have been made to improve these drawbacks by blending compounds such as guanidine sulfamate, diguanidine phosphate, dicyandiamide, or melamine singly or as a mixture, or blending methylolated products of these compounds. For example, Japanese Patent Publication No. 52-25447 discloses a composition using a composition consisting of 1 to 20 parts of diguanidine phosphate to 100 parts of guanidine sulfamate.
-25448 contains ammonium sulfamate as the first
The second component is guanidine sulfamate, and the third component is an organic nitrogen-containing compound selected from dicyandiamide, methylolated dicyandiamide, and hexamethylenetetramine, as seen in JP-A-53-125395. JP-A No. 54-64117 discloses a method of treating with a composition containing guanidine sulfamate as a main component and melamine-formalin-based and melamine-formalin-alcohol reaction products as active ingredients, A composition in which dicyandiamide-methylolated product is added as an essential component to a composition consisting of guanidine sulfamate and diguanidine phosphate as disclosed in Japanese Patent Publication No. 52-25447, and a formalin reaction with guanidine sulfamate as seen in Japanese Patent Publication No. 54-70698. It has been proposed that the main component is dicyandiamide and one type of subcomponent selected from the group of diguanidine phosphate and guanylurea phosphate as an active ingredient. However, even in the method of using these organic nitrogen-containing compounds in combination, it is necessary to use a large amount in order to produce a flame retardant treatment effect, and some may improve thermal stability but may not have sufficient flame retardant effect. However, there still remain problems such as the paper is hard, the strength is significantly reduced, and it is susceptible to rust. Furthermore, Japanese Patent Application No. 1987-87457 describes a flame retardant treatment agent containing a methylolated product of diguanidine phosphate as an essential component, which has various properties required as a flame retardant compared to conventionally known ones. The results are markedly improved, particularly in high-temperature thermal stability. In other words, diguanidine phosphate, which has conventionally had excellent performance as a flame retardant but had limited solubility in water, has been limited in use, but by converting it into a methylol compound, its water solubility has been improved, resulting in a high-performance flame retardant. The company is praised for making it possible to provide processing agents. However, a drawback of methylolated organic nitrogen-containing compounds used as flame retardant treatment agents, including methylolated diguanidine phosphate, is that free formaldehyde is generated during and after processing. Therefore, although each of them has properties of improving flame retardancy, heat resistance stability, and physical properties of treated paper, there are still restrictions on their use alone or in their blending ratio. A major use of flame-retardant paper is wallpaper, and the standard for wallpaper is JIS A6921, which stipulates that the amount of formaldehyde released is 2mg/or less, and the amount of formalin released can also be increased when used for other purposes. It is desirable that there be fewer. The main object of the present invention is to improve the problems of conventional flame retardant treatment agents containing methylolated organic nitrogen-containing compounds, especially methylolated diguanidine phosphate, as an active ingredient, and to provide excellent flame retardant properties. The purpose of the present invention is to provide a flame retardant treatment agent that has various properties such as heat resistance and rust prevention, and also emits extremely little formaldehyde. As a result of intensive studies to achieve this objective, the present inventors have found that by adding a certain nitrogen-containing organic compound to a flame retardant treatment agent containing a methylolated product of diguanidine phosphate, flame retardancy and thermal stability can be improved. The present invention was achieved by discovering that the amount of formaldehyde released can be suppressed without impairing various properties such as. The flame retardant treatment agent of the present invention is a flame retardant treatment agent containing a methylolated product of diguanidine phosphate as an active ingredient, and which contains one or more nitrogen-containing organic compounds selected from cyclic alkylene ureas, amino compounds, or amides. It is characterized by the addition of a compound, and it can be used alone or in combination with other flame retardant components, such as diguanidine phosphate or guanidine sulfamate, or mixtures thereof. It also includes. The methylolated diguanidine phosphate, which is an essential component of the flame retardant treatment agent of the present invention, is produced, for example, by the following method. A slurry of guanidine carbonate and water is heated to 50-60°C, formaldehyde is added, and the methylolation reaction is carried out until complete dissolution. Next, phosphoric acid is added to neutralize the mixture to obtain an aqueous solution of methylolated guanidine phosphate. It can also be produced by adding a formaldehyde aqueous solution whose pH has been adjusted to neutral or weakly alkaline in advance to diguanidine phosphate, and stirring and reacting at 80 to 90°C until diguanidine phosphate is completely dissolved. The methylolated product of diguanidine phosphate used in the present invention is a reaction product obtained by reacting formaldehyde in an amount of up to about 4 moles, preferably 0.5 to 3 moles, and more preferably 0.8 to 2 moles, per mole of diguanidine phosphate. Preferably something. If the number of reactive moles of formaldehyde is too large, the solubility will increase, but flame retardancy will decrease, and hygroscopicity will tend to increase, which is not preferable. Furthermore, if the reaction molar ratio is too low, the solubility will be low and crystals will precipitate at low temperatures, causing inconvenience in handling. Further, thermal stability tends to decrease, which is not preferable. Therefore, in the present invention, it is preferable to use the reaction product of diguanidine phosphate and formaldehyde in the reaction molar ratio as exemplified above. The methylolated product of diguanidine phosphate of the present invention exhibits extremely remarkable flame retardant properties, and also has excellent properties such as good thermal stability of treated paper, no loss of white color, no hygroscopicity, and no corrosiveness to metals. In addition, it has an extremely high solubility in water, so it has the advantage that a highly concentrated treatment liquid can be adjusted as necessary. Furthermore, in addition to single use, by blending with guanidine sulfamate, diguanidine phosphate, or a mixture thereof, these drawbacks can be improved and an excellent synergistic effect not seen with conventional flame retardants can be obtained, resulting in an outstanding Performance is demonstrated. In other words, guanidine sulfamate has improved flame retardancy, reduced hygroscopicity, eliminated metal corrosion, and has the effect of increasing the stiffness of paper, while diguanidine phosphate has remarkable heat resistance stability. Furthermore, it has the effect of improving the problem of hard paper quality and imparting appropriate flexibility. When guanidine sulfamate, diguanidine phosphate, or a mixture thereof is used in combination with methylolated diguanidine phosphate, the ratio of methylolated diguanidine phosphate in the total amount must be 5% by weight or more in terms of solid content. A sufficiently high-performance flame retardant treatment agent can be obtained, but a synergistic effect is particularly exhibited when the ratio is within the range of 5 to 50% by weight. The flame retardant treatment agent of the present invention contains as an essential component, in addition to the above-mentioned methylolated diguanidine phosphate, one or more nitrogen-containing organic compounds selected from cyclic alkylene ureas, amino compounds, or amides as a formalin scavenger. contains. The formalin scavenger used here is not particularly limited as long as it easily reacts with formalin and its product does not dissociate formalin and is harmless and stable, but it should not be limited to substances that generate a bad odor or that are released in the air. Those that are hygroscopic, unstable, or easily decomposed by heating are unsuitable. More importantly, it must not impair the properties of the flame retardant, namely its flame retardant performance and thermal stability, as well as the physical properties of the flame retardant treated paper. The inventors of the present invention have conducted intensive studies to find a substance having such characteristics, and have found that the above-mentioned nitrogen-containing organic compound has extremely excellent properties as a formalin scavenger used in a flame retardant. Specific examples of these nitrogen-containing organic compounds include:
For example, cyclic alkylene ureas include ethylene urea, propylene urea, 5-hydroxypropylene urea, 5-methoxypropylene urea, 5-methylpropylene urea, etc., and amino compounds include aliphatic diamines such as ethylenediamine and dicyandiamide, and melamine. Examples include cyclic amines such as Amides include urea, barbituric acid, semicarbazide hydrochloride, and the like. These nitrogen-containing organic compounds easily react with formaldehyde and turn into stable substances that do not release formaldehyde during or after processing. It also has high solubility in water and can be obtained at low cost. Among these, urea, cyclic alkylene urea and ethylene diamine are particularly preferred. The amount of the nitrogen-containing organic compound added to the flame retardant treatment agent of the present invention may be 1 to 10 parts by weight, preferably 1 to 10 parts by weight, per 100 parts by weight of diguanidine phosphate methylolate.
It is 5 parts by weight. If it is less than 1 part by weight, it will not be sufficiently effective, and it is not necessary to use more than 10 parts by weight. Although each of these nitrogen-containing organic compounds exhibits a good effect when used alone, they may be used in an appropriate mixture, taking into account the solubility and formalin scavenging effect of each. As for the method of adding the nitrogen-containing organic compound to the flame retardant treatment agent, it may be added appropriately in the process of adjusting the flame retardant treatment agent, but it is generally preferable to add a predetermined amount after adjusting the flame retardant treatment agent. . The flame retardant treatment agent of the present invention has the above-mentioned properties of the extremely excellent flame retardant of diguanidine diguanidine phosphate as an extremely excellent flame retardant, and also has the characteristic that the amount of formaldehyde released during or after processing is extremely small. This achieves the JIS A6921 formaldehyde emission standard value of 2mg/or less. The method of applying the flame retardant treatment agent of the present invention to the target substrate may be any conventional method, such as a method of immersing the substrate in an aqueous solution of the flame retardant treatment agent and then drying it, or a method of spraying it. , size press method, etc. are suitable. In this case, the flame retardant treatment agent blended in advance may be dissolved in water, but it is also possible to use a mixture of solutions in which each component is dissolved. Furthermore, the flame retardant treatment agent of the present invention can be used in combination with a sizing agent, a surface treatment agent such as starch, or another treatment agent for paper or fiber. The adhesion amount of the flame retardant treatment agent of the present invention to the base material is suitably 3 to 30% by weight in terms of solid content, particularly 5 to 30% by weight.
20% by weight is preferred. The flame retardant treatment agent of the present invention is suitable as a treatment agent for various cellulosic materials, especially paper, and can also be applied to general synthetic paper and the like. EXAMPLES Next, the present invention will be explained in more detail with reference to Examples, but the present invention is not limited to these Examples. The preparation of the test specimen and each performance test were conducted in the following manner. (1) Preparation of test specimens Toyo Paper No. 1 (weighing 90 g/m ² ) was cut into pieces of 25 x 30 cm as flame retardant treated paper materials, and placed in an aqueous solution of each flame retardant at a temperature of 50°C. approx. in °C
After soaking for 30 to 60 seconds, taking out and squeezing with a wringer (two-roll type pneumatic), dry in a dryer at 105℃ for 30 minutes.
Dry for a minute and place in a humidifier (silica gel deseater)
After leaving it for 24 hours, it was tested. Incidentally, the amount of the drug attached was varied between 5 and 25% by weight. However, for paper property tests, the adhesion amount was standardized at 12% by weight. The main chemicals used as flame retardant treatment agents in this example are as follows. (A) Methylolated diguanidine phosphate: (Diguanidine phosphate: formaldehyde = 1:2 is shown as a reference example.) 327 g (1.814 mol) of guanidine carbonate and 433 g of water
g to make a slurry, warm it and keep it at 55-60°C. Paraformaldehyde while stirring
After adding 136g (3.627mol) and completely dissolving it,
Continue the reaction for 30 minutes. Then 208g of 85% phosphoric acid
was added and further heated for about 30 minutes to prepare a reaction product. This liquid contains 50wt% solids. (B) Guanidine sulfamate is a reagent (Tokyo Kasei Co., Ltd.)
Special grade (manufactured by Co., Ltd.) was used. (C) Diguanidine phosphate is a reagent (manufactured by Kanto Chemical Co., Ltd.)
I used special grade. (D) All other chemicals used were special grade reagents. (2) The test method is as follows. Flame retardant Heating time 10 according to JIS Z2150 “Flame retardant test method for thin materials (45°Metzkelvarna method)”
Tested in seconds. Each test piece was measured as a set of 5 pieces, and the average value was adopted. Thermal stability (whiteness) From each specimen, area 4 x 4
A set of 5 specimens of cm in size were cut out and heated in a hot air dryer at a temperature of 180°C for 5 minutes.
In accordance with JIS P-8123-1961, the Hunter whiteness on the front and back sides of each set of specimens was measured using a color difference meter, and the average value was adopted. Hygroscopicity Cut a test piece with an area of 5 x 5 cm from each test piece and place it in a hot air dryer at a temperature of 110℃ x 1.5 hours.
The amount of weight increase when dried and bone-dry was left in a humidifier at 20°C and 80% relative humidity for 24 hours was determined and expressed as a weight increase rate relative to untreated paper. Rustability A test specimen with an area of 10 x 10 cm was cut from each test specimen, and a metal such as a stapler, insect pin, clip, copper wire, or nail was attached to it at a temperature of 20°C.
The material was left in a humidifier with a relative humidity of 80% for 30 days and visually inspected for rust. (3) The paper properties test method for flame retardant treated paper is as follows. Bending strength Measurement was carried out using an MIT type tester under a load of 0.5 kg in accordance with JIS P8115. Tear strength was measured using an Elmendorf tester in accordance with JIS P-8116. Stiffness (stiffness) Measured using a Gurley stiffness tester. Tensile strength Measured according to JIS P-8113. (4) Formaldehyde release amount Conducted in accordance with JIS A6921. That is, JIS
Normal temperature and humidity conditions specified in Z8703 (20±15℃, humidity
65±20%) for 24 hours, and was measured by acetylacetone colorimetric method. Examples 1 to 5 The flame retardants used in the tests were prepared by using a 50% by weight aqueous solution of a compound obtained by adding 2 mol of formaldehyde to diguanidine phosphate, and adding 1 to 10 parts of a formaldehyde scavenger per 100 parts of solid matter. with a treatment agent,
It was applied to paper (Toyo Paper No. 1) using a predetermined method, and the flame retardant performance was tested and the amount of formaldehyde released was measured. The results are shown in Table-1. As a result, when we measured the amount of formaldehyde emitted from flame retardant-treated paper using JIS A6921, we achieved the specified value of 2 mg/or less by adding scavengers such as 5 parts of ethylene urea and 4 parts of ethylene diamine;
A similar effect was obtained with urea, and the objective was also achieved by mixing two types, such as ethylenediamine-urea. The various properties of the flame retardant, namely flame retardancy, thermal stability, hygroscopicity, and rust resistance, are all superior to conventional products. Comparative Examples 1 to 3 A known composition of guanidine sulfamate-ammonium sulfamate-dicyandiamide methylol compound, guanidine sulfamate-diguanidine phosphate-dicyandiamide methylol compound, or guanidine sulfamate-melamine methylol compound, etc. Flame retardant-treated paper was prepared using the method described above, and formaldehyde and flame retardant performance were measured. Comparative Example 4 shows test results for papers treated in the same manner as Examples 1 to 5 except that no formaldehyde scavenger was added. In both cases, the amount of formaldehyde released exceeds the specified value, which is a major drawback. In terms of performance as a flame retardant, all samples other than Comparative Example 4 have problems in thermal stability, hygroscopicity, rust formation, and other points. Examples 6 and 7 Guanidine sulfamate or diguanidine phosphate was blended with the methylolated product of diguanidine phosphate, and ethylene urea was added to prepare a flame retardant treatment agent. The results of testing the performance of each are shown in Table 1.
Shown below. The drawbacks of guanidine sulfamate and diguanidine phosphate have been improved, and the performance is superior to any of Comparative Examples 1 to 3, and the amount of formaldehyde released is below the specified value.

【table】

[Table] Example 8, Comparative Examples 5 to 6 In order to examine the effect on paper strength of paper treated with the flame retardant of the present invention, handmade paper was subjected to flame retardant treatment and paper strength properties were measured. Similarly, Table 2 shows the results using guanidine sulfamate and diguanidine phosphate as comparative examples. The weight of the handmade paper was 70 g/m ² and the amount of flame retardant attached was 15% by weight. First, the tear degree and bending strength are almost the same as those of guanidine sulfamate, and the tensile strength and stiffness are significantly improved compared to guanidine sulfamate. There are no drawbacks seen with conventional flame retardants, and no decrease in paper strength is observed when treated with the flame retardant of the present invention, other than a slight decrease in tearing compared to untreated paper. Next, as for the influence of paper strength when heat treated (treated at 180°C for 5 minutes), folding durability is seen to decrease, but other tensile strength, stiffness, and tearability are not affected.

【table】

Claims (1)

[Scope of Claims] 1. A flame retardant treatment agent containing a methylolated product of diguanidine phosphate as an active ingredient, to which one or more compounds selected from cyclic alkylene ureas, amino compounds, or amides are added. A flame retardant treatment agent that releases less formaldehyde. 2. The flame retardant treatment agent according to claim 1, wherein the methylolated product of diguanidine phosphate is a product obtained by reacting 1 mole of diguanidine phosphate with 0.5 to 4 moles of formaldehyde. . 3. The flame retardant treatment agent according to claim 1, which contains diguanidine phosphate and/or guanidine sulfamate in addition to the methylolated diguanidine phosphate. 4. The flame retardant treatment agent according to claim 3, wherein the ratio of the methylolated diguanidine phosphate to the total amount of diguanidine phosphate and guanidine sulfamate is 5 to 50% by weight.