JPH04117416A - Polyol composition containing dispersed melamine for flame-retarding polyurethane - Google Patents

Abstract

PURPOSE:To obtain the title composition useful as a starting material for obtaining a polyurethane of excellent flame retardancy at good efficiency on an industrial scale by mixing a polyol with melamine, a specified dispersant and water. CONSTITUTION:The title composition is obtained by mixing 100 pts.wt. liquid polyol with 20-150 pts. wt. powdery melamine of a mean particle diameter of 30-50mum, 0.1-5 pts.wt. dispersant selected from among an alkanolamide nonionic surfactant, a higher alcohol ethoxysultate salt anionic surfactant and an amino acid salt anionic surfactant and 0.2-4 pts.wt. water.

Description

Detailed Description of the Invention [Industrial Application Field 1] The present invention relates to a melamine-dispersed polyol composition for flame-retardant polyurethane, more specifically, to a melamine-dispersed polyol composition for use in flame-retardant polyurethane. The present invention relates to a homogeneously dispersed polyol composition.

[Conventional technology] In recent years, the demand for flame retardancy in industrial materials has been increasing from the point of view of ensuring safety. Polyurethane materials are also being treated with halogen-based, organic Attempts have been made to add flame retardants such as phosphorus, antimony, and inorganic flame retardants.

However, halogen-based flame retardants have drawbacks such as corrosion of equipment, discoloration of materials, and odor problems during manufacturing, and organic phosphorus-based flame retardants have plasticity, so products are It is inevitable that your back will become weak and your use will be limited. In addition, antimony-based flame retardants have the disadvantage of being difficult to mix homogeneously and are hard when used with 7-ohm urethane. When producing the upper foam, it has disadvantages such as poor foaming and poor flame retardancy.

Therefore, recently, melamine has attracted attention as a retardant for polyurethane due to its excellent flame retardant properties and other properties, and attempts have been made to use it (Japanese Patent Application Laid-open No. 1522-15222).
No. 0, Japanese Patent Application Laid-open No. 6248717). However, since this melamine is a powder, when it is added during the production of polyurethane on an industrial scale, it inevitably reduces work efficiency and has the disadvantage that it does not dissolve in polyols. In order to improve these drawbacks of melamine, attempts have been made to use melamine as a derivative (Japanese Unexamined Patent Publication No. 5,589,327). However, in this case, the problem arises that the effect of imparting flame retardancy is not sufficiently exhibited and the cost is inevitably high.

[Problem to be solved by the invention] Under these circumstances, the present invention is a method for homogeneously dispersing melamine, which is used as a raw material to efficiently provide polyurethane with excellent flammability properties on an industrial scale. This is a product made for the purpose of providing a liquid polyol composition.

[Means for Solving the Problems] As a result of intensive research to develop a melamine-dispersed polyol composition having the above-mentioned preferable properties, the present inventors found that melamine, a specific dispersant, and water were added to a polyol. It was discovered that the objective could be achieved by a composition in which each of these components was blended in a predetermined ratio, and the present invention was completed based on this knowledge.

That is, the present invention includes (A) 100 parts by weight of polyol, (B) 20 to 150 parts by weight of melamine, (C) an alkanolamide type nonionic surfactant, a higher alcohol ethoxysulfate salt type anionic surfactant, and For flame-retardant polyurethane, comprising 0.1 to 5 parts by weight of at least one dispersant selected from amino acid salt type anionic surfactants, and (D) 0.2 to 4 parts by weight of water. A melamine-dispersed polyol composition is provided.

The present invention will be explained in detail below.

In the composition of the present invention, the polyol used as component (A) is not particularly limited as long as it is liquid, and may be selected from among liquid polyether polyols, polyester polyols, etc. that have been conventionally used as raw materials for polyurethane. Any one can be selected and used. In addition, the amount of melamine blended depends on the viscosity of this liquid polyol, and in general, low viscosity polyols can contain a large amount of melamine, but stability is often a problem, so choose one with an appropriate viscosity. This is desirable.

In the composition of the present invention, one type of polyol as component (A) may be used, or two or more types may be used in combination.

In the composition of the present invention, melamine is used as component (B). This melamine is used to impart flame retardancy to the resulting polyurethane.The flame retardant effect is due to the fact that it produces carbon when ignited, making it difficult for embers to fall, and also because it acts as a thermal insulator. It is said that.

The melamine may vary depending on the manufacturing method, but
Generally, powder having an average particle diameter of about 30 to 50 μm is used. Of course, it is also possible to use particles with a particle size as low as several micrometers obtained by chemical or physical methods, but although such fine particles have good dispersion stability, the amount of It is disadvantageous when using in large quantities or in terms of cost.

The blending amount of melamine as the component (B) in the composition of the present invention is based on 100 parts by weight of the polyol as the component (A).
It is necessary to select the amount within the range of 20 to 150 parts by weight. If this amount is less than 20 parts by weight, the effect of imparting flame retardancy will not be sufficiently exhibited, and if it exceeds 150 parts by weight, the viscosity of the resulting composition will become too high, resulting in poor handling and workability, as well as physical properties of polyurethane. There is a tendency to have negative effects on

In the composition of the present invention, a dispersant is used as component (C) in order to homogeneously disperse the melamine in the polyol. As the dispersant, at least one selected from alkanolamide type nonionic surfactants, higher alcohol ethquin sulfate salt type anionic surfactants, and amino acid salt type anionic surfactants is used.

The dispersant is preferably one that has excellent electrical affinity for the melamine to be dispersed and provides strong electrical repulsion to the particles covered by it, and from this point of view, the anionic surfactant is advantageous. be. Furthermore, when using the composition for polyurethane foam, it is important that the composition does not impair the performance of the foam, and from this point of view, the nonionic surfactant is advantageous. Therefore, it is desirable to select an appropriate dispersant from among the above-mentioned surfactants depending on the use of the polyurethane.

Examples of the alkanolamide type nonionic surfactant include 1:2 type coconut fatty acid jetanolamide, 1
: l-type coconut fatty acid jetanolamide, 1: l-type lauric acid jetanolamide, 1: type 1 myristic acid jetanolamide, 1: l-type oleic acid jetanolamide, 1: type lauric acid monoethanolamide, Examples include type 11 lauric acid monoisopanolamide.

In addition, examples of higher alcohol ethquin sulfate salt type anionic surfactants include sodium salts and triethanolamine salts obtained by adding 2 to 10 moles of ethylene oxide to lauryl alcohol, triethanolamine salts, and 2 to 10 moles of oleyl alcohol. Examples of amino acid salt-type anionic surfactants include sodium salts and ammonium salts obtained by adding ethylene oxide to sulfate esters, and examples of amino acid salt type anionic surfactants include N-cocoyl-N-methyl-β-alanine sodium salt, -Methyl-β-alanine sodium salt, N-myristoyl-N-methyl-β
-Alanine sodium salt and the like.

In the composition of the present invention, one type of dispersant as the component (C) may be used, or two or more types may be used in combination.
The amount is selected in the range of 0.1 to 5 parts by weight per 00 parts by weight. If this amount is less than 0.1 part by weight, there is a risk that the melamine will become a hard cake and settle, and if it exceeds 5 parts by weight, the effect of improving dispersibility will not be noticeable considering the amount.

In the composition of the present invention, it is necessary to add water as an anti-settling agent in order to further improve the dispersion stability of melamine for the purpose of long-term storage. In this case, the amount of water added is selected in the range of 0.2 to 4 parts by weight per 100 parts by weight of the polyol as the component (A). This addition of water is advantageous when the composition is used for polyurethane foams, since the carbon dioxide generated by the reaction between water and the isocyanate compound contributes to foaming.

Regarding the addition of water, when an anionic surfactant is used as a dispersant, it may be added as an aqueous solution thereof.

If the amount of water added is less than 0.2 parts by weight, the effect of improving dispersion stability will not be sufficiently exhibited, and if it exceeds 4 parts by weight, there is a possibility that it will have an adverse effect on the production of polyurethane.

By adding water in the above range, the composition has extremely good dispersion stability of melamine, and sedimentation of melamine is suppressed even after long-term storage, which is extremely advantageous industrially.

Melamine resins, melamine derivatives, and other flame retardants may be added to the melamine-dispersed polyol composition of the present invention, as desired, within a range that does not impair the purpose of the present invention.

There are no particular restrictions on the formation of polyurethane foam;
Using the melamine-dispersed polyol composition of the present invention, it can be carried out using raw material compositions and methods conventionally used in the production of rigid or flexible polyurethane foams.

Further, foaming is usually performed using carbon dioxide generated by a reaction between water and an incyanate compound such as tolylene diisocyanate or diphenylmethane diisocyanate. At this time, there are no particular restrictions on the foam stabilizer and reaction catalyst that may be used as desired, and those conventionally used in the production of polyurethane foams can be used.

By using the melamine-dispersed polyol composition of the present invention, it is possible to industrially and efficiently produce polyurethane with excellent study properties.

[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 in any way.

The symbols for polyol, melamine, and dispersant have the following meanings.

(1) Polyol I; Efcenol 828 (manufactured by Asahi Glass Co.) ■: Polanol 3022J (manufactured by Dow Chemical Company) ■: Pluronic L
-64 (manufactured by Asahi Denka Co., Ltd.) IV: PPG3000 V: PEG400 (2) Melamine a general melamine (manufactured by Yuka Melamine Co., Ltd.) b general melamine (manufactured by Nissan Chemical Industries, Ltd.) (3) Dispersant A: 1:2 Palm fatty acid jetanol amidronilauryl alcohol etquin sulfate sodium salt (EO
2 molar adduct) C nioleyl alcohol ethoxysulfate ammonium salt (EOIO molar adduct) D2N-lauroyl-N
-Methyl-β-alanine sodium salt E: PEG200 Monolaurate F: Dodecylbenzelsulfonic acid sodium salt Practical example 1 For 100 parts by weight of polyol I, melamine a80
parts by weight, 1 part by weight of dispersant A and 1 part by weight of water as an anti-settling agent.
Add part by weight and mix with a disper disperser at 2000 rpm.
A melamine-dispersed polyol composition was prepared by mixing at m for 2 minutes, and the viscosity and dispersion stability of the composition were determined immediately and after storage for one month.

The viscosity was measured using a B-type viscometer (manufactured by Tokyo Keiki Co., Ltd.) with a No. 4 rotor, 6 rpm, and 60 rpm %20'
The measurement was performed under O conditions. Dispersion stability was expressed as a ratio to the total height of the melamine dispersed layer by placing a 100 mQ sample in a test tube with an inner diameter of 3.5 mm. These results are shown in Table 1.

Next, 4 parts by weight of water (including the water added above) and 5H-190 (manufactured by Toshi Dow Corning Silicone) a foam stabilizer were added to the melamine-dispersed polyol composition per 100 parts by weight of polyol. 1 part by weight, 0.3 parts by weight of amine catalyst DABCO33LV (manufactured by Nippon Nyukazai Co., Ltd.), and 0.25 parts by weight of tin-based catalyst T-9 (manufactured by El Tokasei Co., Ltd.).
Add 2 parts by weight using a disperser disperser.
After mixing for 2 minutes at 00 Orpm, 50 parts by weight of tolylene diisocyanate "Coronate T-1oo" (manufactured by Nippon Polyurethane Kogyo Co., Ltd.) was added thereto, and the mixture was mixed at 200 Orpm.
The mixture was mixed for several seconds and put into a wooden box, and after the foaming became stable, it was cured in an oven at 150°C for 10 minutes to obtain a polyurethane foam.

In this case, the condition was compared with the polyurethane foam produced when a polyol not containing melamine was used, and the foaming stability was judged by ○X.

The results are shown in Table 1.

Examples 2 to 14, Comparative Examples 1 to 3 Melamine-dispersed polyol compositions having the compositions shown in Table 1 were prepared in the same manner as in Example 1, and the viscosity and dispersion stability were determined immediately after preparation and after storage for one month. Ta.

The results are shown in Table 1.

In addition, Example 4.5.6.9.10.13 and Comparative Example 1
．． Regarding No. 3, a foam was prepared in the same manner as in Example, and the foaming stability was determined. The results are shown in Table 1.

Comparative Example 4 A melamine-dispersed polyol composition was prepared in the same manner as in Example 5, except that no dispersant and water were used. In this case, the melamine settled as a hard cake and was not homogeneously dispersed.

A foam was prepared from this composition in the same manner as in Example 5, and the foaming stability was determined. The results are shown in Table 1.

Comparative Example 5 A melamine-dispersed polyol composition was prepared and evaluated in the same manner as in Example 5, except that water was not used. The results are shown in Table 1.

(The following is a blank space) [Advantageous Effects of the Invention 1 The melamine-dispersed polyol composition of the present invention has a composition in which melamine is added to a liquid polyol together with a specific dispersant and water to disperse the melamine homogeneously and with good stability. It has excellent long-term storage stability, and by using this material as a raw material for polyurethane, it is possible to industrially produce polyurethane with excellent flame retardant properties compared to the conventional technology that uses melamine powder as a flame retardant for polyurethane. It can be manufactured efficiently.

Claims (1)

[Claims] 1 (A) 100 parts by weight of polyol, (B) 20 to 150 parts by weight of melamine, (C) alkanolamide type nonionic surfactant, higher alcohol ethoxy sulfate salt type anionic surfactant, and amino acid salt type anionic surfactant A melamine-dispersed polyol composition for flame-retardant polyurethane, comprising 0.1 to 5 parts by weight of at least one dispersant selected from surfactants, and (D) 0.2 to 4 parts by weight of water. .