JPS6040120A - Flame-retardant polyurethane resin - Google Patents

Abstract

PURPOSE:The titled resin obtained by using a novel halogen-containing diol as a flame-retardant as part of a polyol component, having improved resin properties since it has improved solubility of the diol in the polyol component, showing improved flam retardance durability. CONSTITUTION:A polyethoxylated tetrabromobisphenol A having 3-6 average addition moles is used as part of a polyol component, and the polyol component is reacted with an isocyanate component, to give the desired resin. Preferably 3-50pts.wt. polyethoxylated tetrabromobisphenol A is dissolved in 100pts.wt. other polyol component and used.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a flame-retardant polyurethane resin comprising a novel halogen-containing diol as a part of the polyol component, more specifically a polyethoxylated tetrabromo resin having an average number of added moles of 3 to 6. This invention relates to a flame-retardant polyurethane resin using bisphenol A.

Polyurethane resin is manufactured by the reaction of a polyol component and a polyincyanate component, and due to its unique performance, it is used in an extremely wide range of fields such as rigid, semi-rigid or soft spongy foams, urethane resin molded products, paints, rubber, fibers, etc. However, because it is inherently flammable, it is often unsuitable as it is for applications where flame retardancy or non-combustibility is desired, such as building materials, electrical product materials, vehicle parts, etc. 0 Therefore, various methods for making polyurethane resin flame retardant have been proposed, but on the other hand, this kind of flame retardancy has become an increasingly important issue in response to the direction of stricter regulations and the demand for metal substitution for resins. Despite this, the current situation is that there is no industrially advantageous product that satisfies the technical requirements.

Conventionally, two types of flame retardant methods for polyurethane resins are well known: those using additive flame retardants and those using reactive flame retardants. At present, additive-type flame release agents are often used because they are easy to handle and have little effect on the physical properties of the resin.

As additive flame retardants, phosphorus-based halogen-based flame retardants and halogen-based flame retardants are known, and phosphorus-based phosphorus-based halogen-based flame retardants include phosphoric triester such as tricresyl phosphate, triphenyl phosphate,
Tris(2-1'loloethyl)phosphate, tris-
2,3-dichloropropyl phosphate, tris-2,
Examples of halogenated flame retardants include tribromophenol, hexabromobenzene, decabromonaphthalin, and tetrabromobisphenol A.

However, all phosphoric acid triesters are susceptible to hydrolysis, and are easily hydrolyzed by trace amounts of coexisting moisture or moisture in the air, producing acidic partial phosphate esters, which can lead to resin deterioration and It has drawbacks such as the flame retardant leaching onto the resin surface and falling off.

Most halogen-based flame retardants are powder products, which makes it difficult to disperse them uniformly into the resin, or they tend to leach onto the surface due to poor compatibility with the resin, or they tend to evaporate and evaporate gradually even under natural conditions. However, when the resin is stored for a long period of time, its flame retardancy is significantly reduced.

In order to avoid the drawbacks of these additive flame retardants, we use bisethoxylated bisphenol A and tetrahydrogen as reactive flame retardants that have active hydrogen groups in their molecules and take into account their reactivity with incyane-1-groups. Bromo terephthalate, etc.

However, these are all crystalline solids with high melting points and are difficult to dissolve uniformly with the polyol component and polyisocyanate component, making it difficult to use them advantageously in existing processes.

In view of the above-mentioned circumstances, the inventors of the present invention have conducted intensive research to solve the conventional difficulties and obtain a technically and industrially advantageous flame-retardant polyurethane resin. Ethoxylated tetrabromobisphenol A is a primary polyol component that imparts flame retardancy, and since it is liquid itself, it is easy to handle when added to a reaction system, and is highly soluble in polyol components and polyisocyanate components. The present invention was achieved based on the discovery that the polyisocyanate component has properties, is easily homogenized, and reacts with the polyisocyanate component.

That is, the present invention provides a polyurethane resin obtained by the reaction of a polyol component and a polyisocyanate component, wherein the average number of moles added as part of the polyol component is 3.
-6 polyethoxylated tetrabromobisphenol A
The present invention provides a flame-retardant polyurethane resin made using the following.

The halogen-containing diol used in the present invention can be obtained by subjecting tetrabromobisphenol A to an addition reaction with ethylene oxide in the presence of an alkali or acidic catalyst. The distribution of the number of moles of ethylene oxide added and the number of moles of ethylene oxide added at this time has a large influence on the flame retardance and other physical properties of the polyurethane resin using the ethylene oxide-containing diol. The average number of moles of ethylene oxide added for the purpose of the present invention is 3 to 6. From the viewpoint of homogenizing the reaction with the incyanate component, a chlorine-containing diol having an average number of added moles of 3 to 6 and having 3 to 6 moles of adduct in an amount of 70% or more by weight is more preferable.

When the average number of moles of ethylene oxide added to the halogen-containing diol is less than 3, the obtained halogen-containing diol will be solid or close to it, and the presence of tetrabromobisphenol A, which is a raw material, will often be observed, and polyurethane In any case, it is undesirable because the uniform reactivity is extremely poor when obtaining a resin, and there is a mixture of substances with different reaction rates. In addition, when the average number of moles of ethylene oxide added to the halogen-containing diol exceeds 6, the obtained halogen-containing diol is liquid and has good uniform dispersibility, but the flame retardance of the polyurethane resin in which it is used may be affected. The purpose of addition, the rodan content, decreases, and a large amount of addition is required to impart the desired flame retardancy9.
As a result, there are many drawbacks such as unfavorable effects on the physical properties of the resulting polyurethane resin.

The method for producing polyurethane resin is already well known to experts in this field, and the flame-retardant polyurethane resin using the halogen-containing diol according to the present invention can also be produced by the following conventional method. That is, in polyurethane foams, polyol components having at least two active hydrogen groups in the molecule, such as polyether polyols obtained by the reaction of polyhydric alcohols and alkylene oxides, or polybasic carboxylic acids and polyhydric alcohols, are used. 1 of the polyester polyol obtained by reaction with
00 parts by weight, dissolve 1 to 60 parts by weight, preferably 3 to 50 parts by weight, of the halogen-containing diol of the present invention, and add a foam stabilizer, an amine-based foaming catalyst, and, if necessary, an organometallic-based foam to the solution. A polymerization catalyst and a blowing agent are added and mixed with stirring, and this mixture is reacted with a polyisocyanate component such as tolylene diisocyanate, diphenylmethane diisocyanate, phenylene diisocyanate, xylene diisocyanate, cyclohexyl diisocyanate, hexamethylene diisocyanate, etc. A polyurethane foam is obtained. And at this time,
By appropriately selecting the combination of the polyol component and the polyinsyanate component, a soft, semi-rigid or rigid polyurethane foam can be obtained. The same applies to flame retardation of polyurethane elastomers, polyurethane paints, etc. In producing these flame-retardant polyurethane resins, the required number of halogen-containing diols for flame retardancy is appropriately changed depending on the use of the flame-retardant polyurethane resin to be produced, the desired properties thereof, and the like.

The flame-retardant polyurethane resin of the present invention thus obtained is
Compared to conventional polyurethane resins made flame retardant with additive flame retardants such as phosphoric acid triester and hexabromobenzene, it is particularly superior in flame retardant persistence, that is, flame retardancy when stored for a long period of time. The halogen-containing diol of the present invention has much better solubility in polyol components than conventional reactive flame retardants such as bis-ethoxylated bis-7E, Nord A, etc., and improves the physical properties of the resulting polyurethane resin. It is also excellent in terms of

Hereinafter, the present invention will be described in more detail with reference to Examples, but the present invention is not limited thereto.

・Adjustment of flame retardant The flame retardants listed in Table 1 were prepared.

Table 1 Note: F-1 to F-7 are polyethoxylated tetrabromobisphenol; AXF-8 is) lichlorethyl phosphate. EO is ethylene oxide. The person in charge is a weight dumpling. Average E
The number of moles of O addition and 3 to 6 moles of EO addition adduct were measured by liquid chromatography.Test Category 1 A flexible polyurethane foam was prepared using the flame retardant adjusted in Table 1, and its flame retardant properties were determined. etc. were evaluated. law treatment,
The ordering method and evaluation method are as follows. The results are shown in Table 2.

(1) Foaming treatment note) Silicone DC is a silicone activator manufactured by Dow Chemical Company.

(2) Foaming method Add the flame retardants F-1 to F-8 to commercially available PPG-3000, and after equalization, add silicone DC as a foam stabilizer and a triethylenediamine aqueous solution (triethylene,
diamine with water) and mix well,
Tolylene diisocyanate was added and stirred for 5 seconds to obtain a foam, which was then cured at 120° C. for 1 hour.

(3) Evaluation method 1) Combustion test: American Standard of Testing Method
D1692-68 (hereinafter abbreviated as ASTM) and Motor Vehicle 5afe'ty Standard 16302 (
(hereinafter abbreviated as MVSS), all were evaluated in terms of combustion distance. The distance of the test piece from the first marked line to the second marked line is 10c111 for ASTM and 2 for MVSS.
5.4 C11l.

11) Scorch: The degree of coloring of the foam at the time of manufacture was evaluated as: 0 - same level as blank without discoloration), Δ = slightly colored.

111) Appearance: The produced foam was cut and the beauty of the cut surface and the uniformity of the bubbles were evaluated: ◎ = beautiful cut surface and close to uniform foaming, Δ - cut surface is slightly rough, × - cut surface It was rated as "rough".

-Test Category 2 Rigid polyurethane foam was created using the flame retardant prepared in Table 1, and its flame retardance etc. were evaluated. foaming treatment,
The foaming method and evaluation method are as follows. The results are shown in Table 3.

Note) *1-Mitsui Toatsu Chemical Co., Ltd., l) PG-S
U-450Lo*2 = Manufactured by Fujidori (USA), DAB
CO-33LVo*3 - Same as test category 1. *4-MDI CR manufactured by Mitsui Toatsu Chemical Co., Ltd.

(2) Foaming method Add the above flame retardant F-1 to the commercially available rigid polyether polyol.
~F-8 was added, and after homogenization, Series-1-7DC,
g) Ethylenediamine catalyst, dimethylmethanolamine, and trifluoromethane were added and mixed well, then diphenylmethane diisocyanate was added and stirred for 15 seconds to obtain a foam, which was then cured at 120° C. for 1 hour.

(3) Evaluation method The combustion test and appearance were conducted in the same manner as in Test Category 1.

-Test results The results of the aforementioned test categories 1 and 2 are shown in Tables 2 and 3, respectively. In each table, actual examples are shown, ratios are comparative examples, and blanks are those in which no flame retardant is used.

Table 2 (Results of test category 1) Note) Parts are parts by weight. Ratio 1 indicates that the flame retardant precipitated in the system and it was not possible to obtain a good foam. Ratio 4 is the same as ratio 1 in Table 2.

As is clear from the results in Tables 2 and 3, the polyurethane foam (actual) according to the present invention is

It can be seen that the material also exhibits good flame retardancy.

Claims (1)

[Scope of Claims] 1. A polyurethane resin obtained by the reaction of a polyol component and a polyisocyanate component, which uses polyethoxylated tetrabromobisphenol A having an average added mole number of 3 to 6 as part of the polyol component. Flame-retardant polyurethane resin. The flame-retardant polyurethane resin according to claim 1, which uses polyethoxylated tetrabromobisphenol A in which the proportion of polyethoxylated tetrabromobisphenol A having a mole number of 3 to 6 is 70% by weight or more.