JPS58225116A - Highly flame-retardant, low-smoke-polluting polyurethane resin composition - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a high kojicho low smoke pollution f1 polyurethane resin composition, which has particularly high flame retardancy, generates little smoke when exposed to flame, and solidifies without melting and dripping. There are some related to polyurethane Φ tan resin compositions.

Methods for making polyurethane resin made by reacting polyisocyanate and polyol with -C include adding a flame retardant, using a reactive flame retardant polyol, and modifying the structure of the urethane resin. is known C
There is.

In the method of adding a flame retardant, C is an organic or inorganic flame retardant;
There are halogen-containing phosphorus compounds and nitrogen-containing phosphorus compounds, and the latter include metal oxides and hydroxides. iNI type fuel agent C
is a cognate phosphoric acid, for example, Tris(2).
Typical examples that have good compatibility with urethane raw materials include -chloro'-del)noAsufuL-to, tris(chloropropylene)phosphate, and 1-lis(2,3-dibromob [Jpil) Δsufuto. However, these are low molecular weight liquids that may transfer to the materials they come in contact with and have an adverse effect on C.
It has the disadvantage that it evaporates when the temperature rises, reducing the wholesale combustion effect. In addition, powdered compounds containing halogens, such as decabromodiphenyl needle and deli-Denbras, do not have problems with migration or volatilization, but on the other hand, they emit a large amount of smoke when exposed to flame, and are also toxic. It has the disadvantage of generating corrosive hydrogen-containing gas.

The method of using reactive flame-retardant polyols exhibits the feature of long-lasting flame retardancy, but flame-retardant polyols contain phosphorus, halides, nitrogen, etc. in their molecules, and are different from ordinary polyols in terms of isocyanate and flame retardant polyols. Many of them have significantly different reactivities, and a composition that provides stable processability and a good characteristic f1 cured resin is still not sufficiently known.

Flame retardant methods by structural modification of urethane resins include introducing heat-resistant structures such as isocyanure-1 to M, imide groups, A-kyrizolidone groups, and carbodiimide groups into the molecular structure;
1) It is possible to use raw materials that have heat resistance and form a structure when flame retardant.

By the way, flame retardancy due to structural modification (Fuji C) has the disadvantage that the cured product becomes hard and brittle, and a soft elastic cured product, which is one of the characteristics of polyurethane resins, cannot be obtained.

As mentioned above, each of the conventional techniques used to make polyurethane resin flame retardant has its drawbacks, and C is still insufficient for polyurethane resin compositions that are 8 degrees flame retardant and have low smoke pollution. Nothing has been proposed.

The practical application of the above-mentioned flame retardant polyurethane resin is being carried out mainly for polyurethane foam.
Work t! 1. Due to the different characteristics required for cured resins, the technical knowledge of flame retardant polyurethane foam cannot often be applied to non-foamed systems.

The present invention has been made in view of the above, and its objectives are to improve the workability of injection impregnation, coating, etc., to have high flame retardancy, low smoke generation even when exposed to flame, and The object of the present invention is to provide a polyurethane resin composition with high fuel efficiency and low smoke pollution, which becomes a solidified product without being melted and dripped.

・i The feature of the present invention is that diezyl N, N-1jisu (2-human [
A polyol component consisting of a phosphorus-containing polyol mainly covering 1-xylene diisocyanate) aminomethylphosphone-1, a polyisocyanate component mainly consisting of a trimer of hexylene diisocyanate, a flame retardant mainly consisting of hydrated alumina, and It is composed of other compounding agents, and 150 to 400 parts by weight of the flame retardant -C is added to the total i1100 parts of the polyol component and the polyisocyanate component.
The point is that it is a polyurethane resin composition.

Here, the polyol component used in the present invention has a molecular concentration of 2.
55, a low viscosity liquid C with a specific gravity of 1.16 (25°C), a phosphorus content of 12%, and a viscosity of 185 CPS (25°C). The polyisocyanate component is a liquid with a viscosity of about 2000 CPS at 25°C, which is mainly composed of trimer of hexylimebulene diisocyanate, and contains a small amount of monomer and Industrial products containing other substances can be used as they are.The flame retardant is an inorganic flame retardant mainly composed of hydrated alumina, but the amount is less than the equivalent of hydrated alumina (less than 50% by weight of the total inorganic flame retardant).
It is also possible to use a combination of inorganic flame retardants such as magnesium hydroxide, zinc borate, and ammonium polyphosphate.

Note that it is important to select the particle size and distribution of the °C-free Ia flame-informing agent in consideration of addability (workability). Grain I (
If it leans toward the small side, the viscosity of the composition will become significantly lower,
Work efficiency decreases and practicality becomes poor. An example of the particle size distribution of hydrated alumina suitable for the composition of the present invention is 74
45% by weight of particles of ~150μIn, 44-74μTn,
25% by weight of particles of 4/lμyn or less, 30% by weight of particles of 4/l μyn or less
There is something that consists of

The present invention uses diethyl N. This does not preclude the use of polyols other than N-bis)2-human['xyedyl)aminomethylphosbonate, and the amount of
It is preferable to use other combustible polyols or ordinary polyols in a proportion less than % by weight.

In addition, as a polyisocyanate component, a trimer of hexylimethylene diisocyanate is used together with Schiff's methane diisocyanate, diphenylmethane diisocyanate liquefied by carbodiimidation modification, a low polycondensate of aniline and formaldehyde, and a reaction with phosgene. Yotsu(
The obtained polynuclear polyisocyanate 1- (so-called crude M, DI or polymeric polyisocyanate) may be used in combination with diethyl N, N=-bis(
Since it reacts rapidly with 2-hydroxyethyl)aminomethylphosphonate and significantly shortens its pot life, the usable amount is itself limited to a small amount.

The polyurethane composition of the present invention basically contains the above three components within a specific range, but other components may be added as necessary.

For example, a coloring agent, a curing accelerating catalyst, an inorganic material fiber, a drawing agent, a non-reactive organic flame retardant, etc. may be used within a range that satisfies the properties.

The ratio of the Polymer component to the polyisocyanate component is such that the ratio of hydroxyl groups to isocyanate groups is 0.6 to 1.
It may be selected as appropriate within the range of 2, taking into consideration workability and properties of the cured product.

Next, specific examples and comparative examples will be described. , 1st
The table shows the ingredients and their proportions in Examples 1 to 6 and Comparative Examples 1 to 4, and Table 2 shows the ingredients and proportions in Examples 7 to 10 and Comparative Examples 5.6. The first
Table 2 shows the initial viscosity before curing, pot life,
The measurement results of workability evaluation, oxygen index after curing, smoke emission coefficient, melt dripping during combustion, and comprehensive evaluation of flame retardancy and low smoke emission are also listed. Comparative examples are shown for reference.

The oxygen index was measured by C according to the JIS K7201 oxygen index method for combustion testing of polymer materials.

The smoke emission coefficient was determined according to JIS Δ1321 Flame retardant test method for building interior materials, using test specimens in which each composition was applied at a rate of 1500 g/m2 to a 220 x 200 x 1 mm steel plate and left at room temperature for 2 days to harden. A surface test was carried out as specified in 11, and the smoke generation coefficient (CA) per area was determined. (j) The smoke conversion coefficient was determined from the following formula by heating the smoke generated when heated in a specified heating furnace in an east smoke box, measuring the intensity of light with a light intensity measuring device.

Therefore, the smaller the smoke generation coefficient, the less smoke generation.

CA = 24011o Q to to / I −
-----(1) Here, 1o: Scariness of light at the start of heating test Lx) I: Minimum value of light intensity during heating test (x) Melt dripping during combustion is 10 #l #IX 10m x 30m
A hardened sample of M was prepared and a combustion test was conducted at 1000°C for 10 minutes using a Bunsen bar with an inner flame adjusted to 30 mm and an outer flame adjusted to 127 mm to determine whether assimilation was insufficient and there were melt droplets during combustion. . In addition. The property tests after curing were conducted after being left at room temperature for 5 days.

tllF before +7) nJ Envoy III G, L, 1
00,000 cps is the workable time, and the viscosity is measured at 25°C with a B-type rotational viscometer, and the viscosity is 1,000 cps.
The time required to reach 00 cps was determined.

Regarding Examples 1 to 6 and Comparative Examples 1 to 4, each blended raw material except for polyisocyanate 1 was collected in a beaker at the blending ratio as shown in Table 1, and after mixing for -1 minute, polyisocyanate (power After stirring thoroughly, the mixture was poured into a mold and allowed to harden at room temperature.
1 to measure the initial viscosity and pot life. The smoke generation coefficient measurement test was made by installing a frame around the steel plate to prevent C from flowing out, and applying and curing U at a rate of 1500 g/bottom.

As can be seen from the measurement results in Table 1, the compositions of Examples 1 to 6 were extremely superior in terms of workability, flame retardancy of cured products, low smoke f1, and no melt dripping during combustion. There is.

On the other hand, when Composition I31 of Comparative Example 1 for C reference and Crude MD1 were mixed, there was a rapid exothermic reaction and hardening occurred for about 1 minute, resulting in extremely poor workability. Comparative example 1
The composition of C has good workability due to the small amount of hydrated alumina blended, but is inferior in flame retardancy and smoke generation compared to Examples 1 to 6. The composition of Comparative Example 3 did not flow because the amount of hydrated aluminum was too large, and it was difficult to pour, impregnate, and apply it.
I can't wait to do these tasks. The composition of Comparative Example 1 is a non-reactive liquid gas refueling agent C1-RinoL NilnoA SunoT
-1- It is effective in preventing the spread of fire in the event of a fire because there are many molten droplets during combustion.
I can't come.

As for Examples 7 to 10 and Comparative Examples 55 and 6, as shown in Table 2, the composition of Example 7 was
''-bis(2-human[1xytodel)amizmedel phosphonate with 4 Jt of another flame-retardant polyol, and the composition of Example 8 was prepared by adding dibdel to the composition of Example 7 as a curing accelerating catalyst. Tin dilaurate is added, Example 9
The compositions used are those using ordinary polyols, and Examples 7 to 10 had good characteristics similar to Examples 1 to 6.
Show 1. On the other hand, Comparative Examples 5 and 6 are inferior to the compositions of Examples in terms of workability and flame retardancy.
11 As explained above, according to the present invention, the workability of injection impregnation, coating, etc. is poor, and it has high flammability,
Even if it comes in contact with flame, it will emit smoke and become an assimilate without melting and dripping, so it can be expected to have a fire spread prevention effect. It has the effect of providing a polyurethane composition suitable as a polyurethane composition.

Claims (1)

[Claims] In a polyurethane resin composition comprising a polyol component, a polyisocyanate component, a retardant, and a combination thereof, the polyol component is diethyl N, N'-bis(
A phosphorus-containing polyol mainly composed of 2-hydroxy 1 del) amizmedel small sulfonate], the polyisosyphnate component is mainly composed of a trimer of hexamethylene diisocyanate 1, and the flame retardant is hydrated alumina. 150 to 40,011 parts of the above flame retardant are added to 100 parts by weight of the polyol component and the polyisocyanate component. Low smoke pollution polyurethane resin composition.