JPH09310016A - Flame retardant composition for flexible polyurethane foam - Google Patents

Abstract

(57) Abstract: A novel flame retardant is provided for a flexible polyurethane foam. In a flame retardant composition for flexible polyurethane foam, component (a) dibromoneopentyl glycol (DBNPG), component (b) tribromoneopentyl alcohol (TBNPA), and component (c) flame retardant organic phosphorus compound The total amount of the component (a) and the component (b) is 1 to 30 parts by weight with respect to 100 parts by weight of the total composition, and these are dissolved in 99 to 70 parts by weight of the component (c). And the proportion of component (a) is 95 to 50 parts by weight and the proportion of component (b) is 5 to 50 parts by weight, with the total amount of component (a) and component (b) being 100 parts by weight. A composition comprising:

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a flame retardant composition for imparting flame retardancy to a flexible polyurethane foam.

[0002]

Flexible polyurethane foams made from polyols and isocyanates are relatively inexpensive to obtain,
In addition, since it has characteristics such as excellent moldability, it is used in cushioning materials for automobiles, interior materials, furniture such as beds and sofas, and many other fields. However, polyurethane foam is generally a flammable substance, and imparting flame retardancy to the polyurethane foam is an important issue from the viewpoint of disaster prevention when used for the above applications. Today, in some fields of application of polyurethane foam such as automobile cushioning materials and interior materials, flame retardation is obligatory.

As a method of imparting flame retardancy to a polyurethane foam, a method of adding a flame retardant at the time of producing a polyurethane foam is generally taken, and various compounds have been proposed as the flame retardant. For example, halogen-containing phosphoric acid ester, halogen-containing condensed phosphoric acid ester, organic phosphoric acid ester such as triaryl phosphate, antimony trioxide, inorganic compound such as aluminum hydroxide, and DBNP
G, TBNPA (US Pat. No. 3,933,693, US Pat. No. 4,052,346 and US Pat. No. 4,363,882)
Etc. have been proposed.

However, each of these conventionally used flame retardants has problems, and is not always in a satisfactory state. That is, when inorganic compounds and DBNPG and TBNPA are used as flame retardants, since these compounds are solid at room temperature, in order to uniformly mix and disperse them in the polyurethane raw material, for example, the polyol component, another container or a special mixture is used. A device is required, the equipment becomes complicated, and a huge capital investment is required. Also TB
When NPA alone is mixed with a flame-retardant organophosphorus compound and added to a flexible polyurethane foam, this compound gives 7%.
Despite having a high bromine content of 3.8%, a polyurethane foam having a relatively high air permeability can be obtained, so that sufficient flame retardancy cannot be obtained.

When DBNPG alone is mixed with a flame-retardant organic phosphorus compound as proposed in US Pat. No. 4,363,882, a high flame-retardant effect can be obtained while having two hydroxyl groups in one molecule. It is involved in the polyurethane forming reaction and the closed-cell property becomes high, which causes deterioration of physical properties of the polyurethane foam, particularly compression residual strain, air permeability, etc., and the commercial value thereof decreases. The official name of DBNPG is 2,2-bis (bromomethyl) propane-1,3-
Since it is a diol and has a melting point of 110 ° C, its compatibility with flame-retardant organic phosphorus compounds is poor, and DBNP can be used at high concentrations.
When G is dissolved in a flame-retardant organic phosphorus compound, DBNPG crystals may precipitate in a short time depending on the type of the flame-retardant organic phosphorus compound.

Further, a halogen-containing aliphatic phosphate ester,
For example, tris- (chloroethyl) phosphate (hereinafter,
TCEP), tris- (chloropropyl) phosphate (hereinafter abbreviated as TCPP), tris- (dichloropropyl) phosphate (hereinafter abbreviated as TDCP), halogen-containing condensed phosphate ester, triaryl phosphate, etc. When used, it requires the addition of a large amount of flame retardant to impart the required flame retardancy, which hinders the urethane-forming reaction during foaming, making smooth foam formation difficult. It causes the inconvenience. For example, the inhibition of the urethane-forming reaction requires a long time from the start to the end of foam foaming, which not only lowers the productivity but also significantly lowers the physical properties of the foam produced and reduces its commercial value.

Further, in the production of slab foam, when the amount of these flame retardants added is large, heat generated by the urethane forming reaction is difficult to escape from the inside of the foam to the surface, and "burn" or scorch is generated in the central portion of the foam. There was a problem such as a significant decrease in product value.
As described above, the flame retardants proposed hitherto have some problems, and hitherto no sufficiently satisfactory flame retardant flexible polyurethane foam has been obtained.

[0008]

The present invention maintains that it is liquid at room temperature, is easy to add in the production of flame-retardant flexible polyurethane foam, does not inhibit the urethane-forming reaction, and has good physical properties. Flame retardant flexible polyurethane foam having specific properties is provided.

[0009]

Means for Solving the Problems The present inventors have overcome the above-mentioned drawbacks, retain a liquid state at room temperature, and do not inhibit the urethane forming reaction in the production of a flame-retardant flexible polyurethane foam, and As a result of various studies to develop a flame retardant composition for obtaining a flame-retardant flexible polyurethane foam having good physical properties, the inventors have found that the following flame retardant composition is effective and arrived at the present invention.

That is, the present invention provides a flame retardant composition for flexible polyurethane foams, wherein component (a) dibromoneopentyl glycol (DBNPG), component (b) tribromoneopentyl alcohol (TBNPA), and component (c) flame retardant. A total amount of the component (a) and the component (b) is 1 to 30 parts by weight, and these are 99 to 70 parts by weight of the component ( c), and the proportion of component (a) is 95 to 50 parts by weight and the proportion of component (b) is 5 based on the total amount of component (a) and component (b) being 100 parts by weight.
˜50 parts by weight.

In the case of dissolving DBNPG and TBNPA, it can be easily made into a solution at a temperature below the melting point by adding it to a flame-retardant organic phosphorus compound and heating and stirring at 60 to 70 ° C., and the solubility of TBNPA. It has been found that TBNPA also acts as a compatibilizing agent for the flame-retardant organic phosphorus compound of DBNPG because it is good, and can maintain a liquid state even after returning to room temperature. Also,
When added alone to a flame-retardant organophosphorus compound and dissolved,
DBNPG and TBNPA even though some TBNPA that does not necessarily exhibit sufficient flame retardancy is added
It was also found that the use of a mixture of 2 and 3 does not impair the flame retardancy obtained by adding and dissolving DBNPG alone.

[0012]

DETAILED DESCRIPTION The flame retardant composition provided by the present invention is characterized by suppressing the inhibition of foam forming reaction and providing a flame retardant flexible polyurethane foam having good physical properties. Here, DBNPG and TBNPA forming the flame retardant composition in the present invention may be any commercially available ones, and they are used as a mixture. Examples of commercially available products include dibromo neopentyl glycol (FR-1138 manufactured by Albemarle;
Bromochem Far East FR-522), tribromoneopentyl alcohol (Bromo Chem Far East FR-513) and the like.

Next, the other component forming the flame retardant composition, the flame-retardant organic phosphorus compound, is a halogen-containing organic phosphorus compound, a non-halogen organic phosphorus compound and oligomers thereof. Examples of halogen-containing organic phosphorus compounds include T
Monophosphates such as CPP, TCEP, TDCP,
2,2-Bis (chloromethyl) -1,3-propane-bis (chloroethyl) phosphate (2XC-20: manufactured by Akzo Nobel Chemicals, Inc.), diethylene glycol bis (chloropropyl) phosphate (Phiroll DPF: Akzo Kashima Co., Ltd.) And halogen-containing phosphoric acid ester oligomers (hereinafter abbreviated as DPF).

The non-halogen organophosphorus compound is triphenyl phosphate, tricresyl phosphate,
Aromatic phosphates such as cresyl diphenyl phosphate (hereinafter abbreviated as CDP), xylenyl diphenyl phosphate, resorcin bis (diphenyl phosphate), bisphenol A bis (diphenyl phosphate), bisphenol A bis (dicresyl phosphate), etc. Oligomer Aromatic Phosphate, Aliphatic Phosphate such as Triethyl Phosphate, Tributyl Phosphate, Aromatic Aliphatic Mixed Phosphate such as 2-Ethylhexyldiphenyl Phosphate, Decyldiphenyl Phosphate, Dimethylmethylphosphonate and Diethylethylphosphonate, and their Oligomers And the like (Phiroll 51 manufactured by Akzo Nobel).

These flame-retardant organic phosphorus compounds can be used alone or in admixture of two or more. DBNP
As a method for producing a flame retardant composition from G, TBNPA and the above-mentioned flame-retardant organic phosphorus compound, a predetermined amount of DBNPG and 60 ° C. to 70 ° C. are heated with stirring and a predetermined amount of DBNPG and TBNPA is gradually added to form a uniform flame retardant composition.

In this case, the mixing ratio of DBNPG, TBNPA and flame-retardant organophosphorus compound is such that the total amount of component (a) DBNPG and component (b) TBNPA is 100% by weight of the total composition.
It is dissolved in 99 to 70 parts by weight of the component (c) flame-retardant organic phosphorus compound in a ratio of 1 to 30 parts by weight with respect to parts by weight. Here, the mixing ratio of the component (a) and the component (b) is 95 to 50% by weight of the component (a) and 100% by weight of the component (a) and the component (b). 5-
Consists of 50% by weight.

Preferably, in the flame retardant composition for flexible polyurethane foam, the total amount of component (a) DBNPG and component (b) TBNPA is 10 to 20 parts by weight based on 100 parts by weight of the total composition. (C) The flame-retardant organic phosphorus compound is dissolved in 90 to 80 parts by weight.
Here, the mixing ratio of the component (a) and the component (b) is 95 to 50 wt% of the component (a) and 5 of the component (b) with the total amount of the component (a) and the component (b) being 100 wt%. -50% by weight.

When the content of DBNPG and TBNPA is less than 1 part by weight, the effect of addition as a flame retardant is not exerted, and when it is more than 30 parts by weight, the flame retardant composition keeps its uniformity at room temperature. It is not preferable because it causes difficulties such as difficulty. If desired, various additives can be added to the flame retardant composition of the present invention. Examples of the additive include antioxidants such as 2,6-di-t-butyl-4-methylphenol, hindered phenol compounds such as 2- (1-methylcyclohexyl) -4,6-dimethylphenol, and tris. Examples thereof include phosphite compounds such as (dinonylphenyl) phosphite and triphenylphosphite, and other stabilizers, colorants, pigments and the like.

[0019]

EXAMPLES Next, the present invention will be described more specifically by way of examples. In the examples, "parts" means "parts by weight" and means parts by weight per 100 parts by weight of polyol. In the examples, the rise time means the time from the start of foaming to the completion of foaming, and the results of each item of foam physical properties were measured according to the following measuring methods. Density: vertical, horizontal and 50 mm thick test pieces are taken from the center of the polyurethane foam. However, the thickness direction was the foaming direction, and the average value of three test pieces was calculated by the following formula.

[0020]

[Equation 1]

Compressive Residual Strain: A test piece having a square shape with a thickness direction of 50 mm or more and a thickness of 20 mm or more was compressed and fixed at 70 ° C. and RH 50% for 22 hours, and then released at room temperature for 30 minutes. Was measured and calculated by the following formula.

[0022]

[Equation 2]

Air permeability: Measured using a woven fabric air permeability tester (manufactured by Toyo Seiki Co., Ltd.). Flammability: Measured by the MVSS-302 flammability test method.

Example 1 55 parts of TDCP and 30 parts of TCPP were placed in a mixing vessel equipped with a stirrer and heating equipment, and heated to 60 ° C. with stirring. Here are 11 parts of DBNPG and TBNPA
4 parts was gradually added, and after all the DBNPG and TBNPA had been added, the mixture was kept at 60 ° C. for 1 hour. Then, the mixture was gradually cooled to room temperature to obtain a liquid flame retardant composition.

Examples 2 to 10 and Comparative Examples 1 to 6 55 parts of TDCP used in Example 1, TCPP
30 parts, 11 parts of DBNPG, and 4 parts of TBNPA were used instead of 4 parts of the compounds shown in Table 1.
The same operation as in Example 1 was performed to obtain a liquid flame retardant composition. Further, the flame-retardant composition obtained by the following formulation was stored in a refrigerator (2 to 3 ° C.), and crystal nuclei were mixed therein to investigate dissolution stability. Table 1 shows the presence or absence of crystal precipitation.

[0026]

[Table 1]

Effects of the flame retardant compositions obtained in Examples 2, 5, 6, 8, 9, 10 and Comparative Examples 1 to 6 on the foam-forming reaction and their effects The physical properties of the obtained flame-retardant flexible polyurethane foam were investigated. Flame-retardant flexible polyurethane foam was prepared by the usual method using the formulation shown in Table 2, and the length was 300 mm.
A foam having a size of 300 mm in width and 300 mm in height was manufactured, the state during foaming was observed, and the flame retardancy and physical properties of the resulting foam were measured to obtain the results shown in Table 3.

[0028]

[Table 2]

[0029]

[Table 3]

Regarding flame retardancy, 38.0 mm or less is SE, which means self-extinguishing property, and the numbers are the combustion distance from the marked line (m
m) is shown. As described above, when the blending amount of DBNPG with respect to the flame-retardant organic phosphorus compound is large, the heat resistance is excellent,
Lack of compatibility with flame-retardant organophosphorus compounds tends to hinder the urethane formation reaction and deteriorate the physical properties of urethane foam. TBNPA alone has excellent compatibility but cannot provide sufficient flame retardancy. . DBN found in the present invention
In the case of using the flame retardant composition in which PG and TBNPA are used in combination with the flame retardant organic phosphorus compound, the liquid state is kept at room temperature,
In addition, it is possible to obtain a flexible polyurethane foam having a high flame-retardant effect in which the residual compression property of urethane foam and the air permeability are improved.

[0031]

EFFECTS OF THE INVENTION When a flame-retardant flexible polyurethane foam is produced using the flame retardant composition provided by the present invention, since it is liquid at room temperature, crystallization and precipitation of the flame retardant composition in the polyurethane foam production process occur. In addition, it has the effect of being able to produce a good flame-retardant flexible polyurethane foam that has little effect of inhibiting the reaction during the urethane formation reaction, and because the flame-retardant flexible polyurethane foam has few closed cells, it has a compression residual strain. It also has excellent physical properties such as breathability, cushion material,
There is an effect that it can be suitably applied to the use as an interior material.

Claims (2)

[Claims] 1. A flame retardant composition for a flexible polyurethane foam, comprising a component (a) dibromoneopentyl glycol (DBNP).
G), component (b) tribromoneopentyl alcohol (TBN
PA) and component (c) flame-retardant organic phosphorus compound, and the total of component (a) and component (b) is 1 to 30 parts by weight with respect to 100 parts by weight of the total composition, These are 9
Is dissolved in 9 to 70 parts by weight of component (c), and the proportion of component (a) is 95 to 50 parts by weight, with the total amount of components (a) and (b) being 100 parts by weight; A composition, wherein the ratio of the component (b) is 5 to 50 parts by weight. 2. The composition according to claim 1, wherein 2 to 50 parts by weight is added to 100 parts by weight of the polyol component during the production of the flexible polyurethane foam.