JP2882724B2 - Low fogging flame retardant polyurethane composition - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

FIELD OF THE INVENTION The present invention relates to a composition for a low fogging flame retardant polyurethane. Specifically, the present invention relates to a liquid composition which imparts flame retardancy to polyurethane and has an extremely low fogging property.

[0002]

2. Description of the Related Art Polyurethane organic polymers, which are typical thermosetting resins, are relatively inexpensive and have excellent properties such as easy molding. It is widely used in daily necessities, including parts. However, since these organic polymers are flammable and burn out of control once ignited, various efforts have been made in the industry to produce flame retardant foams. Nowadays, flame retardancy is required by law in some applications of polyurethane, such as automotive interior parts. Furthermore, in recent years, environmental problems have been socially highlighted, and while dioxin problems and chlorofluorocarbon problems are in turmoil, fogging properties are also viewed as a problem in polyurethane foam automotive parts.

In order to impart flame retardancy to polyurethane,
In general, a method of adding a halogen-containing phosphate ester flame retardant is used, but when the flame retardant rises in summer, the monomer component and the hydrochloride of the amine formed by decomposition are scattered and fog the glass. It has also been found to have an adverse effect on the human body. Generally, flame retardants mainly use monomer components such as tris (chloroethyl) phosphate and tris (chloropropyl) phosphate. However, since the molecular weight is small, they are easily scattered, and the flame retardancy of the foam is reduced. There is a disadvantage of doing so.

In order to increase the molecular weight, halogen-containing condensed phosphoric acid esters have been provided, all of which are constituted as oligomers, and about 5 to 20% of tris (chloroethyl) phosphate or tris (chloropropyl) phosphate. And the same tendency as described above.

[0005] Further, flame retardants have been provided in which the degree of condensation is further increased and the monomer component is reduced as much as possible. On the other hand, the viscosity increases and the workability is difficult. Or, it may adversely affect other physical properties such as scorch properties.

Accordingly, an object of the present invention is to provide a liquid low fogging flame retardant polyurethane composition which does not contain a low molecular weight component, has heat resistance, and can impart excellent flame retardancy. .

[0007]

The present invention provides a compound of the formula (I):

[0008]

Embedded image (Wherein, R ₁ and R ₂ are the same or different lower alkyl groups or hydrogen atoms, and Z is —CH ₂ CH ₂ —, —CH ₂ CH ₂ O
CH ₂ CH ₂ -,

[0009]

Embedded image A liquid low fogging comprising 50 to 100 parts by weight of an organic phosphorus compound represented by the formula, 50 to 0 parts by weight of a non-reactive organic phosphorus compound acting as a flame retardant plasticizer, and 0 to 5 parts by weight of an antioxidant. A composition for a flame retardant polyurethane is provided. The lower alkyl group represented by R ¹ and R ² in the above formula (I) includes a linear or branched alkyl group having 1 to 4 carbon atoms, for example, methyl, ethyl, propyl, i-propylbutyl.

The organic phosphorus compound of the above formula (I) includes C
R-733S [m-phenylenebis (diphenylphosphate ) ] (manufactured by Daihachi Chemical), m-phenylenebis (dicresylphosphate), 2,2-bis [ 4- [bis (methylphenoxy) phosphoryloxy] phenyl ] Examples include propane, tetrakis (phenyl) ethylene diphosphate, and tetrakis (phenyl) diethylene diphosphate.

Examples of the flame-retardant plasticizer having an average molecular weight of 350 or more include tris (dichloropropyl) phosphate and antiphrase 78 [chlorinated polyphosphonate].
(Manufactured by A & W), Thermolin 101 [tetrakis (2-
Chloroethyl) ethylene diphosphate] (manufactured by Ohlin), Fosgard 2XC20 [2,2-bis (chloromethyl) -1,3-propanebis (chloroethyl) diphosphate (manufactured by Monsanto), CR-530, CR-
507, CR-509 [halogen-containing phosphate phosphonate oligomer ester] (manufactured by Daihachi Chemical Co., Ltd.) (Japanese Patent Application No. 57-61762), CR-504 [tetrakis (chloropropyl) oxydiethylene diphosphate]
(Manufactured by Daihachi Chemical), cresyl diphenyl phosphate,
And tricresyl phosphate.

The antioxidant used in the composition of the present invention is represented by the formula (II)

[0013]

Embedded image (Wherein, R ′ ₁ , R ′ ₂ , R ′ ₃ and R ′ ₄ each represent a hydrogen atom or a C ₁ -C ₁₄ alkyl group) and / or a trivalent organic phosphorus Compound.

Specific examples of the above hydroquinone compound include hydroquinone, 2,5-di-tert-amylhydroquinone, 2,5-dioctylhydroquinone, tert-
Amyl hydroquinone, tert-butyl hydroquinone,
Octyl hydroquinone and the like, and particularly as a hydroquinone compound having excellent heat resistance, 2,5-di-tert-
Amyl hydroquinone, 2,5-di-tert-butyl hydroquinone and the like can be mentioned.

Specific examples of the above trivalent organic phosphorus compounds include triphenyl phosphite, tris (nonylphenyl) phosphite, diphenylisodecyl phosphite, and tris (2,4-di-tert-butylphenyl) pentaerythritol. Diphosphite, tetrakis- (2,
4-di-tert-butylphenyl) -4,4-diphenylenediphosphonite and the like.

The low fogging composition for flame retardant polyurethanes of the present invention comprises 50 to 100 parts by weight of an organic phosphorus compound of the formula (I), 50 to 0 parts by weight of a flame retardant plasticizer and, if desired, antioxidation. 0 to 5 parts by weight of the agent
Heat to 5 ° C, stir and dissolve to form a formulation.

According to one aspect of the present invention, there is provided a method of producing a flame retardant polyurethane foam having low fogging properties.
That is, a polyol and toluene diisocyanate (T
In the reaction of DI), the above composition is added in the presence of a catalyst, water or a foaming agent, a dispersant, and the like, and the mixture is stirred and heated to produce the composition. In this case, as the catalyst, tertiary amine catalyst (triethylenediamine, dimethylethanolamine, N- ethylmorpholine, etc.) and tin-based catalyst (SnCl ₄ and the like) is used. Blowing agents include water, fluorocarbons, low boiling compounds such as methylene chloride. The composition is used in an amount of 2 to 60 parts by weight based on 100 parts by weight of the raw material polyol.

According to another aspect of the present invention, there is provided a flame-retardant polyurethane foam having low fogging properties.

The polyurethane foam of the above composition of the present invention has extremely low fogging properties while maintaining flame retardancy, as compared with conventional halogen-containing phosphate esters or oligomers, and has a high heat resistance. , The burn (scorch) inside the foam can be suppressed.

As described above, a product having excellent flame retardancy, fogging property and scorch property and preferable physical properties for the automobile and furniture industries can be obtained.

[0021]

Next, the present invention will be described with reference to examples, but these examples are not intended to limit the scope of the present invention. All parts are by weight unless otherwise specified. <Liquid preparation>

Example 1 A flame retardant CR-733S (manufactured by Daihachi Chemical Co., Ltd.) (95 g) was placed in a mixing vessel and heated to about 60 ° C. While continuously stirring, 5 g of hydroquinone was added. The resulting mixture was stirred and heated to 60 ° C. under reduced pressure for about 1 hour. The liquid mixture was then gradually cooled to about 25 ° C and held at that temperature for about 24 hours. The mixture was examined to determine if the solid hydroquinone precipitated upon cooling. The mixture contains no solids at 25 ° C
Had a viscosity of 820 centipoise.

Examples 2 to 5 Preparations were made in the same manner as in Example 1 except that the flame retardants shown in Table 1 were used.

Example 6 Only those listed in Table 1 were used as flame retardants.

COMPARATIVE EXAMPLES A-E Prepared and used alone as in Example 1, using components outside the scope of the invention. Table 1 shows the states of the liquids obtained by the respective formulations of the examples and comparative examples.

[0026]

[Table 1]

Next, the flame retardancy and fogging properties of the flame retardant composition obtained by the above formulation were tested, and the results are shown in Table 2.

(Production of flame-retardant polyurethane foam with low fogging properties) Formulation Polyol (Mitsui Toatsu Chemicals, polyether polyol, molecular weight 3000) 100 parts Isocyanate (Mitsui Toatsu Chemicals, Tolylene diisocyanate 2,4 / 2) , 6 80/20) 55.1 parts Silicon oil (trade name L-520, manufactured by Nippon Unica) 1.2 parts Tin-based catalyst (tin octylate manufactured by Mitsui Organic Synthesis Co., Ltd. ) 0.3 part Amine-based catalyst (US Air) by Products and Chemicals, Inc., triethylenediamine) 4.5 parts 0.2 parts water methylene chloride predetermined portions flame retardant predetermined portions (amount shown in Table 2) one-shot process in the above formulation was prepared soft urethane foam.

Production Method The polyol, silicone oil, catalyst, water, and flame retardant are mixed in the amounts indicated in the above formulation, stirred for 1 minute with a stirrer having a rotation speed of 3000 rpm, and uniformly mixed. After further stirring at 3000 rpm for 5 to 7 seconds, the contents were quickly poured into a square cardboard box. Foaming occurred immediately and reached a maximum volume after a few minutes. This was cured in an oven at 80 ° C. for an additional 30 minutes. The obtained foam had a white soft open cell structure. From the various foams obtained by the above method, samples were cut out and subjected to a combustion test (combustion test method MVSS-302). Further, in the examination of fogging properties, the adhesion to glass was measured at 110 ° C. for 3 and 16 hours based on DIN 75201 (European fogging test method). Regarding physical properties, the density (JIS K-7222) [Kg /
m ³ ] and air permeability (JIS L-1004, ASTM D
-737-46) [ml / cm ² / sec] was measured.

Table 2 shows the results.

[0031]

[Table 2]

[0032]

From these results, the low-fogging flame-retardant polyurethane foam using the flame retardant of the present invention maintains the flame retardancy and has extremely good fogging properties as compared with the comparative example. . In addition, the foam has no closed cells, has good air permeability, and as a result, has good physical properties.

Continuation of the front page (51) Int.Cl. ⁶ identification code FI C08K 5:13 5: 524) (58) Field surveyed (Int.Cl. ⁶ , DB name) C08L 75/04-75/16 C08K 5 / 13 C08K 5/521-5/523

Claims (4)

(57) [Claims] 1. A compound of formula (I): (Wherein, R ₁ and R ₂ are the same or different lower alkyl groups or hydrogen atoms, and Z is —CH ₂ CH ₂ —, —CH ₂ CH ₂ O
CH ₂ CH ₂ —, embedded image A liquid low fogging comprising 50 to 100 parts by weight of an organic phosphorus compound represented by the formula, 50 to 0 parts by weight of a non-reactive organic phosphorus compound acting as a flame retardant plasticizer, and 0 to 5 parts by weight of an antioxidant. A composition for flame-retardant polyurethane. 2. A non-reactive organic phosphorus compound is comprised of chlorinated phosphate esters or oligomers thereof, chlorinated phosphonate ester or its oligomer or halogen-phosphoric acid ester or an oligomer thereof, an average molecular weight of 350 or more Claim 1 which is a compound
The composition for flame-retardant polyurethane having low fogging property described in 1 above. 3. The antioxidant of the formula (II): (Wherein, R ′ ₁ , R ′ ₂ , R ′ ₃ and R ′ ₄ each represent a hydrogen atom or a C ₁ -C ₁₄ alkyl group) and / or a trivalent organic phosphorus The composition for a low fogging flame-retardant polyurethane according to claim 1, which is a compound. 4. The composition for flame-retardant polyurethane having low fogging properties according to claim 1, wherein the composition is used in an amount of 2 to 60 parts by weight based on 100 parts by weight of a polyol raw material for forming the polyurethane during the production of the polyurethane.