Flame retardant and flame retardant polyurethane resin composition

Abstract

The present invention provides a polyurethane which has excellent flame retardance and various excellent performances. A phosphoramidate compound having a specific structure is used as a flame retardant for a polyurethane foam or a polyurethane elastomer. By mixing this flame retardant with a raw material of a polyurethane resin (polyol, polyisocyanate and various additives), a polyurethane reactive raw material composition is obtained. By reacting the polyisocyanate and active hydrogen-containing compounds such as polyol in the polyurethane reactive raw material composition, a curing reaction takes place and a polyurethane foam composition or polyurethane elastomer composition is obtained. The obtained polyurethane resin composition has excellent flame retardance and other excellent performances as the polyurethane foam or polyurethane elastomer.

Claims

1. A flame retardant polyurethane foam reactive raw material composition comprising a flame retardant, a polyol, a polyisocyanate, and a foaming agent, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (I): ##STR00026## wherein R.sub.1 and R.sub.2 are each independently an alkyl group in which the number of carbon atoms is 1 to 3, R.sub.11 and R.sub.12 are each independently an alkylene group in which the number of carbon atoms is 1 to 3, R.sub.13 is an alkylene group in which the number of carbon atoms is 1 to 6, B.sub.1 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6, and A is a hydrogen atom or an organic group represented by general formula (II): ##STR00027## wherein R.sub.3 and R.sub.4 are each independently an alkyl group in which the number of carbon atoms is 1 to 3, R.sub.14 and R.sub.15 are each independently an alkylene group in which the number of carbon atoms is 1 to 3, and B.sub.2 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6; and wherein when A is a hydrogen atom, then B.sub.1 is an alkyl group in which the number of carbon atoms is 1 to 6, and B.sub.1 and R.sub.13-A are bound to form a nitrogen-containing heterocycle with the nitrogen atom in formula (I), and when A is an organic group represented by the general formula (II), B.sub.2 is an alkyl group in which the number of carbon atoms is 1 to 6, and B.sub.1 is an alkyl group in which the number of carbon atoms is 1 to 6, then B.sub.1 and B.sub.2 may be bound to form a nitrogen-containing heterocycle with the nitrogen atom in formula (I), the nitrogen atom in formula (II) and R.sub.13.

2. A polyurethane foam comprising a flame retardant, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (I): ##STR00028## wherein R.sub.1and R.sub.2 are each independently an alkyl group in which the number of carbon atoms is 1to 3, R.sub.11 and R.sub.12 are each independently an alkylene group in which the number of carbon atoms is 1 to 3, R.sub.13 is an alkylene group in which the number of carbon atoms is 1 to 6, B.sub.1 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6, and A is a hydrogen atom or an organic group represented by general formula (II): ##STR00029## wherein R.sub.3 and R.sub.4 are each independently an alkyl group in which the number of carbon atoms is 1 to 3, R.sub.14 and R.sub.15 are each independently ar alkylene group in which the number of carbon atoms is 1 to 3, and B.sub.2 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6; and wherein when A is a hydrogen atom, then B.sub.1 is an alkyl group in which the number of carbon atoms is 1 to 6, and B.sub.1 and R.sub.13-A are bound to form a nitrogen-containing heterocycle with the nitrogen atom in formula (I), and when A is an organic group represented by the general formula (II), B.sub.2 is an alkyl group in which the number of carbon atoms is 1 to 6, and B.sub.1 is an alkyl group in which the number of carbon atoms is 1 to 6, then B.sub.1 and B.sub.2 may be bound to form a nitrogen-containing heterocycle with the nitrogen atom in formula (I), the nitrogen atom in formula (II) and R.sub.13.

3. A flame retardant polyurethane elastomer reactive raw material composition comprising a flame retardant, a polyol for an elastomer, a polyisocyanate, and a foaming agent, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (I): ##STR00030## wherein R.sub.1 and R.sub.2 are each independently an alkyl group in which the number of carbon atoms is 1 to 3, R.sub.11 and R.sub.12 are each independently an alkylene group in which the number of carbon atoms is 1 to 3, R.sub.13 is an alkylene group in which the number of carbon atoms is 1 to 6, B.sub.1 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6, and A is a hydrogen atom or an organic group represented by general formula (II): ##STR00031## wherein R.sub.3 and R.sub.4 are each independently an alkyl group in which the number of carbon atoms is 1 to 3, R.sub.14 and R.sub.15 are each independently an alkylene group in which the number of carbon atoms is 1 to 3 , and B.sub.2 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6 ; and wherein when A is a hydrogen atom, then B.sub.1 is an alkyl group in which the number of carbon atoms is 1 to 6 , and B.sub.1 and R.sub.13-A are bound to form a nitrogen-containing heterocycle with the nitrogen atom in formula (I), and wherein A is an organic group represented by the general formula (II), B.sub.2 is an alkyl group in which the number of carbon atoms is 1 to 6, and B.sub.1 is an alkyl group in which the number of carbon atoms is 1 to 6, then B.sub.1 and B.sub.2 may be bound to form a nitrogen-containing heterocycle with the nitrogen atom in formula (I), the nitrogen atom in formula (II) and R.sub.13.

4. A polyurethane elastomer comprising a flame retardant, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (I): ##STR00032## wherein R.sub.1 and R.sub.2 are each independently an alkyl group in which the number of carbon atoms is 1 to 3, R.sub.11 and R.sub.12 are each independently an alkylene group in which the number of carbon atoms is 1 to 3, R.sub.13 is an alkylene group in which the number of carbon atoms is 1 to 6, B.sub.1 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6 , and A is a hydrogen atom or an organic group represented by general formula (II): ##STR00033## wherein R.sub.3 and R.sub.4 are each independently an alkyl group in which the number of carbon atoms is 1 to 3, R.sub.14 and R.sub.15 are each independently an alkylene group in which the number of carbon atoms is 1 to 3, and B.sub.2 is a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6; and wherein when A is a hydrogen atom, then B.sub.1 is an alkyl group in which the number of carbon atoms is 1 to 6, and B.sub.1and R.sub.13-A are bound to form a nitrogen-containing heterocycle with the nitrogen atom in formula (I), and when A is an organic group represented by the general formula (II), B.sub.2 is an alkyl group in which the number of carbon atoms is 1 to 6, and B.sub.1 is an alkyl group in which the number of carbon atoms is 1 to 6, then B.sub.1 and B.sub.2 may he bound to form a nitrogen-containing heterocycle with the nitrogen atom in formula (I), the nitrogen atom in formula (II) and R.sub.13.

5. The flame retardant polyurethane foam reactive raw material composition according to claim 1, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (III): ##STR00034## wherein R.sub.1, R.sub.2, R.sub.11 and R.sub.12 are the same as the definitions in the general formula (I), and R.sub.16 is an alkylene group in which the number of carbon atoms is 2 to 12.

6. The flame retardant polyurethane foam reactive raw material composition according to claim 1, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (IV): ##STR00035## wherein R.sub.1, R.sub.2, R.sub.11, R.sub.12 and R.sub.13 are the same as the definitions in the general formula (I), R.sub.3, R.sub.4, R.sub.14 and R.sub.15 are the same as the definitions in the general formula (II), and R.sub.6 and R.sub.7 are each independently a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6.

7. The flame retardant polyurethane foam reactive raw material composition according to claim 1, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (V): ##STR00036## wherein R.sub.1, R.sub.2, R.sub.11, R.sub.12 and R.sub.13 are the same as the definitions in the general formula (I), R.sub.3, R.sub.4, R.sub.14, and R.sub.15 are the same as the definitions in the general formula (II), and R.sub.17 is an alkylene group in which the number of carbon atoms is 2 to 12.

8. The polyurethane foam according to claim 2, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (III): ##STR00037## wherein R.sub.1, R.sub.2, R.sub.11 and R.sub.12 are the same as the definitions in the general formula (I), and R.sub.16 is an alkylene group in which the number of carbon atoms is 2 to 12.

9. The polyurethane foam according to claim 2, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (IV): ##STR00038## wherein R.sub.1, R.sub.2, R.sub.11, R.sub.12 and R.sub.13 are the same as the definitions in the general formula (I), R.sub.3, R.sub.4, R.sub.14 and R.sub.15 are the same as the definitions in the general formula (II), and R.sub.6 and R.sub.7 are each independently a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6.

10. The polyurethane foam according to claim 2, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (V): ##STR00039## wherein R.sub.1, R.sub.2, R.sub.11, R.sub.12 and R.sub.13 are the same as the definitions in the general formula (I), R.sub.3, R.sub.4, R.sub.14 and R.sub.15 are the same as the definitions in the general formula (II), and R.sub.17 is an alkylene group in which the number of carbon atoms is 2 to 12.

11. The flame retardant polyurethane elastomer reactive raw material composition according to claim 3, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (III): ##STR00040## wherein R.sub.1, R.sub.2, R.sub.11 and R.sub.12 are the same as the definitions in the general formula (I), and R.sub.16 is an alkylene group in which the number of carbon atoms is 2 to 12.

12. The flame retardant polyurethane elastomer reactive raw material composition according to claim 3, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (IV): ##STR00041## wherein R.sub.1, R.sub.2, R.sub.11, R.sub.12 and R.sub.13 are the same as the definitions in the general formula (I), R.sub.3, R.sub.4, R.sub.14 and R.sub.15 are the same as the definitions in the general formula (II), and R.sub.6 and R.sub.7 are each independently a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6.

13. The flame retardant polyurethane elastomer reactive raw material composition according to claim 3, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (V): ##STR00042## wherein R.sub.1, R.sub.2, R.sub.11, R.sub.12 and R.sub.13 are the same as the definitions in the general formula (I), R.sub.3, R.sub.4, R.sub.14 and R.sub.15 are the same as the definitions in the general formula (II), and R.sub.17 is an alkylene group in which the number of carbon atoms is 2 to 12.

14. The polyurethane elastomer according to claim 4, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (III): ##STR00043## wherein R.sub.1, R.sub.2, R.sub.11 and R.sub.12 are the same as the definitions in the general formula (I), and R.sub.16 is an alkylene group in which the number of carbon atoms is 2 to 12.

15. The polyurethane elastomer according to claim 4, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (IV): ##STR00044## wherein R.sub.1, R.sub.2, R.sub.11, R.sub.12 and R.sub.13 are the same as the definitions in the general formula (I), R.sub.3, R.sub.4, R.sub.14 and R.sub.15 are the same as the definitions in the general formula (II), and R.sub.6 and R.sub.7 are each independently a hydrogen atom or an alkyl group in which the number of carbon atoms is 1 to 6.

16. The polyurethane elastomer according to claim 4, wherein the flame retardant comprises a non-halogen-containing phosphoramidate compound represented by general formula (V): ##STR00045## wherein R.sub.1, R.sub.2, R.sub.11, R.sub.12 and R.sub.13 are the same as the definitions in the general formula (I), R.sub.3, R.sub.4, R.sub.14 and R.sub.15 are the same as the definitions in the general formula (II), and R.sub.17 is an alkylene group in which the number of carbon atoms is 2 to 12.

Description

EXAMPLES

(1) Hereinafter, the present invention is described in further detail by showing Synthesis Examples, Reference Examples, Examples, and Comparative Examples.

Synthesis Examples

Synthesis Example 1

(2) Synthesis of a Compound of Formula (1)

(3) ##STR00015##

(4) As the first step reaction, 312.6 g of neopentyl glycol (3.00 mol) and 109.5 g of 1, 4-dioxane were charged in a 1 L four-necked flask equipped with a stirrer, a thermometer, a reflux tube connected to a hydrochloric-acid-recovering device, an aspirator, a dropping funnel, and a heating device. The resulting liquid was heated to 50 C. Subsequently, 460.5 g of phosphorus oxychloride (3.00 mol) was added thereto over 2 hours while the reaction temperature was maintained at 45 to 55 C. After the completion of addition, generated hydrochloric acid was collected while the mixture was further stirred at 80 C. for 1 hour, followed by dehydrochlorination at 80 C. at a reduced pressure of 80 kPa for 3 hours to thereby obtain 662.8 g of a white slurry.

(5) 100.6 g of the white slurry obtained above in the first step reaction of Synthesis Example 1 and 214.3 g of 1,4-dioxane were charged in a 1 L four-necked flask equipped with a stirrer, a thermometer, a dropping funnel, and a water bath. While the reaction temperature was maintained at 30 to 40 C., 61.8 g of triethylamine (0.61 mol) was added thereto over 30 minutes. Subsequently, 44.3 g of piperidine (0.52 mol) was gradually added thereto over 1 hour. After the completion of addition, the resulting liquid was stirred at 40 C. for 4 hours. Then, 169.3 g of water was added to this reaction slurry, and the mixture was stirred for 30 minutes, followed by filtration. Thereafter, a step of performing 30-minute repulp washing using water with the same weight as that of the filter cake and filtration was repeated until the filtrate was neutralized. The obtained solid was dried at 80 C. under 2.7 kPa for 8 hours to obtain 100.5 g (83.0% yield) of a flame retardant compound in which compound (1) is the main component. Phosphorus content percentage: 13.3% by weight. Nitrogen content percentage: 6.0% by weight. The obtained flame retardant compound was used in the following Examples.

Synthesis Example 2

(6) Synthesis of a Compound of Formula (4)

(7) ##STR00016##

(8) According to the same method except that 15.6 g of ethylenediamine (0.26 mol) was used in place of the piperidine in Synthesis Example 1, 71.6 g of a solid (77.4% yield) was obtained. Phosphorus content percentage: 17.3% by weight. Nitrogen content percentage: 7.8% by weight. The obtained flame retardant compound was used in the following Reference Examples and Examples.

Synthesis Example 3

(9) Synthesis of a Compound of Formula (10)

(10) ##STR00017##

(11) According to the same method except that 22.4 g of piperazine (0.26 mol) was used in place of the piperidine in Synthesis Example 1, 79.1 g of a solid (79.6% yield) was obtained. Phosphorus content percentage: 16.2% by weight. Nitrogen content percentage: 7.3% by weight. The obtained flame retardant compound was used in the following Reference Examples and Examples.

Synthesis Example 4

(12) A Phosphoramidate Compound Represented by the Following Formula (a Compound of Formula (5))

(13) ##STR00018##

(14) According to the same method except that 22.9 g of diaminobutane (0.26 mol) was used in place of the piperidine in Synthesis Example 1, 75.9 g of a solid (76.4% yield) was obtained. Phosphorus content percentage: 16.2% by weight. Nitrogen content percentage: 7.3% by weight. The obtained flame retardant compound was used in the following Examples.

Synthesis Example 5

(15) A Phosphoramidate Compound Represented by the Following Formula (a Compound of Formula (6))

(16) ##STR00019##

(17) According to the same method except that 30.2 g of hexamethylene diamine (0.26 mol) was used in place of the piperidine in Synthesis Example 1, 78.5 g of a solid (73.3% yield) was obtained. Phosphorus content percentage: 15.0% by weight. Nitrogen content percentage: 6.7% by weight. The obtained flame retardant compound was used in the following Examples.

Reference Example 1

(18) 0.7 parts by weight of SN-thickener A-812 (produced by San Nopco Limited) was added as a thickener to 20 parts by weight of the flame retardant compound obtained in Synthesis Example 2, 20 parts by weight of ion exchanged water, 40 parts by weight of commercially available acrylic resin emulsion (VONCOAT AB-886, produced by DIC Corporation; solid content: 50%), and 0.4 parts by weight of a 28% aqueous ammonia solution. The resulting mixture was homogenized with a homogenizer to obtain a back-coating agent having a viscosity of 15,000 mPa.Math.s (BM-type viscometer, No. 4 rotor, 12 rpm).

(19) The back-coating agent obtained above was uniformly applied to the back surface of a polyester knit of 250 g/m.sup.2 such that a dry weight was 60 g/m.sup.2. Thereafter, it was dried at 150 C. for 3 minutes, and thereby a flame retardant fiber fabric was obtained.

Reference Example 2

(20) A flame retardant fiber fabric was obtained according to the same method as Reference Example 1 except that the flame retardant compound obtained in Synthesis Example 3 was used in an amount of 20 parts by weight as the flame retardant compound.

Comparative Example 1

(21) A flame retardant fiber fabric was obtained according to the same method as Reference Example 1 except that a silane-coated product of ammonium polyphosphate (FR CROS 486, produced by Budenheim; hereinafter referred to as APP), which is a polyphosphate-based flame retardant, was used in an amount of 20 parts by weight as the flame retardant compound.

Comparative Example 2

(22) A flame retardant fiber fabric was obtained according to the same method as Reference Example 1 except that a compound having the following structure:

(23) ##STR00020##
which is a phosphoric acid ester-based flame retardant, was used in an amount of 20 parts by weight as the flame retardant compound.

(24) The flame retardance of the flame retardant fiber fabrics of Reference Examples 1 to 2 and Comparative Examples 1 to 2, and the solubility of the flame retardant compounds in hot water were measured.

(25) [Flame Retardance Test]

(26) The flame retardance test was performed in accordance with the test method of the U.S. Federal Motor Vehicle Safety Standards, FMVSS 302. The test was performed five times in each of horizontal and vertical directions; and when all of the test results satisfied any of the following, the tested fiber fabric was considered to have flame retardance, and given a Pass evaluation: 1) self-extinguished before the marked line A (38 mm); 2) burnt distance after the marked line A was 50 mm or less, and the burning time was 60 seconds or less; and 3) the burning rate after the marked line A was 80 mm/minute or less.

(27) [Solubility Test in Hot Water]

(28) Five parts by weight of each of the flame retardant compounds of Synthesis Examples 2 and 3 and the flame retardant compounds of Comparative Examples 1 and 2 was added to 45 parts by weight of water. The resulting mixture was stirred at 90 C. for 1 hour, and the phosphorus content in the solution obtained by filtration when the mixture was hot was measured to determine the solubility in hot water at 90 C. It should be noted that when the flame retardant compound was fully dissolved, the solubility in hot water was regarded as >10%.

(29) The following Table 1 shows the results of the flame retardance test and the results of the solubility in hot water test, as well as the phosphorus content percentage and nitrogen content percentage of the flame retardant compounds used.

(30) TABLE-US-00001 TABLE 1 Phosphorus Nitrogen content content Solubility of percentage of percentage of Flame compound in compound compound retardance hot water Reference 17.3% 7.8% Pass 0.7% Example 1 Reference 16.2% 7.3% Pass 0.4% Example 2 Comparative 31.3% 14.1% Pass 5.9% Example 1 Comparative 17.3% Failure >10% Example 2

(31) From Table 1, the fiber fabrics of Reference Examples 1 and 2 exhibit good flame retardance, even though the phosphorus content percentage and nitrogen content percentage of the flame retardant compounds of Reference Examples 1 and 2 which are believed to contribute to flame retardance were less than those of the fiber fabric of Comparative Example 1, which phosphorus content percentage and nitrogen content percentage. Further, it is understood that the solubility in hot water of the flame retardant compounds used in the fiber fabrics of Reference Examples 1 and 2, which causes water spot formation, is low. In contrast, Comparative Example 1, in which APP was used as the flame retardant compound, was given a Pass evaluation in the flame retardance test; however, this fiber fabric has high solubility in hot water, and thus it is likely to cause water spot formation.

(32) The water spot formation as used herein refers to a phenomenon in which adherence of high-temperature vapor used in the production of seats for vehicles as well as moisture, such as rain, sweat, and the like, to the surface of a fiber product causes dissolution of the water-soluble components of the flame retardant, and thereafter the portion which had been wetted turns into a white spot or stain when it is dried.

(33) Further, in Comparative Example 2, a phosphoric acid ester having excellent flame retardance for use in a high-temperature absorption exhaustion treatment for fiber was used as the flame retardant compound. In this regard, the flame retardant compound of Comparative Example 2 is a phosphoric acid ester having a structure similar to that of the flame retardant compound of Reference Example 1, and the phosphorus content of the flame retardant compound of Comparative Example 2 is also equal to that of the flame retardant compound of Reference Example 1. However, as shown in Table 1, the flame retardant compound of Comparative Example 2 has low flame retardance and a high solubility in hot water, and is thus not suitable as a flame retardant for back-coating. From these, it is understood that a back-coating agent containing a phosphoramidate represented by the general formula (I) is very effective as a flame retardant back-coating agent.

Reference Example 3

(34) [Production of Surface Skin Layer]

(35) One hundred parts by weight of a polyurethane material (produced by DIC Corporation, CRISVON MP120; nonvolatile component: 30% by weight) was mixed with 30 parts by weight of toluene in the ratio to prepare a solution, and thereby a resin composition for forming a surface skin layer was prepared.

(36) Further, the resin composition solution for forming the surface skin layer prepared above was applied to a release paper (produced by Dai Nippon Printing Co., Ltd., DE73) using an applicator which was set to 320 m. The resulting applied film was dried at 110 C. for 4 minutes to prepare a coating film for a surface skin layer, which coating film has a post-drying average film thickness of 40 m.

(37) [Preparation of Resin Composition for Forming Adhesive Layer]

(38) A resin composition for forming an adhesive layer was prepared by using 100 parts by weight of a polyurethane material for adhesion (produced by DIC Corporation, CRISVON 4010; nonvolatile component: 50% by weight), 10 parts by weight of an isocyanate-based crosslinking agent (produced by DIC Corporation, BURNOCK D-750; nonvolatile component: 75% by weight), 3 parts by weight of a crosslinking accelerator (produced by DIC Corporation, CRISVON Accel HM, nonvolatile component: 15% by weight), 6.45 parts by weight of the flame retardant compound of Synthesis Example 2 (nonvolatile component: 100% by weight) as a flame retardant, and 22.8 parts by weight of toluene.

(39) [Preparation of Synthetic Leather]

(40) The above-described resin composition for forming an adhesive layer was further applied to the upper surface of the above-described coating film for a surface skin layer by using an applicator which was set to 320 m, and a base fabric (a polyester knit; weight per area: 250 g/m.sup.2) was laminated thereon, and pressure-bonded. The resulting product was heated at 110 C. for 4 minutes to accelerate curing while the solvent was removed. Then, aging was performed at 25 C. for three days to complete the curing of the adhesive layer, and the release paper was peeled off to complete a flame retardant synthetic leather. The adhesive layer had a thickness of 150 m.

(41) [Flame Retardance Test]

(42) The flame retardance test was performed on the above-described flame retardant synthetic leather in accordance with the test method of the U.S. Federal Motor Vehicle Safety Standards, FMVSS 302. The test was performed a total of 5 times, and when self-extinguishment was observed before the marked line A (38 mm) in all of the test results, the leather was judged as having flame retardance and given a Pass evaluation. The results are shown in Table 2.

Reference Example 4

(43) A synthetic leather was obtained in the same manner as that in Reference Example 3, except that the flame retardant compound of Synthesis Example 3 was used as the flame retardant. The flame retardance was then measured. The results are shown in Table 2.

Comparative Example 3

(44) A synthetic leather was obtained in the same manner as that in Reference Example 3, except that the phosphoric acid ester flame retardant compound which was used in Comparative Example 2 was used as the flame retardant. The flame retardance was then measured. The results are shown in Table 2.

Comparative Example 4

(45) A synthetic leather was obtained in the same manner as that in Reference Example 3 except that 20 parts by weight of tetrakis(2,6-dimethylphenyl)-m-phenylene bisphosphate, which is a phosphoric acid ester widely used as a flame retardant for resins, and 39.2 parts by weight of toluene were used. The flame retardance was then measured. The results are shown in Table 2.

(46) TABLE-US-00002 TABLE 2 Maximum Phosphorus Content burnt content percentage of distance in percentage compound in flame of compound adhesive retardance (% by layer test Flame weight) (% by weight) (mm) retardance Reference 17.3% 10% 13 mm Pass Example 3 Reference 16.2% 10% 27 mm Pass Example 4 Comparative 17.3% 10% 44 mm Failure Example 3 Comparative 9.0% 25.7% 48 mm Failure Example 4

(47) From Table 2, it is understood that the synthetic leathers of Reference Examples 3 and 4 have higher flame retardance than the synthetic leathers of Comparative Examples 3 and 4 in which a phosphoric acid ester having excellent flame retardance for use in a high-temperature absorption exhaustion treatment for fiber was used.

EXAMPLES

(48) In the below-described examples, the following was used as the raw material. (1) Polyol: A polyether-type triol based on glycerin and propylene oxide, molecular weight: about 3000, hydroxyl value: 56.0, produced by Mitsui Chemicals, Inc., trade name: Actcol T-3000 (2) Silicone foam stabilizer: Produced by Momentive Performance Materials Japan LLC., trade name: Niax Silicone L-638J (3) Amine-based catalyst: Produced by Air Products and Chemicals, Inc., trade name: DABCO 33LV Produced by Air Products and Chemicals, Inc., trade name: DABCO BL-11 (4) Tin-based catalyst: Produced by Air Products and Chemicals, Inc., trade name: DABCO T-9) (5) Foaming agent: Water dichloromethane (6) Polyisocyanate: Tolylene diisocyanate (TDI)

(49) (produced by Mitsui Chemicals, Inc., trade name: Cosmonate T-80)

(50) (2,4-isomer/2,6-isomer=80/20 (% by weight)) (7) Flame retardant: The following flame retardants A to G were used.

(51) (Flame Retardant A) A Phosphoramidate Compound Represented by the Following Formula (a Compound of Formula (1))

(52) ##STR00021##

(53) (Flame Retardant B) A Phosphoramidate Compound Represented by the Following Formula (a Compound of Formula (4))

(54) ##STR00022##

(55) (Flame Retardant C) A Phosphoramidate Compound Represented by the Following Formula (a Compound of Formula (10))

(56) ##STR00023##

(57) (Flame Retardant D) A Phosphoramidate Compound Represented by the Following Formula (a Compound of Formula (5))

(58) ##STR00024##

(59) (Flame Retardant E) A Phosphoramidate Compound Represented by the Following Formula (a Compound of Formula (6))

(60) ##STR00025##

(61) (Flame Retardant F) Phosphoric acid, oxydi-2,1-ethanediyl tetrakis(2-chloro-1-methylethyl) ester

(62) (Flame Retardant G) Antiblaze V-66 (Produced by Albemarle Corporation) Main component: 2,2-bis(chloromethyl)-1,3,-propanediol bis[bis(2-chloroethyl)phosphate]

Example 1

(63) (Production Method)

(64) According to the formulation shown in Table 3, a polyol, a silicone foam stabilizer, an amine-based catalyst, a tin-based catalyst, a foaming agent, and flame retardant A were mixed, and stirred using a stirrer at a rotation rate of 3000 rpm for 1 minute to homogeneously admix the blended formulation. Thereafter, a polyisocyanate was further added thereto, and the liquid was stirred at a rotation rate of 3000 rpm for 5 to 7 seconds, and immediately the contents were poured into a cubic cardboard box (height: about 200 mm) of which the bottom is square (one side: about 200 mm).

(65) Foaming occurred immediately and the volume reached the maximum after several minutes. Thereafter, the maximum volume was approximately maintained. The obtained foamed article was stood and cured in a furnace at temperature of 80 C. for 30 minutes to obtain a polyurethane foam (foamed article). The obtained foamed article had white flexible open cell-type cell structure. The flame retardance, anti-fogging characteristics, residual distortion by compression, and scorch characteristic thereof were evaluated by the following methods.

(66) (Flame Retardance Evaluation)

(67) A sample was cut from the obtained foamed article and a combustion test was carried out under the following condition.

(68) Test method: FMVSS-302 method (test method of safety standards for automobile upholstery)

(69) Horizontal burning test of a polyurethane foam

(70) Test condition: adjusted such that the air-permeability was 200 ml/cm.sup.2/sec.

(71) (The air-permeability was measured according to the JIS K6400-7B method.)

(72) Sample: 160 mm length, 70 mm width, 13 mm thickness

(73) Valuation criteria: NB: a burnt distance is 38 mm or less SE: a burnt distance is 39 mm or more and 88 mm or less BN: a burnt distance is 89 mm or more.

(74) (Anti-Fogging Characteristics Evaluation)

(75) A sample was cut from the obtained foamed article and anti-fogging characteristics test was carried out under the following condition.

(76) Test condition: A windscreen fogging tester (produced by Suga Test Instruments Co., Ltd.) was used, and a sample of a polyurethane foam (diameter: 80 mm, thickness: 10 mm) was placed in the lower portion of a container thereof. The sample was heated at 100 C. for 16 hours. The amount of substances which were scattered from the sample and attached to aluminum foil at the upper portion of the container was measured as an aluminum-attaching amount (mg).

(77) (Residual Distortion by Compression (%))

(78) Residual distortion by compression (%) was measured in accordance with JIS K6400-4:2004.

(79) (Scorch (YI))

(80) The obtained foamed article was maintained in a microwave for 3 minutes and then at 70 C. for 4.5 minutes. Thereafter, a color-difference meter (Nippon Denshoku Industries Co., Ltd., Color Meter ZE2000) was used to measure a yellowing degree (whiteness degree) for the center portion of the foamed article, which was at a high temperature, and the side portion, which was at a low temperature. The color difference between them was expressed in YI.

(81) The results are shown in Table 3.

Examples 2 to 5 and Comparative Examples 5 and 6

(82) Foamed articles were produced in the same manner as that in Example 1 except that flame retardant B, C, D, E, F, or G was used in place of flame retardant A as shown in Table 3. The flame retardance, anti-fogging characteristics, residual distortion by compression, and scorch characteristic thereof were evaluated. The results are shown in Table 3.

Examples 2A to 5A and 2B to 5B and Comparative Examples 5B and 6B

(83) Foam articles were produced in the same manner as that in Example 1 except that the type and amount of a flame retardant were changed as shown in Tables 4 and 5. The flame retardance, anti-fogging characteristics, residual distortion by compression, and scorch characteristic thereof were evaluated. The results are shown in Tables 4 and 5.

(84) TABLE-US-00003 TABLE 3 Comparative Example Example 1 2 3 4 5 5 6 Polyol T-3000 100 100 100 100 100 100 100 Silicone L-638J 1 1 1 1 1 1 1 foam stabilizer Amine- DABCO 0.2 0.2 0.2 0.2 0.2 0.2 0.2 based 33LV catalyst DABCO 0.05 0.05 0.05 0.05 0.05 0.05 0.05 BL11 Tin-based DABCO T9 0.3 0.3 0.3 0.3 0.3 0.3 0.3 catalyst Foaming Water 4.3 4.3 4.3 4.3 4.3 4.3 4.3 agent Dichloro- 8 8 8 8 8 8 8 methane Poly- T-80 58.1 58.1 58.1 58.1 58.1 58.1 58.1 isocyanate Flame Flame 16 retardant retardant A Flame 16 retardant B Flame 16 retardant C Flame 16 retardant D Flame 16 retardant E Flame 16 retardant F Flame 16 retardant G Flame Burnt 37 23 35 25 23 93 96 retardance distance (mm) Evaluation NB NB NB NB NB BN BN Anti- Amount 5.1 <0.1 <0.1 <0.1 <0.1 2.6 0.6 fogging attached characteristics to aluminum (mg) Residual % 6 4 2 8 4 4 4 distortion by compression Scorch YI 30 3 1 69 63 3 87

(85) TABLE-US-00004 TABLE 4 Example 2A 3A 4A 5A Polyol T-3000 100 100 100 100 Silicone L-638J 1 1 1 1 foam stabilizer Amine-based DABCO 33LV 0.2 0.2 0.2 0.2 catalyst DABCO BL11 0.05 0.05 0.05 0.05 Tin-based DABCO T9 0.3 0.3 0.3 0.3 catalyst Foaming Water 4.3 4.3 4.3 4.3 agent Dichloro- 8 8 8 8 methane Poly- T-80 58.1 58.1 58.1 58.1 isocyanate Flame Flame 14 retardant retardant B Flame 14 retardant C Flame 14 retardant D Flame 14 retardant E Flame Burnt 37 43 37 36 retardance distance (mm) Evaluation NB SE NB NB Anti- Amount <0.1 <0.1 <0.1 <0.1 fogging attached to characteristics aluminum (mg) Residual % 3 2 4 4 distortion by compression Scorch YI 3 1 65 60

(86) TABLE-US-00005 TABLE 5 Comparative Example Example 2B 3B 4B 5B 5B 6B Polyol T-3000 100 100 100 100 100 100 Silicone L-6383 1 1 1 1 1 1 foam stabilizer Amine-based DABCO 33LV 0.2 0.2 0.2 0.2 0.2 0.2 catalyst DABCO BL11 0.05 0.05 0.05 0.05 0.05 0.05 Tin-based DABCO T9 0.3 0.3 0.3 0.3 0.3 0.3 catalyst Foaming Water 4.3 4.3 4.3 4.3 4.3 4.3 agent Dichloro- 8 8 8 8 8 8 methane Poly- T-80 58.1 58.1 58.1 58.1 58.1 58.1 isocyanate Flame Flame 18 retardant retardant B Flame 18 retardant C Flame 18 retardant D Flame 18 retardant E Flame 18 retardant F Flame 18 retardant G Flame Burnt 18 29 20 19 87 88 retardance distance (mm) Evaluation NB NB NB NB SE SE Anti- Amount <0.1 <0.1 <0.1 <0.1 2.7 0.7 fogging attached to characteristics aluminum (mg) Residual % 4 2 4 4 4 5 distortion by compression Scorch YI 3 1 69 66 4 90

(87) From the above results, the evaluations on flame retardance in Examples 1 to 5, 2A to 5A, and 2B to 5B were each NB or SE, and the results for residual distortion by compression and scorch characteristic were both good. Only in Example 3A, the evaluation on flame retardance was SE, not NB. However, since the burnt distance was 43 mm, it is a level that will not be a problem if it is not for special use requiring very high flame retardance. It should be noted that while the evaluations on flame retardance in Comparative Examples 5B and 6B were also SE, the burnt distance in Comparative Examples 5B and 6B was 87 to 88 mm and the flame retardance in Example 3A was significantly excellent in comparison with that in Comparative Examples 5B and 6B. In addition, regarding Examples 2 to 5, 2A to 5A, and 2B to 5B, anti-fogging characteristics were very good and almost no scattered components were observed. In particular, Examples 2 to 3, 2A to 3A, and 2B to 3B (flame retardants B and C) attained <0.1 of the value of anti-fogging characteristics, 5 or less of the value of residual distortion by compression, and 5 or less of scorch characteristic, and were confirmed as having comprehensively very high performances. With regard to Example 1, the anti-fogging characteristics thereof is slightly lower than those of Comparative Examples 5 to 6, and the scorch thereof is also slightly lower than that of Comparative Example 5. However, it is not a level that will be a problem if it is for general use other than special use requiring very high performances for anti-fogging characteristics and scorch. For example, in conventionally known flame retardants, there are those giving a worse result in performance of anti-fogging characteristics than Example 1. In addition, for scorch, the result of Example 1 is better than that of Comparative Example 6. Thus, as comprehensive evaluation including flame retardance and residual distortion by compression, Example 1 is better than Comparative Examples 5 to 6, and it can be evaluated that the flame retardant of Example 1 is comprehensively more excellent than conventional flame retardants. In Examples 4, 5, 4A, 5A, 4B, and 5B, the values of scorch characteristic thereof are slightly high. However, they can be sufficiently used if they are for general use other than special use requiring very high performance for scorch characteristic.

(88) In contrast to this, the evaluations on flame retardance in Comparative Examples 5 to 6 were BN. That is, they were given a Failure evaluation in the flame retardance test and were deficient in flame retardance. In Comparative Examples 5B and 6B where the additive amount was increased, the evaluation on flame retardance were SE, however, the burnt distance values were near 89 mm, that is, there is almost no difference from the range to be evaluated as BN. Specifically, in Comparative Examples 5B and 6B, the difference in flame retardance from the Examples was remarkable. As described above, comprehensively very excellent results were confirmed in the Examples for performances as a flame retardant in comparison with the Comparative Examples. The compounds used as a flame retardant in Comparative Examples 5, 6, 5B, and 6B are such a type of compounds that are conventionally known to have high flame retardance. Compared to conventional flame retardants known as such high performance flame retardants, the flame retardant of the present invention was confirmed as having very high performances.

INDUSTRIAL APPLICABILITY

(89) According to the present invention, provided are flame retardant polyurethane foam compositions and elastomer compositions being excellent in flame retardance, anti-fogging characteristics, distortion characteristic, and scorch characteristic by using a phosphoramidate compound having a non-halogen-containing specific structure as a flame retardant.

(90) A urethane foam for which a flame retardant of the present invention has been used is excellent in flame retardance and are excellent in a variety of performances required for urethane foams, and can be used for various applications for which urethane foams have been conventionally used.

(91) A urethane elastomer in which a flame retardant of the present invention has been used is excellent in flame retardance and is excellent in a variety of performances required for the urethane elastomers, and can be used for various applications where urethane elastomers have been conventionally used.

(92) The present invention has been exemplified so far with reference to the favorable embodiments of the present invention, but it should not be construed that the present invention is restricted by the embodiments. It is understood that the scope of the present invention should be construed only by the claims. It is understood that those who are skilled in the art can carry out an equivalent range based on the description of the present specification and technical common sense from the description of the specific favorable embodiments of the present invention. It is understood that the contents of the patents, patent applications and literatures cited in the present specification should be herein incorporated by reference, similarly to the case where the contents themselves are described specifically in the present specification.