JPH08217846A - Low-staining and flame-retardant polyurethane foam - Google Patents

Abstract

PURPOSE: To obtain the low-staining and flame-retardant polyurethane foam little in a fogging phenomenon and in the discoloration of the foam ground, and useful for furnitures, etc., by using a polyol, a polyisocyanate, water, a metal catalyst, an amine catalyst and a halogen-free flame retardant. CONSTITUTION: This low staining and flame retardant polyurethane foam is produced from (A) a polyol such as a polyesterpolyol, (B) a polyisocyanate such as tolylene diisocyanate, (C) water, (D) a foaming agent such as trichlorofluoromethane, (E) a metal catalyst such as cuprous octenate, (F) an amine catalyst having one or more functional groups, such as dimethylaminohexanol, and (G) a halogen-free flame retardant such as a tricresylphosphate of the formula (R1 -R3 are H, alkyl). The components G and F are used in amounts of 1-40 pts.wt. and 0.1-2 pts.wt., respectively, based on 100 pts.wt. of the component A.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a flame-retardant polyurethane foam used in combination with furniture, a seat for automobiles, trains, etc., and a cover material.

[0002]

2. Description of the Related Art Conventionally, flame-retardant polyurethane foams have been prepared by adding and blending a flame-retardant agent to the main raw material such as polyether or polyester polyol, isocyanate, water, foaming agent, surfactant, metal-containing catalyst, amine catalyst. It is made by.

Generally, TCE is used as a flame retardant to be blended.
P (tris (chloroethyl) phosphate), TDC
Halogen-containing compounds such as P (tris (dichloropropyl) phosphate), phosphoric acid esters, etc., or inorganic compounds such as zinc oxide and antimony trioxide (PET) are commonly used.

As the amine catalyst, triethylenediamine (TEDA) or a product obtained by diluting it with diethylene glycol (DEG) or dipropylene glycol (DPG) is mainly used.

[0005]

Polyurethane foam, which is used in combination with fabrics, for furniture or, in particular, seat covers or interior materials for automobiles, trains, etc., is used in order to provide safety in case of fire. The standards for flame retardancy are set respectively, and a polyurethane foam having flame retardancy is required based on these standards.

By the way, the flame retardant used for polyurethane foam is often a so-called addition type flame retardant which does not usually react with the urethane raw material. Therefore, the flame retardant is mixed and adhered in the foam as it is. Therefore, for example, when the interior of a vehicle is hermetically sealed and often used in places exposed to high temperatures, for example, the flame retardant is decomposed by heat to generate halogen, and It volatilizes by reacting with the amine catalyst in the polyurethane foam, and the volatilized reaction product adheres to the glass inside the room, resulting in a white mist (this is called fogging). As a result, the visibility deteriorates, and there is a possibility that the light of the light may become unclear, especially when driving at night.

Further, the halogen contained in the flame retardant or the residual amine may react with a substance in the fabric used in combination to cause discoloration of the fabric (surface material). Is also occurring. An object of the present invention is to obtain a low-staining and flame-retardant polyurethane foam that does not cause the above-mentioned problems such as the fogging phenomenon and discoloration of the fabric.

[0008]

As a means for solving this problem, the inventors of the present invention, as described in claim 1, have a polyol, a polyisocyanate, water, a blowing agent,
In a polyurethane foam prepared by using an ordinary raw material for a flexible polyurethane foam such as a metal catalyst or an amine catalyst, both (1) a halogen-free flame retardant and (2) an amine catalyst having at least one functional group are used. It was found that when used in combination, a polyurethane foam with low pollution resistance and flame retardancy can be obtained as compared with the conventional one.

The details of the present invention will be described below. First, the main raw material of the polyurethane foam is not particularly limited, and examples of the polyol as the main raw material include polyether polyol, polyester polyol, polyether ester polyol, polyacrylic polyol, liquid diene-based polyol, and the like. Examples of polyether polyols include linear and / or liquid-phase polyethers that are substantially free of functional groups other than a plurality of ether bonds and at least two hydroxyl groups. Specific examples of the polyether polyol include polyethylene glycol, polypropylene glycol, polybutylene glycol and the like.

Further, copolymers and copolymers of polyoxyalkylene polyols and block polymers such as ethylene oxide and propylene oxide can also be used.
Particularly preferred polyoxyalkylene oxide polyol polymers include ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, triethylene glycol, 2-ethylhexanediol-1.3-glycerin, 1,2,6-hexanetothiol. Ethylene oxide, at least one compound selected from the group consisting of trimethylolpropane, trimethylolethane, tris (hydroxyphenyl) propane, triethanolamine, triisopropanolamine, ethylenediamine and ethanolamine.
Examples thereof include adducts with at least one compound selected from the group consisting of propylene oxide and butylene oxide.

Examples of the organic polyisocyanate used in the present invention include ordinary aromatic, aliphatic and alicyclic ones. For example, tolylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, xylylene diisocyanate,
Examples thereof include naphthalene diisocyanate and derivatives of these modified products, crude products, and isocyanate prepolymers obtained by reacting the isocyanate with polyhydric alcohols or polyols. However, it is not limited to these.

As the surfactant used in the present invention,
It is a component for forming desired cells in polyurethane foam and stabilizing the foam. Examples of the surfactant in this case include L-520 (manufactured by Nippon Unicar Co., Ltd.),
F-242T (Shin-Etsu Silicon Co., Ltd.), SRX-294A
(Manufactured by Toray Dow Corning Co., Ltd.) and the like. But,
It is not limited to this.

The metal-containing catalyst used in the present invention is a component added as a reaction catalyst for polyol and polyisocyanate. Specific examples of such metal-containing catalysts include:
Examples thereof include stannous octoate and stannous dibutyl laurate.

As the foaming agent used in the present invention, water and an organic compound having a low boiling point can be used alone or in combination.
Low-boiling organic compounds include trichloromonofluoromethane, dichlorodifluoromethane, monochlorodifluoromethane, trichlorotrifluoroethane, methylene chloride and the like.

In the present invention, in addition to the above-mentioned components, known components, additives and the like can be added. Examples of such substances include pigments, antioxidants, antistatic agents, bubble communicating agents, antibacterial agents and the like, which can be added during the production of polyurethane foam. These components are appropriately blended in order to impart desired properties to the flame-retardant urethane foam produced.

The halogen-free flame retardant used in the present invention includes, for example, triaryl phosphate. As a precaution, the general formula of triaryl phosphate is shown below.

Embedded image However, R ₁ , R ₂ and R ₃ may be the same and represent a hydrogen atom or an alkyl group. Tricresyl Phosphate (TCP), Cresyl Diphosphate (CD)
P), triphenyl phosphate (TPP), and the like. In addition, halogen-free flame retardants include trimethyl phosphate (TMP), triethyl phosphate (TEP), tributyl phosphate (TB).
P), trialkyl phosphates such as trioctyl phosphate (TOP), tributoxy phosphate (TBXP), or diphenyl octyl phosphate (DOP), diethyl N.P. N-bis (2-hydroxyethyl) aminomethyl phonate etc. are mentioned.

It is preferable to add 1 to 40 parts by weight, preferably 5 to 30 parts by weight, of these flame retardants to 100 parts by weight of the polyol. If more than this amount is added, the flame retardant will interfere with the urethane reaction and the physical properties of the foam will deteriorate significantly.

Next, at least 1 used in the present invention
Examples of amine catalysts having three or more functional groups include dimethylaminohexanol, dimethylaminoethoxyethanol, dimethylethanolamine, dimethylaminoethoxyethanol, trimethylaminoethylethanolamine, methylhydroxyethylpiperazine, tetramethylhydroxypropylenediamine, and hydroxyethoxymorphomorph. Examples include phosphorus. These amine catalysts have a hydroxyl group at the terminal, and the reaction between this hydroxyl group and isocyanate causes no amine to remain in the foam.
Further, even if there is an unreacted substance, it has a boiling point higher than that of a conventional amine catalyst (TEDA or the like) by 30 ° C. or more, and thus is less likely to volatilize.

Regarding the functional groups of the amine catalyst, those having an activated hydrogen such as a hydroxyl group or a carboxyl group at the terminal, and the number of functional groups must be at least one or more.

[0020]

EXAMPLES Further examples of the present invention will be shown below, but of course the present invention is not limited to these examples. Example 1 Polyether polyol (molecular weight 300
0, Mitsubishi Kagaku Dow, "Boranol 3010") 10
0 parts by weight, tolylene diisocyanate (TDI-80,
Sumitomo Bayer Urethane Co., Ltd., Sumidule T-80) 4
2.8 parts by weight, water 3 parts by weight, dimethylaminohexanol ("Kaolyzer No. 25" manufactured by Kao Corporation)
0.12 parts by weight, silicone foam stabilizer (F-242T manufactured by Shin-Etsu Silicon Co., Ltd.) 1.2 parts by weight, stanna octoate 0.2 parts by weight, methylene chloride 3.0 parts by weight, flame retardant CDP (Dahachi) (Chemical company) 5 parts by weight are mixed and stirred,
A polyurethane foam having a density of 24.8 kg / m ³ was obtained.

Example 2 Except that in Example 1 above, 0.5 parts by weight of dimethylaminohexanol and 10 parts by weight of the CDP flame retardant were used as the amine catalyst at the same time.
The same composition as in Example 1 above was mixed and stirred to give a density of 25.
A polyurethane foam of 1 kg / m ³ was obtained.

[Example 3] In the same manner as in Example 1, except that dimethylaminohexanol was 1.0 part by weight and the flame retardant CDP was 20 parts by weight at the same time as the amine catalyst.
The same composition as in Example 1 above was mixed and stirred to give a density of 25.
2 kg / m ³ of polyurethane foam was obtained.

[0023]

Example 4 In the above Example 1, as the amine catalyst,
Example 1 above except that 1.5 parts by weight of dimethylaminohexanol and 30 parts by weight of the CDP flame retardant were used at the same time.
Mixing and stirring with the same composition as above, the density is 25.4 kg / m ³
A polyurethane foam of was obtained.

[0024]

Comparative Example 1 The same composition as in Example 1 was used except that 5 parts by weight of TDCP (manufactured by Akzo) was used in place of 5 parts by weight of the flame retardant CDP in Example 1 above, and the mixture was stirred to obtain the density. To obtain a polyurethane foam having a weight ratio of 25.1 kg / m ³ .

[0025]

Comparative Example 2 The same composition as in Example 2 was mixed and stirred except that 10 parts by weight of TDCP (manufactured by Akzo Co.) was used instead of 10 parts by weight of the flame retardant CDP in Example 2 above.
A polyurethane foam having a density of 25.2 kg / m ³ was obtained.

[0026]

[Comparative Example 3] In the same manner as in Example 3, except that 20 parts by weight of TDCP (manufactured by Akzo Co.) was used instead of 20 parts by weight of the flame retardant CDP, the mixture was mixed and agitated in the same manner as in Example 3,
A polyurethane foam having a density of 25.4 kg / m ³ was obtained.

[0027]

Comparative Example 4 In the above Example 1, DABC was used in place of 0.12 part by weight of the amine catalyst dimethylaminohexanol.
O33LV (manufactured by Sankyo Air Products Co., Ltd.) was mixed and stirred with the same composition as in Example 1 except that 0.5 part by weight was used.
A polyurethane foam having a density of 24.3 kg / m ³ was obtained.

[0028]

Comparative Example 5 In the above Example 2, DABCO was used instead of 0.5 part by weight of the amine catalyst dimethylaminohexanol.
33 LV (manufactured by Sankyo Air Products Co., Ltd.) was mixed and stirred with the same composition as in Example 2 except that 1.0 parts by weight was used to obtain a polyurethane foam having a density of 25.1 kg / m ³ .

[0029]

Comparative Example 6 DABCO was used instead of 1.0 part by weight of the amine catalyst dimethylaminohexanol in Example 3 above.
33 LV (manufactured by Sankyo Air Products Co., Ltd.) was mixed and stirred with the same composition as in Example 3 except that 1.5 parts by weight was used to obtain a polyurethane foam having a density of 25.3 kg / m ³ .

The following comparative evaluation tests were carried out on the polyurethane foams obtained in the above Examples and Comparative Examples. The formulation of each Example and Comparative Example and the results of the following evaluation tests are shown in Table 1 later.

[Evaluation items] (1) Adhesion amount (DIN-75-201 5.3Apparatus
Conforms to "cloudiness test". ) A foam with a thickness of 10 mm and 80 mmΦ is placed in a wide-mouthed bottle, and the lid is covered with a glass plate that is transparently polished from above. After heating at 110 ° C. for 3 hours, the amount (mg) of the deposit on the glass was measured. (2) Transmittance (haze) (%) Transmittance measuring device (Suga Tester HR-TR) is used to measure the transmittance (haze) of the glass plate to which the deposits are attached by the method of (1).
It was measured at. The adhered amount (mg) is 1.0 mg or less, and the transmittance (haze) (%) is 10% or less. (3) Discoloration test A foam of 100 mm x 50 mm x 10 mm thickness is folded in half, sandwiched between cloths, and stapled at 10 places around it. And color difference meter (Nippon Denshoku Industries, SZ-
After the b value was measured with Σ80), it was placed in a beaker and covered with an aluminum cover. After heating at 110 ° C for 192 hours, take it out,
The b value was measured again, and the difference Δb from the b value before heating was calculated. The color change determination criterion is that Δb is 3.0 or less. (4) Flame retardance: Pass MVSS No. 302. The results are shown in Table 1 below.

[0032]

[Table 1]

[0033]

As described above, the present invention, that is, the combined use of the halogen-free flame retardant and the amine catalyst having at least one functional group, simply replaces the halogen-free flame retardant with the fogging phenomenon. Or, rather than improving the discoloration of the fabric, by additionally using an amine catalyst having at least one or more functional groups, the cause of discoloration due to the reaction between the fabric and the amine catalyst,
By preliminarily reacting with isocyanate or the like during the reaction for producing a polyurethane foam and sealing its moving hands, it was possible to obtain a flame-retardant polyurethane foam in which these problems were more clearly prevented.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI Technical display area C08L 75/08 NGD C08L 75/08 NGD // (C08G 18/48 101: 00) C08L 75:08

Claims (2)

[Claims] 1. A polyol, a polyisocyanate, water,
In a polyurethane foam prepared by using raw materials such as a foaming agent, a metal catalyst and an amine catalyst, it is necessary to use both (1) a halogen-free flame retardant and (2) an amine catalyst having at least one functional group. Low pollution characteristics characterized by
Flame-retardant polyurethane foam. 2. With respect to 100 parts by weight of the polyol,
1 to 40 parts by weight of the halogen-free flame retardant of (1),
The low-staining and flame-retardant polyurethane foam according to claim 1, wherein 0.1 to 2 parts by weight of the amine catalyst having at least one functional group of (2) is used in combination.