JPH07149854A - Composition for polyurethane foam - Google Patents

Abstract

PURPOSE:To obtain a composition for polyurethane foam useful for interior materials, etc., having excellent flame retardancy and thermally fusing properties without damaging mechanical strength and compression set by using both a specific urethane polyol and a halogenated aromatic compound. CONSTITUTION:This composition for polyurethane foam uses both (A) an end hydroxyl group-containing urethane polyol comprising (i) a polyol such as ethylene glycol, (ii) a halogen atom-containing low-molecular polyol such as a halogenated ethylene glycol and (iii) a polyisocyanate such as 2,4-tolylene diisocyanate and (B) a halogenated aromatic compound such as decabromodiphenyl ether in the blending ratio of the component A and B of 80/20-99/1 by weight. A bromine atom-containing aromatic compound soluble in the component A, having <=350 deg.C melting point is preferable as the component B.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a polyurethane foam composition containing a urethane polyol and having excellent flame retardancy and heat fusion property, and more particularly to a flexible polyurethane foam composition.

[0002]

2. Description of the Related Art Conventionally, as a method for making a flexible urethane foam flame-retardant, a flame retardant such as a phosphoric acid ester, a halogenated phosphoric acid ester and a chlorinated paraffin is added at the time of foaming, or these are added to a produced foam. A method of impregnating with a flame retardant is adopted. By these methods, the foam itself becomes self-extinguishing and the initial purpose can be achieved. However, when these soft urethane foams with flame retardancy are covered with a cloth or vinyl chloride or other exterior material to form a composite material such as a cushion material, the composite material loses its self-extinguishing property and becomes flammable. .

Further, when a phosphoric acid ester, a halogenated phosphoric acid ester or the like is simply added, the urethane foam is softened and mechanical strength and the like are lowered. As a method for solving these problems, the present inventors have proposed a method using a halogen-containing urethane polyol obtained by reacting a halogen atom-containing low-molecular polyol with a polyisocyanate, as in JP-A-4-55420. However, it has been found that the method tail is excellent in flame retardancy and foam strength, but the compression set is deteriorated.

Further, although the addition of halogenated aromatic compounds generally used for flame retarding plastics such as ABS can be expected to have a great flame retarding effect, since these halogenated aromatic compounds are insoluble in the starting polyol, There is a problem that a uniform and good flame-retardant foam cannot be obtained.

[0005]

DISCLOSURE OF THE INVENTION The present invention provides a urethane foam composition capable of exhibiting excellent flame retardancy in a composite material without deteriorating the physical properties of the foam, particularly mechanical strength and compression set. It is intended to be developed.

[0006]

The present inventors have completed the present invention as a result of various studies in view of the above problems.

That is, the present invention relates to (A) polyol,
(B) a halogen atom-containing low-molecular-weight polyol, (C) a urethane polyol (i) having a terminal hydroxyl group consisting of polyisocyanate, and a halogenated aromatic compound (ii) are used in combination, a polyurethane foam composition,
Preferably, the composition for flexible urethane foam, preferably the halogenated aromatic compound (ii) is soluble in the urethane polyol (i), preferably the halogenated aromatic compound has a melting point of 350 ° C. or less and bromine. It is an aromatic compound having atoms, preferably a halogenated aromatic compound, preferably a mixing ratio of the urethane polyol (i) and the halogenated aromatic compound (ii) is 80 /
20 to 99/1 (weight ratio).

The polyurethane foam composition of the present invention can exhibit excellent flame retardancy in a composite material without impairing the physical properties of the foam.

(Constitution) The polyol (A) of the present invention is selected from various polyols, and preferably selected from the following (a) to (g).

The polyoxyalkylene polyol of the component (a) of the present invention is obtained by adding an alkylene oxide (ethylene oxide, propylene oxide, epichlorohydrin) to a low molecular weight polyhydroxy compound having 2 to 4 functional groups. , Preferably, a molecular weight of 300 to
5,000 can be used. The low molecular weight polyhydroxy compound has 2 to 4 functional groups and a molecular weight of 60 to
300 is preferable, for example ethylene glycol,
1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, 1,3-butylene glycol, 1,4-butylene glycol, 1,6-hexamethylene glycol, bishydroxyethoxybenzene or p
-Glycols such as xylene glycol and neopentyl glycol, and polyfunctional polyhydroxy compounds such as glycerin, trimethylolpropane, hexanetriol, triethanolamine, pentaerythritol, and ethylenediamine can be used.

The alkylene oxide adduct of the aromatic dihydroxy compound as the component (b) has a molecular weight of 23.
The term refers to an aromatic nucleus-containing polyether diol in the range of 0 to 5,000, preferably 250 to 2,000. Of these, typical examples of aromatic dihydroxy compounds include catechol, hydroquinone or bishydroxyethoxybenzene. , Or general formula [I]

[0012]

[Chemical 1]

(In the formula, R and R'represent a hydrogen atom or an alkyl group respectively) or the general formula [II].

[0014]

[Chemical 2]

Although there is an aromatic dihydroxydiphenyl compound represented by the following, bisphenol A, bisphenol F, bisphenol S, etc. are particularly preferable in view of easy availability of raw materials and physical properties as a flexible polyurethane foam. On the other hand, typical examples of the alkylene oxide used for addition with the aromatic dihydroxy compound include ethylene oxide,
Propylene oxide, epichlorohydrin or 1,2
-Butylene oxide or mixtures thereof.

As the polyester ether polyol as the component (c), a polyoxyalkylene polyol having a molecular weight of 300 to 5,000 alone or in combination with a low molecular weight polyhydroxy compound is used as an alcohol component. The same low molecular weight polyhydroxy compound used in the components (a) and (a) can be used. On the other hand, the aliphatic dicarboxylic acid as the acid component is preferably one having 3 to 14 carbon atoms, for example, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, 1,9 -Nonamethylene dicarboxylic acid, 1,10-decamethylene dicarboxylic acid, 1,12
-Dodecamethylenedicarboxylic acid and the like. The aromatic dicarboxylic acid includes, for example, orthophthalic acid, isophthalic acid, terephthalic acid, anthracene dicarboxylic acid or phenanthrene dicarboxylic acid, but it is needless to say that their anhydrides or various derivatives can also be used. The above mixture may be used, but orthophthalic acid, isophthalic acid or terephthalic acid is particularly preferable.

As the aromatic nucleus-containing diol having a molecular weight of 230 to 5,000 obtained by adding an alkylene oxide to the aromatic dihydroxy compound as the component (d), the same diol as the component (c) can be used. The same polyhydroxy compound used as the alcohol component is used. As the aliphatic dicarboxylic acid as an acidic component, one having 3 to 6 carbon atoms is used, and examples thereof include malonic acid, succinic acid, glutaric acid and adipic acid used in the component (c). As the aromatic dicarboxylic acid, the same ones as the above-mentioned component (c) can be used.

The polyester ether polyol as the component (e) has a molecular weight of 500 to 6,000, and the diol containing an aromatic nucleus can use the component (b) as it is. Further, as the low molecular weight polyhydroxy compound,
The same compound as the low molecular weight polyhydroxy compound used in the component (a) can be used. As the long-chain aliphatic dicarboxylic acid, those having 7 to 14 carbon atoms are suitable. For example, among the dicarboxylic acids listed as the component (c), pimelic acid to 1,12-dodecamethylenedicarboxylic acid are used. it can. Azelaic acid and sebacic acid having 9 or 10 carbon atoms are preferable. When an aliphatic dicarboxylic acid having a carbon number of 6 or less is used, the elongation of the flexible urethane foam decreases, and conversely, when 15 or more is used, the hardness and strength of the foam decrease. However, both are not preferable. As the aromatic dicarboxylic acid, those described in the above component (b) are used.

The aromatic dicarboxylic acid and the long-chain aliphatic dicarboxylic acid are used in a molar ratio of 1/9 to 9/1, but 5/5 to 9 in terms of mechanical properties of the obtained foam. The range of / 1 is preferable.

As the component (f) used as the polyol of the present invention, polyoxytetramethylene glycol having a molecular weight of 500 to 5,000 can be used.

The component (g) is the same compound as the low molecular weight polyhydroxy compound used in the component (a), the same aliphatic and aromatic dicarboxylic acid as the component (c), and their anhydrides. An acid alcohol condensation type polyester polyol obtained from at least one of various derivatives and a mixture thereof, or a polylactone type polyester polyol obtained by polymerizing ε-caprolactone and a mixture thereof can be used.

As the halogen atom-containing low-molecular weight polyol as the component (B), a part of hydrogen atoms bonded to carbon atoms of the same low-molecular weight polyhydroxy compound used as the component (a) is a halogen atom. A compound substituted with (fluorine atom, chlorine atom, bromine atom, iodine atom) can be used. For example, halogenated ethylene glycol, monohalogenated propylene glycol, dihalogenated propylene glycol, di (halogenated ethylene) glycol, monohalogenated butylene glycol, dihalogenated butylene glycol, monohalogenated butylene glycol, dihalogenated butylene glycol, tetrahalogen Butylene glycol, monohalogenated hexamethylene glycol, dihalogenated hexamethylene glycol,
Trihalogenated hexamethylene glycol, tetrahalogenated hexamethylene glycol, monohalogenated neopentyl glycol, dihalogenated neopentyl glycol and the like can be used. Preferable examples include monohalogenated neopentyl glycol and dihalogenated neopentyl glycol in which a hydrogen atom is not bonded to the carbon adjacent to the carbon bonded to the halogen atom due to the stability of the halogen atom. Further, these compounds can be used in combination of two or more kinds.

In order to prepare the above-mentioned polyester ether polyol or polyester polyol by using the above-mentioned various raw materials, conventionally known esterification technology carried out by using a vacuum and / or a catalyst can be adopted. Among them, as a typical one, a method of reacting glycols and a dicarboxylic acid under atmospheric pressure, a method of esterifying under vacuum, or an esterification in the presence of an inert solvent such as toluene is performed. , A method in which condensed water and a solvent are azeotropically distilled to remove them out of the reaction system.

It is of course possible to carry out the reaction in the absence of a catalyst, but usually, in order to make the esterification reaction proceed smoothly, inorganic or organic acids; Li, Na,
K, Rb, Ca, Mg, Sr, Zn, Al, Ti, V, Cr, Mn, Fe, C
o, Ni, Cu, Zr, Pb, Sn, Sb or Pb and other metal chlorides, oxides, hydroxides or fatty acid salts such as acetic acid, oxalic acid, octylic acid, lauric acid or naphthenic acid; sodium methylate , Alcohols such as sodium ethylate, aluminum triisopropoxide, isopropyl titanate or n-butyl titanate; phenolates such as sodium phenolate; or Al, Ti, Zn, Sn, Zr, or Pb.
It is preferable to use all the catalysts used for ordinary esterification and transesterification, such as other metal compounds of metals such as. In that case, the amount of the catalyst used is in the range of 0.00001 to about 5% by weight, preferably 0.
The range of 001 to 2% by weight is suitable. The reaction temperature at this time is usually in the range of 100 to 250 ° C.

The terminal OH group-containing urethane polyol of the present invention can be produced by using the above-mentioned various raw materials based on a usual method for producing a urethane prepolymer. That is, 50 to 100
℃, under nitrogen atmosphere OH / NCO = 1-5 / 1 (molar ratio),
It is preferably 1.2 to 1.5 / 1 (molar ratio) and can be produced by a one-step method or a sequential reaction method.

The polyisocyanate (C) used in the present invention is, for example, 2,4-tolylene diisocyanate or 2,6-tolylene diisocyanate or a mixture thereof, m- or p-phenylene diisocyanate, p-xylene diisocyanate, Ethylene diisocyanate, tetramethylene-1,4-diisocyanate,
Hexamethylene-1,6-diisocyanate, diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyl-diphenylmethane-4,4'-diisocyanate, 3,3'-dimethyl-4,4'-biphenylene diisocyanate, 3 , 3'-Dichloro-4,4'-biphenylene diisocyanate, 4,4'-
Mention may be made of biphenylene diisocyanate or 1,5-naphthalene diisocyanate, crude diphenylmethane diisocyanate and various derivatives of diphenylmethane diisocyanate.

In carrying out the present invention, a combination of at least one polyol (A) selected from the above-mentioned (a) to (g) and a halogen atom-containing low-molecular polyol (B) is used in combination with a polyisocyanate (C). ) To obtain a urethane polyol having a terminal OH group. The flexible urethane foam using such a urethane polyol containing terminal OH groups has the effect of re-bonding due to a chemical bond when a frame (flame) is applied and strengthening the adhesive force with the base material (heat fusion property). Further, those in which an ester bond is introduced into the polyols (a) to (g) are particularly preferable because they enhance the strength and heat fusion of the foam.

The halogenated aromatic compound used in the present invention is a compound in which a halogen atom is directly attached to an aromatic ring, and preferably has a melting point of 350 ° C. or lower, further 50 to 350.
Aromatic compounds in which the halogen atom is bromine at ° C are preferred. For example, decabromodiphenyl ether (305
C), octabromodiphenyl ether (70-150
C.), hexabromodiphenyl ether, and a brominated aromatic compound represented by the following structural formula represented by pentabromodiphenyl ether.

[0029]

[Chemical 3]

(However, X + Y = 4 to 10)

The mixing ratio of the urethane polyol (i) having a terminal hydroxyl group of the present invention and the halogenated aromatic compound (ii) is not particularly limited, but the solubility of the halogenated aromatic compound in the polyol is not limited. From the surface, the weight ratio is 8
0/20 to 99/1 is desirable. The compound (ii) is 2
When it is more than 0, the compound becomes difficult to dissolve in urethane polyol, and when it is less than 1, flame retardancy cannot be improved.

Immediately after the production of the urethane polyol having a terminal hydroxyl group, the urethane polyol (i) having a terminal hydroxyl group of the present invention is mixed with the halogenated aromatic compound (ii) at room temperature because the halogenated aromatic compound does not dissolve. And can be mixed at a temperature of about 50 to 130 ° C. to uniformly dissolve them.

The urethane polyol having terminal OH groups characteristically used for carrying out the method of the present invention is, as described above, a heat-melting material having excellent stability, physical properties of foam, heat-sealing property and scorch resistance. Since it gives an adhesive flexible polyurethane foam, the above-mentioned specific components should be exclusively used, but if necessary, those having a functional group number of 2 to 8 and a molecular weight of 500 to 7,000, such as polyoxypropylene. Polyol, polyoxyethylene polyol and polyoxyethylene propylene polyol (block or random polymer), polyether polyol such as polyoxytetramethylene glycol, adipic acid-based polyester polyol such as polyethylene adipate and polybutylene adipate, lactone-based poly It does not prevent in any way the use and mixed ester polyols and polyfunctional components thereof (trimethylolpropane, pentaerythritol, hexane triol) a polyol was introduced within a range not to impair the physical properties to a specific polyol supra.

The above raw materials may be used to produce a flexible urethane foam by a conventionally known method such as a one-shot method or a prepolymer method. The prepolymer method is a method of previously reacting a polyol and a polyisocyanate to obtain one kind of prepolymer, and then reacting this with a polyhydroxy compound in the presence of a foaming agent, a catalyst, a foam stabilizer and other additives, or The one-shot method is a method of reacting an organic polyisocyanate with a polyhydroxy compound in the presence of a catalyst, a foaming agent, a foam stabilizer and other additives, and a flexible polyurethane foam can be produced by these methods. Here, as the polyisocyanate, those mentioned above can be used.

The catalyst used in the present invention may be one commonly used in the production of polyurethane foams, and examples thereof include organotin compound catalysts and amine catalysts. Examples of the organotin compound catalysts include stannous octoate, stannase oleate, dibutyltin dilaurate, dibutyltin di-2-ethylhexoate and dibutyltin diacetate.

In the present invention, the foam stabilizer used may be a general silicone foam stabilizer for producing polyurethane foam. Further, in the present invention, water (which produces carbon dioxide gas when reacted with an organic isocyanate) is mainly used as a foaming agent, but if necessary, a low boiling point organic compound such as monofluorotrichloromethane or methylene chloride is used. Compounds and air can also be used.

In addition to the above-mentioned components, a filler, an antistatic agent, a colorant, a flame retardant, etc. may be added depending on the performance required of the foam, as long as the object of the present invention is not exceeded. The flame retardant used in the present invention may be a commonly used one, for example, trischloroethyl phosphate, trischloropropyl phosphate, trisdichloropropyl phosphate, trimethyl phosphate, triethyl phosphate, tributoxyethyl toephate, tricresyl foci. Fate or CR-5
05, UF-504, CR-530, UF-530 (Daihachi Chemical Products), Amgard V6, V500D (Albright & Wilson Products), Thermolin 101
A halogen-containing condensed phosphoric acid ester such as (Asahi Aurin product) can also be used.

In order to make the composite material of the present invention, a flexible polyurethane foam is formed and then (1) a method of laminating it with an adhesive (for example, urethane type, ethylene-vinyl acetate type) is used, and (2) urethane by flame. A composite material is obtained by a frame lamination method in which the foam surfaces are melted and bonded together, and (3) a method in which high-frequency bonding is performed.

Materials to be laminated include cloth, woven fabric, knitted fabric, synthetic leather, leather, etc., which are mainly made of polyester, nylon, vinyl chloride, polyurethane and the like. Particularly, in the case of polyester, nylon, or a blended fabric thereof, the polyurethane foam of the present invention exhibits excellent flame retardancy.

The applications of the present invention, which are used due to the flame retardancy, are interior materials (ceiling, walls), vehicles (vehicles, trains,
Airplane) seats, chairs, leisure goods, etc.

[0041]

EXAMPLES Examples of the present invention will now be described, but the present invention is not limited thereto. In the text, "part" and "%" are based on weight.

Example 1 1,500 parts of polyoxypropylene diol having a molecular weight of 1,500 was mixed with 2,4 / 2,6-tolylene diisocyanate (2,4 / 2,6 = 80/20 mixing ratio, hereinafter T).
380 parts (referred to as DI-80) were reacted at 80 ° C. in a nitrogen atmosphere to obtain a urethane prepolymer containing NCO groups at both ends. Then, 524 parts of dibromoneopentyl glycol was reacted under the same conditions to prepare a urethane polyol having a terminal OH group (hydroxyl value = 48.5). After completion of the reaction, 264 parts of octabromodiphenyl ether was added and uniformly dissolved at 80 ° C to obtain a polyol.

20 parts of the above polyol has a molecular weight of 3,000.
80 parts by weight of polyoxypropylene triol, and 0.1 parts of triethylenediamine dissolved in 4.0 parts of water, silicon SH-194 (manufactured by Dow Corning) 1.
Add 0 parts, stanas octoate 0.25 parts, methylene chloride 5.0 parts, flame retardant UF-504 (manufactured by Daihachi Chemical Co., Ltd.) 15 parts, and then add TDI-80 (NCO index 110) and stir vigorously. To obtain a flexible urethane foam [I].

Example 2 A polyester polyol (hydroxyl value = 53.5) obtained from 374 parts of polyoxypropylene diol having a molecular weight of 600, 146 parts of adipic acid and 39 parts of ethylene glycol was obtained. 2,120 parts of the obtained polyester polyol was reacted with 348 parts of TDI-80 to form a terminal NCO group-containing prepolymer, and then 524 parts of dibromoneopentyl glycol was reacted to obtain a urethane polyol (hydroxyl value = 35.3) containing an terminal OH group. After completion of the reaction, 332 parts of octabromodiphenyl ether was added and uniformly dissolved at 80 ° C. to obtain a polyol.

20 parts of the above polyol has a molecular weight of 3,000.
80 parts by weight of polyoxypropylene triol, and 0.1 parts of triethylenediamine dissolved in 0.4 parts of water, Silicon SH-194 (manufactured by Dow Corning) 1.
0 part, stanna octoate 0.25 part, methylene chloride 5.0 part, flame retardant UF-504 (manufactured by Daihachi Chemical Co., Ltd.) 10
Then, TDI-80 (NC0 index 110) was added, and the mixture was vigorously stirred and poured into an appropriate mold to obtain a flexible urethane foam [II].

Example 3 1,300 parts of an aromatic nucleus-containing diol having a molecular weight of 1,300 obtained by adding propylene oxide to bisphenol A was reacted with 348 parts of TDI-80 to prepare an NCO-terminated urethane prepolymer, and then , 346 parts of dichloroneopentyl glycol are reacted to produce a urethane polyol containing a terminal OH group (hydroxyl value = 5
6.3) was adjusted. After completion of the reaction, 351 parts of octabromodiphenyl ether was added and uniformly dissolved at 80 ° C to obtain a polyol.

25 parts of the above polyol has a molecular weight of 3,000.
75 parts by weight of polyoxypropylene triol, and 0.1 parts of triethylenediamine dissolved in 4.0 parts of water, Silicon SH-194 (manufactured by Dow Corning) 1.
Add 0 parts, stanas octoate 0.25 parts, methylene chloride 5.0 parts, flame retardant UF-504 (manufactured by Daihachi Chemical Co., Ltd.), further add TDI-80 (NCO index 110) and stir vigorously. Flexible urethane foam [I
II] was obtained.

Comparative Example 1 2 parts of octabromodiphenyl ether was added to 99 parts of polyoxypropylene triol having a molecular weight of 3,000 which is used in a usual flexible urethane foam as a raw material polyol, and an attempt was made to dissolve it at 100 ° C. Since it could not be dissolved in, the uniform polyol could not be obtained.

Comparative Example 2 TDI-80348 was added to 1,500 parts of polyoxypropylene diol having a molecular weight of 1,500.
Parts were reacted at 80 ° C. under a nitrogen atmosphere to obtain urethane prepolymers containing NCO groups at both ends. Then, 524 parts of dibromoneopentyl glycol was reacted to prepare a urethane polyol containing an OH terminal (hydroxyl value = 48.5).

Urethane polyol 3 containing the above-mentioned terminal OH group
70 parts of polyoxypropylene triol having a molecular weight of 3,000 was mixed with 0 part of this, and triethylenediamine 0.1
Dissolved in 4.0 parts of water, Silicon SH-194
(Dow Corning) 1.0 part, stanna octoate
0.25 parts, methylene chloride 5.0 parts, flame retardant UF-50
No. 4 (manufactured by Daihachi Chemical Co., Ltd.) was added, and TDI-80 (NCO index 110) was further added. After vigorous stirring, the mixture was poured into an appropriate mold to obtain a flexible urethane foam [IV].

[Test] The urethane foams [I] to [IV] obtained in Examples and Comparative Examples are shown in Table 1 with respect to the test results of physical properties, flame retardancy and heat-sealing property.

[0052]

[Table 1]

(Test method) Foam physical property measurement method: foam hardness, compression set J
IS K-6401 Tensile strength, elongation ASTM D 1564 Tear strength JIS K-6301 Flammability measuring method: MVSS-302 The composite material used in the flammability measuring test is [I] to [I].
Slice the V] urethane foam to a thickness of 15 mm,
A polyester cloth heat-sealed was used.

[0054]

The combined use of the urethane polyol (i) having a terminal hydroxyl group of the present invention and the halogenated aromatic compound (ii) has excellent foam physical properties (improvement of compression set) and excellent flame retardancy and It is possible to provide a flexible polyurethane foam having a heat fusion property.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display area C08G 101: 00)

Claims (5)

[Claims] 1. A polyurethane foam composition comprising: (A) a polyol, (B) a halogen atom-containing low-molecular-weight polyol, and (C) a polyisocyanate-containing urethane polyol (i) having a terminal hydroxyl group.
And a halogenated aromatic compound (ii) in combination, for use in a polyurethane foam composition. 2. The urethane foam composition according to claim 1, wherein the urethane foam is a flexible polyurethane foam. 3. The polyurethane foam composition according to claim 1, wherein the halogenated aromatic compound (ii) is soluble in the urethane polyol (i). 4. The halogenated aromatic compound has a melting point of 35.
The composition for a polyurethane foam according to claims 1 to 3, which is an aromatic compound having a bromine atom at 0 ° C or lower. 5. The mixing ratio of the urethane polyol (i) and the halogenated aromatic compound (ii) is 80/20 to 99.
It is / 1 (weight ratio), The composition for polyurethane foams of Claims 1-4 characterized by the above-mentioned.