JPH0455420A - Urethane polyol and composition for polyurethane form using the same - Google Patents

Abstract

PURPOSE:To obtain the title polyol containing terminal OH, consisting of a polyol, a halogen atom-containing low-molecular polyol and a polyisocynate and capable of providing a flexible polyurethane foam having excellent foam physical properties as well as excellent flame retardancy and heat-melting property. CONSTITUTION:The objective polyol consisting of (A) a polyol [preferably (i) polyoxyalkylene polyol having 300-5000 molecular weight, (ii) an aromatic nucleus-containing diol obtained by adding an alkylene oxide to an aromatic dihydroxy compound having 230-5000 molecular weight, (iii) a polyoxyalkylene glycol having 300-5000 molecular weight and (iv) an aromatic nucleus-containing diol obtained by adding an alkylene oxide to an aromatic dihydroxy compound and having 230-5000 molecular weight, (B) a halogen atom-containing low- molecular polyol (e.g. monohalogenated neopentyl glycol) and (C) a polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a urethane polyol and a composition for urethane foam containing the same that has excellent V1 flammability, thermal adhesion and foam properties, particularly flexible polyurethane foam. It is something.

(Prior art and its problems) Conventional methods for making soft urethane foam flame retardant include adding flame retardants such as phosphate esters, halogenated phosphate esters, and chlorinated paraffins during foaming, or adding flame retardants to the foam produced. A method of impregnating these flame retardants has been adopted. By these methods, the foam itself becomes self-extinguishing and the initial objective can be achieved. However, when these flame-retardant soft urethane foams are covered with exterior materials such as cloth or vinyl chloride to make composite materials such as cushioning materials, the composite material as a whole loses its self-extinguishing properties and becomes flammable. Become.

This is because when the composite material is exposed to high temperatures, the soft urethane foam melts, adheres to the exterior material, or penetrates into the interior, and the exterior material begins to burn, which then causes the soft urethane foam to melt, resulting in a combustion cycle. This is because the composite material as a whole becomes flammable.

In order to solve these problems, methods have been proposed in which ceramic powder, carbonaceous fibers, etc. are added to the raw materials.

However, in this method, there are problems in that the addition of ceramics or carbonaceous fibers to the raw materials increases the viscosity and significantly reduces the cushioning properties and feel required of the soft urethane foam.

(Problems to be Solved by the Invention) The present invention provides a polyol for polyurethane that can exhibit excellent flame retardancy in a composite material without impairing foam physical properties, foam compression properties, foam feel, etc. The present invention relates to a composition for urethane foam containing the following.

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

(Means for Solving the Problems) That is, the present invention provides a urethane polyol having a terminal hydroxyl group consisting of (A) polyol, (B) halogen atom-containing low-molecular polyol, and (C) polyisocyanate, and a polyurethane foam using the same. The present invention provides a composition, preferably a flexible urethane foam, and preferably a specific urethane polyol.

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

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

The polyoxyalkylene polyol as component (a) of the present invention is prepared by adding alkylene oxide (ethylene oxide, propylene oxide, butylene oxide, styrene oxide, epichlorohydrin) to a low molecular weight polyhydroxy compound having 2 to 4 functional groups. and preferably those having a molecular weight of 300 to 5.000 can be used. The low molecular weight polyhydroxy compound preferably has a functional group number of 2 to 4 and a molecular weight of 60 to 300,
For example, ethylene glycol, 1,2-propylene glycol, 1,3-propylene glycol, diethylene glycol, 1,3-butylene glycol, 14-butylene glycol, 1,6-hexamethylene glycol, bishydroxyethoxybenzene or P-xylene glycol , glycols such as neopentyl glycol,
Glycerin, trimethylolpropane, hexanetriol, triethanolamine, pentaerythritol,
Multifunctional polyhydroxy compounds such as ethylenediamine can be used.

(b) The alkylene oxide adduct of an aromatic dihydroxy compound as a component has a molecular weight of 230 to 5,000.
0, preferably in the range of 250 to 2,000, and representative aromatic dihydroquine compounds include catechol, hydroquinone, bishydroxyethoxybenzene, or There are aromatic dihydroxydiphenyl compounds that are indicated by holes or holes, but when taking into consideration the ease of obtaining raw materials and the physical properties of flexible polyurethane foam, bisphenol A, bisphenol F, or bisphenol S can be used.
On the other hand, typical alkylene oxides used for addition with the aromatic dihydroxy compound include ethylene oxide, propylene oxide, epichlorohydrin, 1,2-butylene oxide, or mixtures thereof.

The polyester ether polyol as component (c) is a polyoxyalkylene polyol with a molecular weight of 300 to 5,000 used alone or in combination with a low-molecular polyhydroxy compound as an alcohol component. The same low-molecular polyhydroxy compound used in component (a) can be used. on the other hand,
The aliphatic dicarboxylic acid as an acid component has 3 to 14 carbon atoms.
Preferred examples include malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, phosphoric acid, azelaic acid, sebacic acid, 1,9-nonamethylenedicarboxylic acid, 1,10-decamethylenedicarboxylic acid, l.

Examples include 11-undecamethylene dicarboxylic acid and 1,12-dodecamethylene dicarboxylic acid. Examples of aromatic dicarboxylic acids include orthophthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenanthenedicarboxylic acid, but it goes without saying that their anhydrides or various derivatives can also be used. Although two or more of these may be used as a mixture, orthophthalic acid, isophthalic acid, or terephthalic acid is particularly preferred.

(d) A molecular weight of 230 to 5 obtained by adding alkylene oxide to an aromatic dihydroxy compound as a component,
As the aromatic nucleus-containing diol 000, the same diol as the component (c) can be used. Further, as the polyhydroxy compound used in combination as the alcohol component, the same low molecular weight polyhydroxy compound as used in component (a) above is used. Further, as the aliphatic dicarboxylic acid as the acid component, those having 3 to 6 carbon atoms are used, such as the above-mentioned (c
) ingredients used in malonic acid, succinic acid, glutaric acid,
Adipic acid is mentioned. Further, as the aromatic dicarboxylic acid, the same ones as those used for component (c) can be used.

The polyester ether polyol as the component (e) has a molecular weight of 500 to 6,000, and the aromatic nucleus-containing diol as the component (b) can be used as it is. Further, as the low-molecular polyhydroxy compound, the same compound as the low-molecular polyhydroxy compound used in component (a) can be used. As the long-chain aliphatic dicarboxylic acid, those having 7 to 14 carbon atoms are suitable; for example, from among the dicarboxylic acids listed above for component (c), pimelic acid,
Up to 12-dodecamethylene dicarboxylic acid can be used.

Preferred are azelaic acid and sebacic acid having 9 carbon atoms or 0 carbon atoms. If an aliphatic dicarboxylic acid with a carbon number of 6 or less is used, the elongation of the soft urethane foam will be reduced, while if an aliphatic dicarboxylic acid with a carbon number of 15 or more is used, the hardness and strength of the foam will be reduced. Both of these are not desirable.

Further, as the aromatic dicarboxylic acid, those described for component (b) above are used.

The aromatic dicarboxylic acid and the long chain aliphatic dicarboxylic acid are used in a molar ratio of 179 to 9/1,
In terms of mechanical properties of the obtained foam, a range of 575 to 9/1 is preferred.

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

Components include the same compound as the low-molecular-weight polyhydroxy compound used in component (a), the same aliphatic and aromatic dicarboxylic acids as component (c), and their anhydrides and various derivatives. Acid alcohol condensation polyester polyols obtained from at least one type of polyester polyol and mixtures thereof, polylactone polyester polyols obtained by polymerizing ε-caprolactone, and mixtures thereof can be used.

In the halogen atom-containing low-molecular polyol as component (B), some of the hydrogen atoms bonded to the carbon atoms of the same compound as the low-molecular polyhydroxy compound used in component (a) are replaced with halogen atoms (fluorine atoms). , 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 butyne glycol, dihalogenated butyne 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. Preferably, in view of the stability of the halogen atom, monohalogenated neopentyl glycol, dihalogenated neopentyl glycol, etc., in which a hydrogen atom is not bonded to the carbon adjacent to the carbon bonded to the halogen atom, are preferred.

In order to prepare the polyester ether polyol or polyester polyol using the raw materials listed above, conventionally known esterification techniques using a vacuum and/or a catalyst can be employed,
Among these, typical methods include a method of reacting glycols and dicarboxylic acids under normal pressure, a method of esterification under vacuum, and a method of esterifying in the presence of an inert solvent such as toluene. There is a method in which the condensed water and the solvent are azeotropically distilled and removed from the reaction system.

Although it is of course possible to carry out the reaction in a system without a catalyst, in order to make the esterification reaction proceed smoothly, inorganic or organic acids; LiNa, Rb,
Ca, Mg, Sr, Zn+ Af, Ti,
V+-Cr+Mn, Fe, Go, Ni+ C
u+ Chlorides, oxides, hydroxides of metals such as Zr, pd, Sn, sb or pb or fatty acid salts such as acetic acid, oxalic acid, octylic acid, lauric acid or naphthenic acid; sodium methylate, sodium ethylate , aluminum triisopropoxide, alcoholades such as isopropyl titanate or n-butyl titanate; phenolates such as sodium phenolate; or ACTi+ Zn, S
It is preferred to work with all the catalysts conventionally used for esterification and transesterification, such as n, Zr or other organometallic compounds of metals such as pb. The amount of catalyst used at that time is 0.00001 to 0.00001 to the total amount of raw materials for preparing the polyester diol.
A range of about 5% by weight, preferably 0.001 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 using the above-mentioned raw materials based on a normal urethane prepolymer production method. That is, OH/NGO = 1 to 5/1 (molar ratio), preferably 1.2 to 1.5/1 (molar ratio) under a nitrogen atmosphere at 50 to 100°C, by the -throwing method or the sequential reaction method. Can be manufactured.

Examples of the polyisocyanate (C) used in the present invention include 2,4-1-lylene diisocyanate, 2,6-)lylene diisocyanate, or a mixture thereof, m- or p-phenylene diisocyanate,
p-xylene diisocyanate, ethylene diisocyanate, tetramethylene-14-diisocyanate, hexamethylene-16-diisocyanate, diphenylmethane-4,4' diisocyanate, 33'-dimethyl-
diphenylmethane-4,4'-diisocyanate, 33
'Dimethyl-4,4'-biphenylene diisocyanate, 3,3'-dichloro-4,4'-biphenylene diisocyanate, 4+4'-biphenylene diisocyanate or 1,5-naphthalene diisocyanate, crude diphenylmethane diisocyanate and various derivatives of diphenylmethane diisocyanate are mentioned. It will be done.

In carrying out the present invention, a combination of at least one polyol (A) of the above-mentioned (a) to (g) and a halogen atom-containing low molecular weight polyol (B) and a polyisocyanate (C) are used. A urethane polyol containing a terminal O1 group is obtained by reacting with the urethane polyol. When a soft urethane foam using such a urethane polyol containing a terminal OH group is exposed to a flame, recombination occurs due to chemical bonding, and the bonding with the base material occurs. It has the effect of strengthening the force (thermal adhesiveness).Also, polyols (a) to (g) in which ester bonds are introduced are particularly preferred because they increase the strength of the foam and the thermal adhesiveness. be.

As mentioned above, the urethane polyol containing a terminal OH group, which is characteristically used in carrying out the method of the present invention, is a heat-sealable polyol with extremely excellent stock solution stability, foam physical properties, heat-sealing properties, and scorch resistance. Since it is intended to provide a flexible polyurethane foam, specific components such as those listed above should be used exclusively, but if necessary, the number of functional groups may be 2.
~8, with a molecular weight of 500 to 7,000, such as polyoxypropylene polyol, polyoxyethylene polyol, polyoxyethylene propylene polyol (block or random polymer), polyether polyol such as polyoxytetramethylene glycol, or polyethylene Adipate, polybutylene adipate, and other adipic acid-based polyester polyols, lactone-based polyester polyols, and polyols into which polyfunctional components (trimethylolbrohane, pentaerythritol, hexanetriol) are introduced are added to the above-mentioned specific polyols without impairing their physical properties. This does not in any way prevent them from being mixed and used within a certain range.

A soft urethane foam may be manufactured using the above-mentioned raw materials by a conventionally known method such as a one-shot method or a prepolymer method. The prepolymer method is a method in which a polyol and a polyisocyanate are reacted in advance to obtain a type of prepolymer, which is then reacted with a polyhydroxy compound in the presence of a blowing agent, a catalyst foam stabilizer, and other additives, or a one-shot method. The method involves reacting an organic polyisocyanate with a polyhydroxy compound in the presence of a catalyst, a blowing agent, a foam stabilizer, and other additives, and flexible polyurethane foam can be produced by these methods. Here, as the polyisocyanate, those listed above can be used.

The catalyst used in the present invention may be one commonly used in the production of polyurethane foam, such as organotin compound catalysts and amine catalysts. Examples of organic tin compound catalysts include stannath octoate, stannath oleate, dibutyltin dilaurate, and dibutyltin di2.
-Ethylhexoate, dibutyltin diacetate, etc.

In the present invention, the foam stabilizer used may be a silicone foam stabilizer commonly used for producing polyurethane foams.

In addition, in the present invention, water (which generates carbon dioxide gas by reaction with organic isocyanate) is mainly used as a blowing agent, but if necessary, low-boiling point foams such as monofluorotrichloromethane or methylene chloride may be used. Organic compounds and air can also be used.

In addition to the above-mentioned ingredients, fillers, antistatic agents, colorants, flame retardants, etc. may be added depending on the performance required of the foam, as long as they do not depart from the purpose of the present invention.

The flame retardants used in the present invention may be those commonly used, such as trichloroethyl phosphate, trisdichloropropyl phosphate, trimethyl phosphate, I-'J ethyl phosphate, tributoxyethyl foveate, tricresyl phosphate, or C
Halogen-containing condensed phosphoric acid esters such as R-505 (Oana Chemical Products) and Thermolin 101 (Asahi Olin Products) can be used.

In order to make the present invention into a composite material, there are two methods: (1) bonding using an adhesive (for example, urethane type, ethylene-vinyl acetate type, etc.) after forming a flexible polyurethane foam;
It is made into a composite material by the flame lamination method, in which the surfaces of the urethane foams are melted and bonded together using flames, and (3) the method in which the urethane foam is bonded together using high frequency waves.

Materials to be bonded include cloth, woven fabrics, knitted fabrics, synthetic leather,
They include leather, etc., and are mainly made of polyester, nylon, vinyl chloride, polyurethane, etc. In particular, the polyurethane foam of the present invention exhibits excellent flame retardancy in fabrics made of polyester, nylon, or a blend thereof.

Applications of the present invention due to its flame retardancy include interior materials (ceilings, walls), vehicle seats (automobiles, trains, airplanes), chairs, leisure goods, and the like.

(Example) Next, the present invention will be explained by examples, but the present invention is not limited thereto. In the text, "part" and "1%" are based on weight.

[Example 1] Polyoxypropylene diol 1 with a molecular weight of 1,500
, 500 parts, 2.4/2.6 to tolylene diisocyanate (2,4/2.6 = 80/20 mixing ratio, hereinafter T
(referred to as DI-80) was heated at 80°C under nitrogen atmosphere.
A urethane polymer containing NCO groups at both ends was obtained. Next, 524 parts of dibromoneopentyl glycol was reacted under the same conditions to prepare a terminal OH group-containing urethane polyol (hydroxyl value=47.9).

70 parts of polyoxypropylene triol having a molecular weight of 3,000 were mixed with 30 parts of the above-mentioned urethane prepolymer containing terminal OH groups, and 0.1 part of triethylenediamine was added to this mixture with 4 parts of water.
．． 0 parts dissolved, 1.0 parts of silicone L5.40 (manufactured by Nihon Nihon Ka), 0.25 L of Stanus octoate
5.0 parts of trichlorofluoroethane, flame retardant CR-50
5 (manufactured by Ohana Kagaku), 7 parts of TDI-8051 (NGO index 110) were added, and after stirring vigorously, the mixture was poured into a suitable mold and the soft urethane foam (1) was poured into l.

[Example 2] Polyester polyol obtained from 374 parts of polyoxypropylene diol with a molecular weight of 600, 146 parts of adipic acid, and 39 parts of ethylene glycol (hydroxyl value = 53.0
) was obtained. Obtained polyester polyol 2,120
part was reacted with 80348 parts of Tl1l-80, and the final @NCO
The group-containing prepolymer was then reacted with 524 parts of dibromoneopentyl glycol to obtain a urethane polyol containing terminal OH groups (hydroxyl value=34.5).

80 parts of polyoxypropylene triol having a molecular weight of 3,000 are mixed with 20 parts of the above-mentioned urethane polyol containing terminal OH groups, and 0.1 part of triethylenediamine is mixed with 4.0 parts of water.
0 parts, 1.0 parts of silicone L540 (manufactured by Nippon Unica), 0.25 parts of stanas octoate, 5.0 parts of trichlorofluoroethane, and flame retardant CR-505 (manufactured by Ohana Kagaku) were added, and further TDI-8051, 4 copies (NG
After stirring vigorously, the mixture was poured into a suitable mold to obtain a soft urethane foam (II).

(Example 3) Aromatic nucleus-containing diol 1,3 with a molecular weight of 1,300 obtained by adding propylene oxide to bisphenol A
00 parts was reacted with 348 parts of TDI-80 to obtain an NGO-terminated urethane prepolymer, and then reacted with 346 parts of dichloroneopentyl glycol to obtain a terminal OH group-containing urethane polyol (hydroxyl value=56.0).

30 parts of polyoxypropylene triol having a molecular weight of 3.000 were mixed with 70 parts of the above-mentioned terminal OH group-containing urethane polyol, and 0.1 part of triethylenediamine was added to 4.0 parts of water.
0 parts, 1.0 part of Silicon L540 (8 pieces manufactured by Unica), 0.25 parts of Stanus Octo-x-to, 5.0 parts of trichlorofluoroethane, and flame retardant CR-505 (manufactured by Ohana Kagaku) were added. Furthermore, TDI-8052, 1 copy (NG
After adding O index 110) and stirring vigorously, the mixture was poured into a suitable mold to obtain a soft urethane foam (II[).

[Example 4] Aromatic nucleus-containing polyether with a molecular weight of 800 obtained by adding propylene oxide to bisphenol A,
Using trimethylolpropane and cepatic acid/isophthalic acid -3/7 (molar ratio), the molecule contains about 3% trimethylolpropane, hydroxyl value 53.5, acid value 0.1
T to 1,050 parts of polyester ether polyol No. 7
174 parts of DI-80 was reacted to obtain a urethane prepolymer containing a terminal NCO group, and then 183 parts of monobromoneopentyl glycol was reacted to obtain a urethane polyol containing a terminal OH group (hydroxyl value = 39.5).

The above terminal OF! 20 parts of group-containing urethane polyol are mixed with 80 parts of polyoxypropylene triol having a molecular weight of 3,000, and 0.1 part of triethylenediamine is mixed with 4 parts of water.
．． 0 parts dissolved in 1.0 parts of Silicon L540 (manufactured by Nippon Nihon Ka), 0.25 parts of Stanus octoate, 5.0 parts of trichlorofluoroethane, flame retardant CR-505 (
(manufactured by Ohana Chemical Co., Ltd.), and further added 5 parts of TDI-8051 (manufactured by Ohana Kagaku).
NGO Index 110) was added, stirred vigorously, and poured into a suitable mold to obtain a soft urethane foam (IV).

[Example 5] 500 parts of polyoxytetramethylene glycol 1 having a molecular weight of 1.500 was reacted with 348 parts of TDI-80 to obtain a urethane prepolymer containing a terminal NCO group, and then 524 parts of dibromoneopentyl glycol was reacted to form a terminal OH Group-containing urethane polyol (hydroxyl value -46,9
) was obtained.

80 parts of polyoxypropylene triol having a molecular weight of 3,000 are mixed with 20 parts of the above-mentioned urethane polyol containing terminal OH groups, and 0.1 part of triethylenediamine is mixed with 4.0 parts of water.
1.0 parts of silicone L540 (manufactured by Nippon Unica), 5.0 parts of dichlorofluoroethane (0.25 L of Stanus octoate), and 5.0 parts of flame retardant CR-505 (manufactured by Ohana Kagaku), and further TDI-8051, 9 copies (NGO
After adding INDEX 110) and stirring vigorously, the mixture was poured into a suitable mold to obtain a soft urethane foam (V).

[Example 6] 1,500 parts of polyethylene/butylene adipate having a molecular weight of 1,500 was reacted with 348 parts of TDI-80 to form a terminal N.
A CO group-containing urethane prepolymer was obtained, and then 524 parts of dibromoneopentyl glycol was reacted to form a terminal OH
A group-containing urethane polyol (hydroxyl value=47.6) was obtained.

80 parts of polyoxypropylene triol having a molecular weight of 3.000 are mixed with 20 parts of the above-mentioned urethane polyol containing terminal OH groups, and 0.1 part of triethylenediamine is mixed with 4.0 parts of water.
0 parts dissolved in 1.0 parts of silicone L540 (8 bottles made by Unica), 0.25 L of Stanus octoate, 5.0 parts of trichlorofluoroethane, flame retardant CR-505 (
(manufactured by Ohana Kagaku) and further added 9 parts of TDI-8051 (N
GO index 110) was added, stirred vigorously, and poured into a suitable mold to obtain a soft urethane foam CVI).

(Comparative Example 1) 100 parts of polyoxypropylene triol with a molecular weight of 3,000, which is used for ordinary flexible urethane foam, was used as a raw material polyol, and 0 parts of triethylenediamine was added to this.
．． 1 part dissolved in 4.0 parts of water, Silicon L-54
0 (manufactured by Nippon Unica) 1.0 part, Stanus Octoate 0
．． 35 parts, trichlorofluoroethane 5.0 parts, flame retardant CR-505 (manufactured by Ohana Kagaku), and further TDI-80
After adding 52.2 parts (NGO index 110) and stirring vigorously, the mixture was poured into a suitable mold to obtain a soft urethane foam [■].

[Comparative Example 2] Polyester ether polyol obtained from adipic acid and an aromatic nucleus-containing polyether with a molecular weight of 2,500 obtained by adding propylene oxide to bisphenol A (hydroxyl value = 28.6, acid value -0, 18, number average molecular weight = 3,900) 55 parts of polyoxypropylene triol (hydroxyl value = 56.1, number average molecular weight =
3000) were mixed to obtain a raw material polyol.

Triethylenediamine 0.1 to 100 parts of the above polyol
Silicon L540 (8 parts) dissolved in 4.0 parts of water.
Manufactured by Unica) 1.0 part, Stanus off t-+: -t 0
．． 2 OL Add 5.0 parts of trichlorofluoroethane and flame retardant CR-505 (manufactured by Ohana Kagaku), and add TDI-
Add 6 parts of 8049 (NGO index 110), stir vigorously, and then pour into a suitable mold to form a soft urethane foam [■
] was obtained.

[Comparative Example 3] Polyoxypropylene diol 1 with a molecular weight of 1 and 500
．． React 500 parts with 80348 parts of TDI-80 to complete the terminal NC.
An O group-containing urethane prepolymer was obtained, and then 124 parts of ethylene glycol was reacted to obtain a urethane polyol containing one (0) terminal group (hydroxyl value = 56.9).

70 parts of polyoxypropylene triol having a molecular weight of 3,000 are mixed with 30 parts of the above-mentioned 0-day terminal group-containing urethane polyol, and 0.1 part of triethylenediamine is mixed with 4 parts of water.
Silicone L540 (manufactured by Nippon Unica), 0 parts, Stanus octoate 0.25X, trichlorofluoroethane 5.0 parts, flame retardant CR-505 (manufactured by Ohana Kagaku) were added, and TDI -8052, 2 copies (NG
After stirring vigorously, the mixture was poured into a suitable mold to obtain a soft urethane foam [IX].

[Comparative Example 4] 5 parts of dibromoneopentyl glycol with a molecular weight of 3.00
Dissolved in 95 parts of polyoxypropylene triol of
In this, 0.1 g of triethylenediamine was dissolved in 4.0 parts of water, 1 silicone L-540 (manufactured by Nihon Nihon Ka)
．． Add 0 parts, 0.30 parts of Stanus octoate, 5.0 parts of trichlorofluoroethane, flame retardant CR-505 (manufactured by Ohana Kagaku), and further add 4 parts of TDI-8055 (NCO I7 Denx 11o). After stirring vigorously, the mixture was poured into a suitable mold to obtain a soft urethane foam [X], but this foam became closed and shrunk, and a good foam could not be obtained.

〔test〕

The test results for physical properties and flame retardance of the urethane foams (I) to [■] obtained in Examples and Comparative Examples are shown in the table below.
Shown in 1.

The composite material used in the flammability test was obtained by slicing the urethane foams of [1) to [IX] into 15 mm thick pieces and heat-sealing them to a polyester/nylon blend cloth. However, since the urethane foam [■] did not exhibit heat fusion properties, it was bonded to the cloth using a urethane adhesive.

(Effects of the Invention) The urethane polyol having a terminal hydroxyl group according to the present invention can provide a flexible polyurethane foam having excellent foam properties as well as excellent M flammability and heat fusion properties.

Claims (1)

[Claims] 1. A urethane polyol having a terminal hydroxyl group consisting of (A) a polyol, (B) a halogen atom-containing low-molecular polyol, and (C) a polyisocyanate. 2. A composition for polyurethane foam, characterized by using the urethane polyol according to claim 1. 3. The composition for urethane foam according to claim 2, wherein the urethane foam is a flexible polyurethane foam. 4. The urethane polyol for polyurethane according to claim 1, wherein the polyol (A) is selected from the following. (a) polyoxyalkylene polyol with a molecular weight of 300 to 5,000, (b) an aromatic nucleus-containing diol obtained by adding alkylene oxide to an aromatic dihydroxy compound with a molecular weight of 230 to 5,000, (c) a molecular weight of 300 to 5 ,000 polyoxyalkylene glycol alone or in combination with a low-molecular-weight polyhydroxy compound is used as the alcohol component, and on the other hand, at least one of aliphatic dicarboxylic acids, aromatic dicarboxylic acids, anhydrides, and various derivatives thereof is used as an acid. A polyester ether polyol having a molecular weight of 500 to 6,000 obtained as a component; (d) An aromatic nucleus-containing diol alone or a low molecular weight having a molecular weight of 230 to 5,000 obtained by adding alkylene oxide to an aromatic dihydroxy compound. The alcohol component is a mixture of polyhydroxy compounds, and on the other hand,
A polyester ether polyol having a molecular weight of 500 to 6,000 obtained using an aliphatic dicarboxylic acid having 3 to 6 carbon atoms and/or an aromatic dicarboxylic acid or their anhydrides and various derivatives as an acid component, (e) aromatic dihydroxy The alcohol component is an aromatic nucleus-containing diol with a molecular weight of 230 to 5,000 obtained by adding alkylene oxide to a compound, or a combination of a low molecular weight polyhydroxy compound, and an aromatic dicarboxylic acid and a carbon number of 7 to 14. (f) Polyester ether polyol having a molecular weight of 500 to 6,000 obtained as an acid component using a long-chain aliphatic dicarboxylic acid or a mixture with their anhydrides or various derivatives; (f) polyoxytetra having a molecular weight of 500 to 5,000; methylene glycol, (g) acid-alcohol condensation polyester polyol and/or ε-caprolactone obtained from a low-molecular polyhydroxy compound and at least one of aliphatic dicarboxylic acids, aromatic dicarboxylic acids and their anhydrides, and various derivatives; A polylactone-based polyester polyol obtained by polymerization.