JPS6361327B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a new and useful composition for a flexible urethane foam that has excellent flame retardancy and foam physical properties. 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 incorporating these flame retardants into the resulting foam. method is being 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 cushion 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.
Furthermore, a combustion cycle is formed that promotes the melting of the soft urethane foam, making the composite material as a whole flammable. In order to solve these problems, methods have been proposed in which ceramic powder or carbon fibers are added to the raw materials. However, in this method, there is a problem in that the addition of ceramic or carbonaceous fibers to the raw material increases the viscosity and significantly reduces the cushioning properties and feel required of the soft urethane foam. The present invention relates to a composition for a soft urethane foam that can exhibit excellent flame retardancy in a composite material without impairing the physical properties of the foam, the foam cushioning properties, the feel of the foam, etc. 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 provides (A) (a) an aromatic nucleus-containing dihydroxy compound with a molecular weight of 230 to 2000 obtained by adding an alkylene oxide to an aromatic dihydroxy compound, and (b) a dihydroxy compound obtained by reacting with an aliphatic and/or aromatic dicarboxylic acid. a polyol component containing a polyester ether polyol with a molecular weight of 800 to 5,000; (B) a polyisocyanate; (C) water and/or a blowing agent; (D) a catalyst, a foam stabilizer, and a flame retardant. A composition for flexible polyurethane foam is provided. The polyurethane foam of the present invention can exhibit excellent flame retardancy in a composite material without impairing the physical properties of the foam, the foam cushioning properties, the feel of the foam, etc. The alkylene oxide adduct (A-a) of the aromatic dihydroxy compound used in carrying out the method of the present invention has a molecular weight of 230 to 2000,
It preferably refers to dihydroxy compounds containing aromatic nuclei in the range of 250 to 1000, among which typical aromatic dihydroxy compounds include catechol, hydroquinone, or bishydroxyethoxybenzene, or compounds with the general formula [However, R and R' in the formula each represent a hydrogen atom or an alkyl group. ] or general formula There are aromatic dihydroxydiphenyl compounds shown in
or bisphenol S, etc. are preferred; on the other hand,
Typical examples of the alkylene oxide used for addition with the aromatic dihydroxy compound include ethylene oxide, propylene oxide, and 1,2-butylene oxide. is suitable. On the other hand, examples of the aliphatic or aromatic dicarboxylic acids (A-b) include saturated dibasic acids having 2 to 10 carbon atoms, unsaturated dibasic acids such as maleic acid and fumaric acid, orthophthalic acid, isophthalic acid, and terephthalic acid. acid, naphthalene dicarboxylic acid, anthracene dicarboxylic acid, phenanthelene dicarboxylic acid, adipic acid, fumaric acid, maleic acid, succinic acid, etc., and it goes without saying that their anhydrides or various derivatives can be used. Although two or more kinds may be used as a mixture, particularly preferred are adipic acid, orthophthalic acid, isophthalic acid, and terephthalic acid. Furthermore, when producing a polyester ether polyol using the raw materials listed above, a polyfunctional low-molecular polyhydroxy compound such as trimethylolpropane, pentaerythritol or hexanetriol can also be added.
These are preferable because they increase the crosslinking density and improve the strength of the foam (form hardness). The polyester ether polyol having a molecular weight of 800 to 5,000 obtained from the components (A-a) and (A-b) is preferably used in an amount of 5 to 70% by weight in the polyol component. The other polyol used in combination with the polyester ether polyol preferably accounts for 30 to 95% by weight of the polyol component, and has a functional group number of 2.
~8. Those with a molecular weight of 500 to 7000, such as polyoxypropylene polyol, polyoxyethylene polyol, and polyoxyethylene propylene polyol (block or random polymer),
Polyether polyols such as polyoxytetramethylene glycol, adipic acid polyester polyols such as polyethylene adipate and polybutylene adipate, lactone polyester polyols, and polyfunctional components (trimethylolpropane, pentaerythritol, hexanetriol) added to them. Also included are introduced polyols. To prepare the polyester ether polyol using the raw materials listed above,
Conventionally known esterification techniques that use vacuum and/or catalysts can be adopted, among which typical methods include a method in which glycols and dicarboxylic acids are reacted under normal pressure, and a method in which esterification is performed under vacuum. There is a method in which esterification is carried out in the presence of an inert solvent such as toluene, and then 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, inorganic or organic acids are usually used to make the esterification reaction proceed smoothly.
Li, Na, K, Rb, Ca, Mg, Sr, Zn, Al, Ti,
V, Cr, Mn, Fe, Co, Ni, Cu, Zr, Pd, Sn,
Chlorides, oxides, hydroxides of metals such as 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; Alcoholates such as isopropyl titanate or n-butyl titanate; phenolates such as sodium phenolate; or Al,
It is preferred to work with all the catalysts conventionally used for esterification and transesterification, such as Ti, Zn, Sn, Zr or other organometallic compounds of metals such as Pb. In this case, the amount of the catalyst to be used is suitably in the range of 0.00001 to about 5% by weight, preferably in the range of 0.001 to 2% by weight, based on the total amount of the raw materials for preparing the polyester diol. The reaction temperature at this time is usually in the range of 100 to 250°C. Typical polyisocyanates (B) of the present invention include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, or mixtures thereof, m- or p-phenylene diisocyanate, p-xylene diisocyanate,
Ethylene diisocyanate, latramethylene
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'-biphenylene diisocyanate or 1,5-naphthalene diisocyanate Examples include polyphenylpolymethylene polyisocyanate. These compounds can be used alone or as a mixture of two or more. A soft urethane foam may be produced using the above-mentioned raw materials by conventionally known methods such as the one-shot method and the prepolymer method. The prepolymer method involves reacting a polyhydroxy compound and a polyisocyanate in advance to obtain a type of prepolymer.
This is then reacted with a polyhydroxy compound in the presence of a blowing agent, a catalyst, and a foam stabilizer, or in the one-shot method, an organic polyisocyanate and a polyhydroxy compound are reacted in the presence of a catalyst, a blowing agent, and a foam stabilizer. By these methods, flexible polyurethane foams can be produced. The catalyst used in the present invention may be one commonly used in producing polyurethane foam.
Examples include organic tin compound catalysts and amine catalysts. Examples of the organic tin compound catalyst include stannath octoate, stannath oleate, dibutyltin dilaurate, dibutyltin di-2-ethylhexoate, and dibutyltin diacetate. In the present invention, the foam stabilizer used may be a silicone foam stabilizer commonly used for producing flexible polyurethane foams. Moreover, the cell diameter of the foam targeted by the present invention can be controlled by appropriately selecting the silicone foam stabilizer. That is, when using a silicone foam stabilizer with low foam stabilizing activity, such as a silicone foam stabilizer for semi-rigid polyurethane foam or for cold cure, a coarse cell foam is obtained, whereas a silicone foam stabilizer with high foam stabilizing activity, For example, when using a hot cure silicone foam stabilizer, a fine cell foam is obtained. In addition, in the present invention, water (which generates carbon dioxide gas by reaction with an organic isocyanate) is mainly used as a blowing agent, but if necessary, a low-boiling point organic material such as monofluorotrichloromethane or methylene chloride may be used as a blowing agent. Compounds and air can also be used. In addition to the above-mentioned ingredients, depending on the performance required for the foam, fillers, antistatic agents, colorants,
and flame retardants, etc., may be added as long as they do not depart from the purpose of the present invention. The flame retardant used in the present invention may be one commonly used, such as trichloroethyl phosphate, trisdichloropropyl phosphate, trimethyl phosphate, triethyl phosphate, tributoxyethyl phosphate, tricresyl phosphate, or Halogen-containing condensed phosphoric acid esters such as CR-505 (Daihachi 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 (e.g. urethane type, ethylene-vinyl acetate type, etc.) after forming a soft polyurethane foam; (2) bonding the surface of the urethane foam with a flame; They can be made into composite materials using the flame lamination method, which involves melting and bonding, and (3) the method of bonding using high frequency. Materials to be bonded include cloth, woven fabrics, knitted fabrics, synthetic leather, 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. The flame retardant properties of the present invention can be used for interior materials (ceilings, walls), vehicles (automobiles, trains,
Airplane) seats, chairs, cashier supplies, etc. [Example] Next, the present invention will be explained using Examples, but is not limited thereto. In the text, "parts" and "%" are based on weight. Example 1 Polyester ether polyol obtained from adipic acid and an aromatic nucleus-containing polyether with a molecular weight of approximately 600 obtained by adding propylene oxide to bisphenol A (hydroxyl value = 57.5, acid value = 0.21, number average molecular weight = 1944) and 70 parts of polyoxypropylene triol (hydroxyl value = 56.1, number average molecular weight = 3000) were mixed to obtain a raw material polyol. Next, a flexible urethane foam (A) was manufactured using this polyol according to the formulation shown in Table 1. Example 2 Aromatic-containing polyether with a molecular weight of about 1000 obtained by adding propylene oxide to bisphenol A and adipic acid/isophthalic acid = 1/
1 (molar ratio) and a polyester ether polyol (hydroxyl value = 47.6, acid value = 0.19, number average molecular weight = 2348) to 45 parts of polyoxypropylene triol (hydroxyl value = 56.1, number average molecular weight = 3000). 55 parts were mixed to obtain a raw material polyol. Manufacturing of the soft urethane foam is carried out in Example 1.
A soft urethane foam (B) was obtained in the same manner as above. Example 3 Polyester ether polyol obtained from adipic acid and an aromatic nucleus-containing polyether with a molecular weight of 300 obtained by adding propylene oxide to bisphenol A (hydroxyl value = 112.0, acid value 0.17, number average molecular weight = 1000) A raw material polyol was obtained by mixing 70 parts of polyoxypropylene triol (hydroxyl value = 56.1, number average molecular weight = 3000) with 30 parts. The soft urethane foam was manufactured in the same manner as in Example 1, and a soft urethane foam [C] was obtained. Example 4 Polyester ether polyol obtained from adipic acid and an aromatic nucleus-containing polyether with a molecular weight of 1800 obtained by adding propylene oxide to bisphenol A (hydroxyl value = 27.8, acid value = 0.23, number average molecular weight = 4000) ) and 45 parts of polyoxypropylene triol (hydroxyl value = 56.1, number average molecular weight = 3000) were mixed to obtain a raw material polyol. Soft urethane foam [D] as in Example 1
I got it.

〔test〕

Table 2 shows test results regarding physical properties and flame retardancy of the urethane foams [A] to [G] obtained in Examples and Comparative Examples. The composite materials used in the flammability test were [A] ~
The urethane foam [F] was sliced to a thickness of 15 mm and covered with a polyester/nylon blend cloth.

【table】

Claims (1)

[Claims] 1 (A) (a) The molecular weight obtained by adding alkylene oxide to an aromatic dihydroxy compound is 230.
~2000 aromatic nucleus-containing dihydroxy compounds,
(b) A polyol component containing a polyester ether polyol with a molecular weight of 800 to 5000 obtained by reacting an aliphatic and/or aromatic dicarboxylic acid, (B) a polyisocyanate, (C) water and/or a blowing agent. , (D) A composition for flame-retardant flexible polyurethane foam, comprising a catalyst, a foam stabilizer, and a flame retardant.