JPS6173717A - Flexible urethane foam - Google Patents

Abstract

PURPOSE:A heat-sealable flexible urethane foam excellent in mechanical properties, scorching resistance, stability of a stock solution, etc., obtained by reacting a specified polyester-ether polyhydroxy compound with a polyisocyanate. CONSTITUTION:An acid component comprising a mixture of an aromatic dicarboxylic acid (e.g., terephthalic acid) and a long-chain aliphatic dicarboxylic acid (e.g., azelaic acid) is reacted with an alcohol component comprising an aromatic ring-containing diol of a MW of 230-5000, obtained by an addition reaction between an aromatic dihydroxy compound (e.g., bisphenol A) and an alkylene oxide or comprising this diol and a bi- to tetra-functional low-MW polyhydroxy compound (e.g., glycerol). The obtained polyester-ether polyhydroxy compound is reacted with a polyisocyanate (e.g., 2,4-tolylene diisocyanate) to obtain the purpose flexible polyurethane foam.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a novel and useful flexible urethane foam that can be heat-sealed and has excellent stability of the stock solution, mechanical properties of the foam, and scorch resistance of the foam. relates to flexible urethane foams comprising the use of specific polyesterether polyhydroxy compounds.

Conventionally, various attempts have been made to impart heat-sealing properties to soft urethane foams. For example, a method using a phosphorus-containing polyether polyol (Japanese Patent Publication No. 4B-3760
0), a method of attaching phosphoric acid to at least one of the urethane foam or the base material before flame lamination (Japanese Patent Publication No. 47-6519), or a method of using a urethane foam made of a polyoxya compound (Japanese Patent Publication No. 46-30309). Publication No.) is known. However, these methods all have problems such as i) poor stability of the stock solution, and ii) poor mechanical properties of the foam.111)
It was not perfect, as it still had problems such as insufficient thermal adhesion and no adhesion at all depending on the type of adherend, and iv) large scorch during foam production.

However, in view of the various drawbacks of the prior art as described above, the present inventors have conducted extensive research to eliminate all of these drawbacks, and as a result, have completed the present invention.

That is, the present invention provides a molecular weight compound obtained by adding an alkylene oxide to an aromatic dihydroxy compound to an acid component consisting of a mixture of an aromatic dicarboxylic acid (a-1) and a long-chain aliphatic dicarboxylic acid (a-2). is 230 to 5000 (b-1) alone, or a low-molecular polyhydroxy compound (b-”2) having a functional group number of 2 to 4.
) is used in conjunction with a polyester ether polyhydroxy compound obtained by using it as an alcohol component.It is characterized by the use of a polyester ether polyhydroxy compound obtained by using a polyester ether as an alcohol component.It is characterized by the stability of the stock solution, the mechanical properties of the foam, and the scorch resistance of the foam.It is heat-sealable. This provides a flexible urethane foam.

As the long-chain aliphatic dicarboxylic acid used in carrying out the method of the present invention, those having 7 to 14 carbon atoms are particularly suitable, preferably azelaic acid or sebacic acid having 9 or 10 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 decrease. Both are unfavorable as they result in a decrease in

Further, typical aromatic dicarboxylic acids mentioned above include orthophthalic acid, isophthalic acid, terephthalic acid, naphthalenedicarboxylic acid, anthracenedicarboxylic acid, and phenanthenedicarboxylic acid, but their anhydrides and various derivatives are also available. They can be used without charge, and they may be used as a mixture of two or more, but
Particularly preferred are orthophthalic acid, isophthalic acid or terephthalic acid.

The aromatic dicarboxylic acid and the long chain aliphatic dicarboxylic acid are used in a molar ratio ranging from 1/9 to 9/1,
In view of the mechanical properties of the resulting foam, a range of 515 to 9/1 is preferred.

On the other hand, the alkylene oxide adduct of the aromatic dihydroxy compound used in carrying out the method of the present invention has a molecular weight of 230 to 5000, preferably 250 to 5000.
It refers to aromatic nucleus-containing polyether diols in the range of 2000, among which typical aromatic dihydroxy compounds include catechol, hydroquinone, bishydroxyethoxybenzene, or the general formula % (or the general formula %). Although there are aromatic dihydroxydiphenyl compounds shown in the table, bisphenol A is particularly preferred when taking into consideration the ease of obtaining raw materials and the physical properties as a soft urethane foam.

Bisphenol F or bisphenol S is preferred, while typical alkylene oxides used for addition with the aromatic dihydroxy compound include ethylene oxide, propylene oxide, epichlorohydrin, 1,2-butylene oxide, or mixtures thereof. is used advantageously.

In addition, when producing polyester ether polyol using the above raw materials, examples of low-molecular polyhydroxy compounds having 2 to 4 functional groups used include glycerin, trimethylolpropane, hexanetriol, triethanolamine, pentaerythritol, and ethylenediamine. Compounds such as can be used. These are preferably added because they increase the crosslinking density and improve the strength of the foam (form hardness).

In order to prepare the polyester diol using the raw materials listed above, conventionally known esterification techniques using vacuum and/or catalysts can be adopted, and among them, representative ones include There are two methods: reacting glycols and dicarboxylic acids under normal pressure, esterifying under vacuum, or esterifying in the presence of an inert solvent such as toluene, and then co-condensing water with the solvent. There are methods such as boiling to remove it from the reaction system.

Although it is theoretically possible to carry out the reaction in a system without a catalyst, inorganic acids or organic acids; Li5Has KSRb are usually used to make the esterification reaction proceed smoothly.
s Cas Mgs Srs ZnxA1% Tl5
V, CrSMn,, Fez C0% Ni
s Cus Zrs Pds Sn, Sb
or chlorides, oxides, hydroxides of metals such as Pb or fatty acid salts such as acetic acid, oxalic acid, octylic acid, lauric acid or naphthenic acid; sodium methylate, sodium ethylate, aluminum triisopropoxide, isopropyl・Titanate or n-
alcoholado cheeks such as butyl titanate; phenolates such as sodium phenolate; or AI,
The catalyst is preferably carried out using all the catalysts conventionally used for esterification and transesterification, such as Tl5Zn, Sn, Zr or other organometallic compounds of metals such as pb. The amount used is 0 based on the total amount of raw materials for preparing the polyester diol.
．． 00001 to about 5% by weight, preferably 0,
A suitable range is 1 to 2% by weight of OO. and,
The reaction temperature at this time is usually in the range of 100 to 250°C.

As mentioned above, the polyester ether polyol that is characteristically used in carrying out the method of the present invention is a heat-fusible soft urethane that has extremely excellent stock solution stability, foam physical properties, heat-fusibility, and scorch resistance. Although the above-mentioned specific components should be used exclusively, if necessary, the number of functional groups is 2 to 8 and the molecular weight is 5.
00-7000 polyoxypropylene polyol, polyoxyethylene polyol and polyoxyethylene propylene polyol (block or random copolymer)
, 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) introduced into them. This does not in any way preclude the use of conventional polyols mixed with the above-mentioned specific polyester ether polyols.

Further, the polyester ether polyol of the present invention preferably contains 5 to 50% by weight of aromatic nuclei, particularly 7 to 4% by weight.
It is preferable to contain 0% by weight.

Polyisocyanates that can be used in the present invention include 2,4-)lylene diisocyanate or 2,6-)
- lylene diisocyanate or mixtures thereof, m
-or 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'-biphenylene diisocyanate or 1,5-naphthalene diisocyanate, Japanese diphenylmethane diisocyanate, and diphenylmethane diisocyanate There are various derivatives of

The flexible urethane foam of the present invention may be manufactured using the above-mentioned raw materials by conventionally known methods such as the one-shot method and the prepolymer method. The prepolymer method is a method in which a polyhydroxy compound and a polyisocyanate are reacted in advance to obtain a type of prepolymer, and then a polyhydroxy compound is reacted with this in the presence of a blowing agent, catalyst, foam stabilizer, and other additives. , or the one-shot method, is a method in which an organic polyisocyanate and a polyhydroxy compound are reacted 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. can. 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 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, 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.

Next, examples of the present invention will be described, but the present invention is not limited thereto. In the text, "parts" and "%" are based on weight.

91 Example 1 Polyester ether diol (hydroxyl value = 57.0, acid value = 0.23, average molecular weight - 1968), 60 parts of polyoxypropylene triol with an average molecular weight of 3000, which is obtained by adding propylene oxide to glycerin, was mixed with 40 parts, and 0.1 part of triethylenediamine was added to this. Add the solution dissolved in 4.0 parts of water, 1.0 part of silicone L-540 (Nihon Uniriki 11!, 0.2 parts of Stanus octoate, and 5 parts of Freon, and then add 2.
4/2.6-Dylene diisocyanate (2, 4/2
, 6 = 80 / 20 parts, referred to as TDT-80, NGO index 105) 50 parts were added and stirred vigorously, then poured into a suitable mold to form a soft urethane foam (A).
I got it.

Example 2 Using sebacic acid/isophthalic acid = 2/8 (molar ratio) instead of the azelaic acid/isophthalic acid mixture, the hydroxyl value was 59.3, the acid value was 0.15, and
A mixture of 50 parts of polyester ether diol with an average molecular weight of 1887 and 50 parts of polyoxypropylene triol with an average molecular weight of 3000, which is obtained by adding propylene oxide to glycerin, was foamed in the same manner as in Example 1 to form a flexible urethane foam (B ) was obtained.

Example 3 An aromatic nucleus-containing polyether with a molecular weight of about 600 obtained by adding propylene oxide to bisphenol A, trimethylolpropane, and sebacic acid/isophthalic acid -3/7 (molar ratio) was used to add about 3% to the molecule. % of trimethylolpropane, a hydroxyl value of 61.0 and an acid value of 0.17, and 55 parts of a polyoxypropylene triol with an average molecular weight of 3000 obtained by adding propylene oxide to glycerin. The material was foamed in the same manner as in Example 1 to obtain a soft urethane foam (C).

Example 4 Aromatic nucleus-containing polyether with a molecular weight of about 350 obtained by adding propylene oxide to bisphenol A and decamethylene dicarboxylic acid/isophthalic acid-171 (
molar ratio) and a polyester ether polyol (hydroxyl value -45.0, acid value = 0.30,
A mixture of 40 parts of polyoxypropylene triol (average molecular weight = 2500) and 60 parts of polyoxypropylene triol with an average molecular weight of 3000, which is obtained by adding propylene oxide to glycerin, was foamed in the same manner as in Example 1 to form a soft urethane foam CD.
) was obtained.

Example 5 Polyester ether polyol (hydroxyl value = 37.4, acid value -0.43, average molecular weight = 3000) and 70 parts of polyoxypropylene triol having a molecular weight of 3000 were mixed in Example 1.
Foaming was carried out in the same manner as above to obtain a soft urethane foam (E).

Comparative Example 1 97 g of polyoxypropylene triol with an average molecular weight of 3000 obtained by adding propylene oxide to glycerin and 3 g of propoxylated phosphoric acid with a hydroxyl value of 330 obtained by adding propylene oxide to 100% phosphoric acid were mixed. The foam was foamed in the same manner as in Example 1 to obtain a soft urethane foam (F).

Comparative Example 2 Urethane foam obtained by adding propylene oxide to glycerin and having an average molecular weight of 13,000 was foamed in the same manner as in Example 1, and 20 g/in of commercially available 85% phosphoric acid.
A soft urethane foam (G) was obtained which was coated at a ratio of (.

Comparative Example 3 2250 parts of polyoxypropylene glycol with an average molecular weight of 1500, which is obtained by adding propylene oxide to propylene glycol, 500 parts of phthalic anhydride, 2.5 parts of triethylamine, and 250 parts of propylene oxide were charged into a pressure-resistant reaction vessel and reacted at 80 to 120°C. I let it happen. After the reaction is complete,
Polyoxypropylene triol 48 with an average molecular weight of 3,000 obtained by adding propylene oxide to glycerin and 50 parts of a polyester ether polyol with a hydroxyl value of 55 and an acid value of 0.20, excluding unreacted propylene oxide and low-boiling compounds under reduced pressure. and 2 g of the propoxylated phosphoric acid used in Comparative Example 1 were mixed and foamed in the same manner as in Example 1 to obtain a flexible urethane foam (H).

Comparative Example 4 Polyester ether polyol obtained from an aromatic nucleus-containing polyether with a molecular weight of about 2,700 obtained by adding propylene oxide to bisphenol A and a mixture of sebacic acid/isophthalic acid -4/6 (molar ratio)
Hydroxyl value -22.4, acid value =0.50, average molecular weight -4
500) and 70 parts of polyoxypropylene triol having an average molecular weight of 3000 were foamed in the same manner as in Example 1 to obtain a flexible urethane foam (I).

(Physical property test) [Heat fusion method] The soft urethane foams (A) to (I) obtained above were sliced into 15 m thick slices, length x width -150 m x 5Qn+
Cut to Xive. The entire surface of these sample forms is melted with a gas burner set to a constant flame and immediately fused onto a given fabric under constant pressure. After leaving it for 24 hours, take a 120mm x 25ms test piece.Jl) JIS
Peel strength was measured based on L-1066-1963.

[Scorch resistance test method]

Polyol 350 used in Example 1-3 and Comparative Example 1.3
0 parts, 3.5 parts of triethylenediamine dissolved in 175 parts of water, 70 parts of Silicone L-54, 1-part of Stanusoff were added, and then TDI-80 (NGO index 120) was added and after vigorous stirring, 70CIIIX
Pour into a 7 Qcm, height 50 (2) mold to create a soft urethane foam. The next day, the center portion was sliced into 7-inch thick slices and the color (yellowness) was measured using a color meter.

Color meter: “Color meter Σ80” manufactured by Nihon Heavy Industries Ltd. The physical properties of the urethane foams (A) to (r) were measured by the above method. The results are shown in Table 1.

It was confirmed that the flexible urethane foam of the present invention has excellent thermal adhesion, scorch resistance, and mechanical properties.

[Stability test method for stock solution]

Put 30g of raw material polyol in a 100cc beaker and
It was stored for 4 weeks under conditions of 0% relative humidity and 50°C, and changes in appearance and acid value over time were measured. The results are shown in Table 2.

It was confirmed that the stock solution of the present invention has excellent stability.

-17-.

Claims (1)

[Claims] The molecular weight obtained by adding an alkylene oxide to an aromatic dihydroxy compound to the acid component (a) consisting of a mixture of an aromatic dicarboxylic acid (a-1) and a long-chain aliphatic dicarboxylic acid (a-2) is 230~ A polyester ether polyhydroxy compound obtained by using, as the alcohol component (b), a diol containing an aromatic nucleus of 5,000 (b-1) alone or in combination with a low-molecular-weight polyhydroxy compound (b-2) having 2 to 4 functional groups. A soft urethane foam characterized by the use of.