JPH0257807B2 - - Google Patents

Description

[Detailed description of the invention]

(Industrial Application Field) The present invention relates to a high performance flexible urethane foam without amine odor. (Prior art) Generally, an amine catalyst is used in the production of urethane foam, so the product has an amine odor.
Particularly in the case of high-density urethane foam having a specific gravity of 30 to 70 Kg/m ³ , the problem was serious because the amine odor was not easily dissipated. Therefore, it has been desired to develop a flexible urethane foam that has excellent performance without using an amine catalyst. (Problems to be Solved by the Invention) The purpose of the present invention is to solve the problem without using an amine catalyst.
The object of the present invention is to provide an amine-free, odorless, high-performance urethane foam that is not mainly composed of closed cells and has excellent strength and elongation properties. (Means for Solving the Problems) The present invention provides a flexible polyurethane foam obtained by reacting a polyol component having at least a difunctional hydroxyl group with an at least difunctional polyisocyanate component. ~4000, using a mixed polyol consisting of a soft foam polyol with an OH value of 40 to 500 and an aromatic amine base polyol, and with a molecular weight of 300.
The present invention relates to an amine-free, odorless, high-performance urethane foam characterized in that the reaction is carried out in the presence of a low molecular weight silicone compound consisting of an alkoxysilane or alkoxysiloxane polymer of ~1000. As the polyol for soft foam used in the present invention, in addition to the usual polyol having a molecular weight of 3000, polyols containing a small amount of a hexafunctional or octafunctional polyol for hardness can be used alone or in combination. For example, commercially available products include
PPG3000 (manufactured by Mitsui Nisso, OH value 56), Actocol
GS18A (Takeda Pharmaceutical, OH value 80), Actocor
Examples include GS18B (same, OH value 450). The preferred molecular weight range of this soft foam polyol is 500 to 4000, and the preferred OH number range is 40 to 500. Further, as the aromatic amine-based polyoxyalkylene polyol, which is another component of the mixed polyol used in the present invention, at least difunctional OH
It has a valence of 200 to 700, and is prepared by known methods such as aromatic monoamines such as aniline or 2,4- and 2,6-tolylene diamine (TDA) and so-called crude TDA, 4,4'-diaminodiphenylmethane. and one or more aromatic diamines and aromatic polyamines, such as polymethylene polyphenylene polyamine, fort- or meta- or para-phenylene diamine, meta- or para-xylylene diamine, obtained by condensation of aniline and formalin, and propylene oxide. It is an at least bifunctional polyol obtained by adding one or more alkylene oxides such as ethylene oxide and ethylene oxide, and has substantially no free primary or secondary amines. GR-30 manufactured by Yakuhin Kogyo falls under this category. In addition, in order to reduce the viscosity of the aromatic amine-based polyol itself and improve processability, the following aliphatic glycols, amines, etc. may be used as co-initiators in addition to aromatic amines at the synthesis stage. can. For example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane,
Examples include polyfunctional aliphatic glycols such as glucose, sorbitol, and sucrose, aliphatic amines and aliphatic alkanolamines such as ethanolamine, diethanolamine, triethanolamine, and ethylenediamine. It is preferable to use it in an equimolar amount or less. In the present invention, the proportion of the above-mentioned flexible foam polyol and aromatic amine-based polyol is preferably 95 to 99 parts (by weight, hereinafter the same) for the former and 1 to 5 parts for the latter. The low molecular weight silicon compound used in the present invention has the function of eliminating closed cells in the urethane foam, and preferably has a molecular weight (MW) of about 300.
~1000 alkoxysilane or alkoxysiloxane polymer, commercially available products include L-3600 and L-3601 (both manufactured by Nippon Unicar).
etc. can be mentioned. This low molecular weight silicon compound is preferably used in an amount of 0.1 to 3 parts per 100 parts of the mixed polyol component. In the present invention, if the foam made from the above-mentioned mixed polyol collapses, a tri- or tetrafunctional amino group-containing polyol may be further used in order to improve the reactivity and the retention of the foam. is preferred. The amino groups contained in these tri- to tetra-functional polyols act as amine catalysts to promote the gasification reaction and also contribute to improving the shape retention of the foam. A typical example is OH value 768). In this case, it is preferable to use 92 to 98.5 parts of the polyol for soft foam, 1 to 5 parts of the aromatic amine-based polyol, and 0.5 to 3 parts of the polyol containing 3- to 4-functional amino groups. If the foam made from the mixed polyol of the present invention shows a slight decrease in elongation, tensile strength, or tear strength, it is preferable to further use a diol having an OH value of 28 to 112. Examples of this diol include Diol1000 [OH value 112], Diol2000
Any material with an OH value of 28 to 112, such as [OH value 56], can be used. In this case, the ratio is 85 to 98 parts of polyol for soft foam, 1 to 5 parts of aromatic amine-based polyol, and 1 to 10 parts of diol, or 82 to 97.5 parts of polyol for soft foam, 1 to 5 parts of aromatic amine-based polyol, 3 It is preferable to use the polyol containing 4 functional amino groups in a proportion of 0.5 to 3 parts and the diol in a proportion of 1 to 10 parts. As the polyisocyanate component used in the present invention, all known at least difunctional polyisocyanates can be used, but aromatic polyisocyanates are particularly preferred, such as 2,4-
and 2,6-tolylene diisocyanate (TDI),
Ortho-toluidine diisocyanate (TODI),
Naphthylene diisocyanate (NDI), acylylene diisocyanate (XDI), 4,4'-diphenylmethane diisocyanate (MDI) and carbon diimide-modified MDI (e.g. Nippon Polyurethane Co., Ltd.
MTL), polymethylene polyphenylisocyanate (PAPI), polymeric polyisocyanate (for example, Sumitomo Bayer Urethane 44V), etc. can be used alone or in combination. In the present invention, when producing urethane foam by reacting polyols with isocyanates, etc., the isocyanate index is preferably 103-130, but can be increased or decreased as appropriate based on desired physical properties. Furthermore, the present invention can be applied not only to soft slab forms but also to mold forms. Furthermore, in the present invention, in order to produce a flexible polyurethane foam, a catalyst, a blowing agent, and a foam stabilizer are used.
Further, flame retardants, pigments, fillers, etc. may be used as necessary, but there are no particular restrictions on these, and all known ones can be used. (Example) Hereinafter, a detailed explanation will be given based on an example. Examples 1 to 10 Soft foams were foamed according to the following procedure using three times the amount of each of the formulations shown in Table 1. First, put Actol GS18A and GS18B in a beaker, warm it to 25℃ in a water bath, and
-30 was added and stirred and mixed for 60 seconds. Next, add Quadrol, Diol, T-9, low molecular weight silicone, silicone foam stabilizer, Freon-11, and water and stir for 60 seconds, then add TDI and stir for 6 seconds.
Free foaming was carried out in a cm metal container. After heating the obtained foam at 100℃ for 10 minutes
After leaving it at room temperature for 24 hours, the apparent density was measured using the ASTM D1564-64T method, the tensile strength, elongation, and tear strength were measured using the JIS K6301 method, and the 25% hardness was measured using the JIS K6401 method. Shown in the table. When the urethane foams obtained in each example were checked for the presence of amine odor, no amine odor was observed in any of the foams. In addition, in the table *1 Polyfunctional polyol manufactured by Takeda Pharmaceutical Co., Ltd. (CH value
80) *2 Multifunctional polyol manufactured by Takeda Pharmaceutical Co., Ltd. (OH value
450) *3 Aromatic amine-based polyol manufactured by Takeda Pharmaceutical Co., Ltd. (OH value 400) *4 Tetrafunctional amino group-containing polyol manufactured by Adeka (OH value 768) *5 Diol 2000 manufactured by Asahi Denka (MW2000, OH value
56) *6 L-3600 (MW500) manufactured by Nippon Unicar *7 High molecular weight silicone F-114 manufactured by Shin-Etsu Chemical *8 Blowing agent manufactured by Mitsui Fluorochemicals *9 Tin catalyst manufactured by Yoshitomi Pharmaceutical *10 TDI- manufactured by Mitsui Nisso 80

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Claims (1)

[Scope of Claims] 1. A flexible polyurethane foam obtained by reacting a polyol component having at least a difunctional hydroxyl group with an at least difunctional polyisocyanate component, the polyol component having a molecular weight of 500 to 4000 and an OH value of 40. ~500 polyol for soft foam and aromatic amine base polyol are used, and the molecular weight is 300~1000.
An amine-free, odorless, high-performance urethane foam characterized in that the reaction is carried out in the presence of a low molecular weight silicone compound comprising an alkoxysilane or alkoxysiloxane polymer. 2. The high-performance urethane foam according to claim 1, further comprising a tri- to tetrafunctional amino group-containing polyol as the polyol component. 3 As a polyol component, the hydroxyl value is 28~
112. The high-performance urethane foam according to claim 1, in which diol No. 112 is used in combination. 4 As a polyol component, the hydroxyl value is 28~
112. The high-performance urethane foam according to claim 2, in which diol No. 112 is used in combination.