JPH06211978A - New polyether polyol and production of polyurethane foam therefrom - Google Patents

Abstract

PURPOSE:To produce a low-density low-hardness flexible polyurethane foam by using a small amt. of water as the blowing agent without using specified chlorofluorocarbons and without detriment to the characteristics such as wet- heat compression set. CONSTITUTION:A polyether polyol having a mol.wt. of 2,000-7,000 is produced by the addition reaction of alkylene oxide using an ethylene oxide adduct of N-aminoethylpiperidine as the intiator. A flexible polyurethane hot-cure foam is produced by using 100 pts.wt. this polyol having a hydroxyl value of 40-80mgKOH/g and 4.6-6.0 pts.wt. water as the blowing agent, and a cold-cure foam is used by using 100 pts.wt. the polyol having a hydoxyl value of 23-50mgKOH/g and 2.5-5.0 pts.wt. water.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to new polyols and a process for producing flexible urethane foams using them. Furthermore, the present invention is directed to the production of a low-density low-hardness flexible urethane foam by a hot cure molding method (hereinafter simply referred to as a hot cure method) and a high elasticity mold foam (hereinafter referred to as HR) by a cold cure molding method (hereinafter simply referred to as a cold cure method). A method suitable for the production of foams) is provided.

[0002]

BACKGROUND OF THE INVENTION Since flexible urethane foam has excellent elasticity, it is widely used for cushions and backing materials for furniture, bedding, automobile members and the like. . Urethane foam is roughly classified into slab foam and mold foam depending on the manufacturing method. The slab foam is a block-shaped foam that is freely foamed, and is cut into an appropriate shape for use. Molded foam is a foam that has a shape by being foamed in a mold made of metal or resin. Of these, most of the mold foams are used for automobile parts.
Techniques for producing a mold foam of this flexible urethane foam are roughly classified into a cold cure method and a hot cure method, each having advantages and disadvantages. That is, the mold form by the cold cure method is usually HR (High
Resilince) foam, which has high impact resilience and SAG coefficient, and thus has excellent physical properties.
Moreover, in terms of moldability, it has an advantage that it can be cured at a low temperature and the curing time is short. Further, it has the advantages that the yield of the obtained foam is high and that cracking and shrinkage of the foam hardly occur. However, the foam produced by this method has a problem that it is limited to high-density cushioning applications because the wet-heat compression set becomes extremely worse if the density is lowered. On the other hand, according to the hot cure method, the curing temperature at the time of molding is high, and a long curing time is required. Depending on the excess or deficiency of the amount of catalyst, the temperature change of the mold, the shape of the mold, etc. There is a problem that defects such as cracks, shrinkage, and loose skin are likely to occur, and the yield of products is poor. However, the hot-cure method has an advantage over the cold-cure method in that a low-density product having excellent compression set can be obtained. Therefore, in the case of the soft urethane foam obtained by the hot cure method, the low density foam is used as a backing material, and the medium density to high density foam is used as a cushion.

As described above, it is necessary to control the density and hardness of the flexible urethane foam depending on the intended use. Generally, when manufacturing slab foam with a density of 22 kg / m ³ or less, the hot molding method for foam is used to reduce the risk of scorch or fire, or to reduce hardness, and for the backing of automobile seats. For the purpose of adjusting the hardness (reducing hardness) and reducing the density when manufacturing with
CFC-11 (trichlorofluorocarbon), which is a specific chlorofluorocarbon, has been used as a foaming agent. However, with the recent regulation of CFCs for the purpose of protecting the ozone layer, it is desired to suppress or eliminate the use of CFCs. Considering the total ban in the near future, there is an urgent need to develop a method for producing a low-density low-hardness foam without using CFC. In the production of slab foams in accordance with the chlorofluorocarbon regulations, CFC-11 is converted to CH ₂ Cl ₂ and the amount of water in the foam production formulation is generally increased. On the other hand, in mold form,
We have improved the polyol and increased the amount of water in the formulation to reduce the amount of CFCs. Recently, in the hot molding method, a method for producing a low-density low-hardness foam by using only water as a foaming agent and setting a mold temperature at the time of injecting a raw material higher than before has been disclosed in, for example, Japanese Patent Laid-Open No. 1761/1993
No. 10, JP-A-3-192109, JP-A-2
No. 11614, Japanese Patent Publication No. 3689/1991, etc. However, when only water is used as the foaming agent, it is difficult to produce a flexible foam having a low hardness and excellent physical properties, as in the case of using CFCs. In order to solve such a problem, a method of using a monool- or diol-based polyoxyalkylene polyol as a part of the polyol component has been proposed, but such a method increases the compression set of the foam. Etc., there is a problem that impairs other physical properties.

However, increasing the amount of water in the foam manufacturing recipe causes carbon dioxide to be generated at -NCO + H ₂ O → ∼NH ₂ + CO ₂ and naturally contributes to the foaming reaction.

[Chemical 1] The crosslinking reaction of (1) also proceeds. This cross-linking and hydrogen bonds generated between the resulting urea bonds inevitably make the foam stiff. Therefore, instead of using CFC-11, increasing the amount of H ₂ O to produce a foam of the same density shows a significant increase in hardness. Furthermore, an increase in the amount of water used significantly deteriorates physical properties such as permanent set. Although the permanent set is considerably improved by the improvement of the polyol, it is difficult to suppress the increase in hardness.

In urethane foams used for the back of automobiles, such an increase in hardness is not acceptable. At present, it is unavoidable that reduction of CFCs is given priority as an urgent issue, and it is often the case that a slight increase in hardness is sacrificed. However, there is a strong demand for a decrease in hardness and there is a persistent one. Certainly, the following methods of decreasing hardness have been known for a long time. That is, NCO index (isocyanate index) at the time of foam production [isocyanate equivalent number to 100 active hydrogen. In the index 100 -NCO and -OH, H ₂ O is 1: corresponds to 1. Hereinafter, it will be referred to as an isocyanate index], a method of lowering the number of functional groups of the polyol by adding monool or diol, and the like. However, such a conventional method has a problem in practical use due to poor moldability, insufficient curing property, and deterioration of physical properties of foam (especially permanent set and wet heat permanent set). On the other hand, HR foams have been gradually increasing in demand due to their excellent properties, but the biggest drawback is that it is difficult to reduce the density as compared with hot cure mold foams.

[0006] Another object of the present invention is to provide a method for producing an HR foam having a low density and a low hardness, which has good moldability without particularly deteriorating the wet heat permanent set in the production of the HR foam. Among HR foam formulations in recent years, there is one called an all-MDI formulation that uses a special MDI. There are many advantages such as high-speed cure, high resistance, and ease of making different hardness foams, and the demand for such foams is expanding. But such form is C
It is difficult to reduce the density without FC-11, and in Japan, it is extremely rarely used except for headrests, which is acceptable even for relatively high-density products. Due to the nature of all-MDI foam, it is not possible to reduce the density like TDI-80 and TM-20 (TDI-80 / Polymeric-MDI = 80/20) foam, but there is still a high demand for lower density. . Although it is possible to produce low density HR foam in the laboratory by simply increasing the amount of water as a foaming agent,
The wet heat permanent set is extremely deteriorated in proportion to the increase of H ₂ O, and at the same time, the formability of the foam is also lowered. Therefore, such foams are not suitable for producing complex or shaped foams.

An object of the present invention is to solve the above problems in the production of low density low hardness flexible urethane foam. More specifically, the object of the present invention is to produce a flexible urethane foam having a low density and a low hardness without deteriorating other physical properties by using substantially only water as a foaming agent without using a specific CFC. To provide. Furthermore, in order to establish such an eco-friendly production method, a novel polyether polyol was created, and by using these special polyether polyols as a part of the polyol, it is not always necessary to use CFC as a blowing agent. It is a main object of the present invention to provide a new method of making foams.

[0008]

[Means for Solving the Problems] In order to achieve the above-mentioned objects, the inventors of the present invention have been earnestly researching with the aim of improving a polyether polyol which is a main raw material having a great influence on moldability and various physical properties of a flexible urethane foam. As a result,
The present inventors have found that the polyether polyol having the following specific structure works extremely specifically in the production of urethane foam using water as the main foaming agent, and conducted further studies to complete the present invention. That is, the present invention relates to a polyether polyol having a molecular weight of 2000 to 7,000 obtained by addition-polymerizing an alkylene oxide using an ethylene oxide adduct of N-aminoethylpiperidine as an initiator. Here, as the "ethylene oxide adduct of N-aminoethylpiperidine" excluding the addition-polymerized portion of alkylene oxide, for example, a compound of the formula

[Chemical 2] The structure represented by (hereinafter referred to as APE structure) can be mentioned.

As the alkylene oxide (oxyalkylene unit, hereinafter referred to as alkylene oxide) which undergoes addition polymerization, ethylene oxide (oxyethylene) and / or propylene oxide (oxypropylene) are preferable. Here, ethylene oxide units and propylene oxide units may be arranged randomly, or these units may form a block. An example of the latter is, for example, the expression

[Chemical 3] [In the formula, W, X and Y are each independently a formula

[Chemical 4] (In the formula, R ¹ and R ² each represent H or CH ₃ ,
m and n are 35 ≦ m + n ≦ 150, molecular weight 2000 to 70
And a polyether polyol represented by the formula:

In the present invention, any polyether polyol may be used as long as it is a polyether polyol having the above APE structure, and a polymer polyol having a polyether polyol having this structure as a base polyol may be used. The polyether polyol (hereinafter sometimes referred to as APE polyol) of the present invention preferably has a molecular weight of 2000 or more. With a polyol having a molecular weight of less than 2000, it is difficult to produce a flexible urethane foam. or,
A molecular weight of 7,000 or less can be used. The structure of the other part of the polyol is the formula

[Chemical 5] A polyol composed of (oxypropylene group, hereinafter may be simply referred to as propylene oxide or PO) is preferable. EO and PO may be appropriately mixed and added. These mixtures may be random. The number of oxyethylene units (ethylene oxide) that undergo addition polymerization is 2
0% or less is preferable. When the amount of oxyethylene units is too large, it is difficult to produce a foam, and a good flexible foam cannot be obtained.

The oxyethylene unit at the terminal of the molecule is effective for producing terminal primary -OH, but if the number of primary OH groups is too large, the foam tends to become closed cells and a good flexible foam cannot be obtained. Sometimes. Therefore,
The oxyethylene unit directly connected to the hydrogen atom at the molecular end is 15% or less when the molecular weight is 4000 or more.
At 4000, 10% or less is preferable. The polyether polyol having this structure can be produced by a known method or a method analogous thereto. Generally, for example, it can be synthesized by the following method. I.e.

[Chemical 6] By heating (aminoethylpiperazine) under a stream of N ₂ and adding at least 2 mol or more of ethylene oxide (EO),

[Chemical 7] [It is called an APE-H structure. That is, the APE structure represents a structure obtained by removing active hydrogen from the APE-H structure. ] Is obtained. When the amount of EO to be added is 3 mol or more, stoichiometrically all have APE-H and APE structure, but even if it is 2 mol or more, APE- as a reaction mixture.
H is included.

KOH was added to the resulting APE-H or mixture containing APE-H,

[Chemical 8] This is to prevent Depending on the use of the polyol, a diol as a by-product may be present. The dehydration can be removed generally by heating to 100 to 130 ° C. and bubbling an inert gas such as N ₂ , heating under reduced pressure, or azeotropic addition of toluene or the like.
The amount of KOH used is 0.1-based on the final reaction product amount.
About 0.4% is suitable. Instead of KOH, NaOH or the like can be used as a catalyst.

Next, EO (ethylene oxide) or PO
(Propylene oxide) is reacted at around 100 to 120 ° C. The added amount of EO and PO naturally changes depending on the setting of the molecular weight of the final product. After adding PO or EO in an amount according to the setting of the molecular weight (hydroxyl value), KOH of the catalyst is added with an acid such as dilute hydrochloric acid, dilute sulfuric acid or phosphoric acid, or an alkali adsorbent such as synthetic magnesium silicate, or both. After being deactivated by the combined use of, the insoluble matter is removed by filtration, and the excess water is removed by depressurization or bubbling with an inert gas. Generally, dehydration is performed to a water content of 0.05% or less.
Next, in order to stably handle the obtained polyether polyol, BHT of at least about 500 ppm to 1000 ppm
It is common to add (2,6-diderbybutylbutyl-4-methylphenol). In this way, the polyether polyol of the present invention can be manufactured. In this polyether polyol, a mixture (polymer polyol) of a polymer of an ethylenically unsaturated bond monomer obtained by polymerizing styrene and / or acrylonitrile in the presence of a radical generator and the polyether polyol of the present invention is prepared. It can be used in the production of flexible urethane foam. The polymer may be partially grafted on the polyether chain, but most of it is only stably dispersed in the polyether polyol.

The polyether polyol of the present invention thus obtained is used for producing a flexible urethane foam. A flexible urethane foam can be produced using the polyether polyol of the present invention by a conventional method. Generally, it can be manufactured as follows. A polyol containing the polyether polyol of the present invention is added with a catalyst, a flame retardant, a stabilizer, a colorant, etc., if necessary, in the presence of a foam stabilizer and a foaming agent, and reacted with an organic polyisocyanate to give a soft urethane. You can get the form. As the polyol, the APE polyether polyol of the present invention may be used alone, or may be mixed with a commercially available product. From the viewpoint of handling, it is preferable to use a blend with general commercial products. The hydroxyl value of the blend polyol is preferably about 20 to 80 mgKOH / g.
As the catalyst and the foam stabilizer, those generally commercially available can be used.

H ₂ O is mainly used as the blowing agent, but CH ₂
Low boiling point organic substances such as Cl ₂ , CFC-11 or HCFC-141b can also be used. As organic isocyanate, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), modified MDI,
Polyphenyl polymethylene polyisocyanate (Polymeric MDI) and mixtures thereof are suitable. The amount used is generally 0.8 to 1.5 equivalents to the equivalents of OH and —H ₂ O of the polyol used. The present polyether polyol can be used for producing urethane foams such as slab foams and mold foams. It is another object of the present invention to provide a method for producing a preferred flexible urethane foam using the above-described APE structured polyether polyol of the present invention.

The present method is particularly suitable for producing a low-density, low-hardness flexible urethane foam by the hot cure method. (I) A hydroxyl value of 40 to 80 mg KO obtained by addition-polymerizing alkylene oxide using the above-mentioned ethylene oxide adduct of aminoethylpiperazine having the structure APE as an initiator.
H / g polyether polyol is used as one component of the polyol, (ii) 4.
The present invention relates to a method for producing a flexible urethane foam, which comprises reacting with an organic polyisocyanate in the presence of 0 to 6.0 parts by weight of water as a foaming agent. As described above, the flexible urethane foam is generally produced by using a polyol, an organic isocyanate, a foam stabilizer, a foaming agent and, if necessary, a catalyst, a softening agent, a colorant and other additives.

In the above method of the present invention, the APE
It is characterized in that a structural polyether polyol is used, and the ethylene oxide content of the polyether polyol used in this method is preferably 20% or less. If it is too large, it becomes difficult to obtain a good open cell foam. Ethylene oxide added to the end is 1 for all polyols
0% or less is preferable. Similarly, if it is too large, closed cells are likely to be formed. It is also possible to use the above-mentioned polyether polyol of the present invention in the total amount of the polyol. However, since the reactivity is extremely fast, it is preferable to use equipment corresponding thereto. When using general equipment, it is preferable to use the polyether polyol of the present invention in a blend with another polyol in an amount corresponding to 40% or less of the total amount of the polyol used. However, if the use amount of the polyol of the present invention is 5% or less, the effect is diminished.

As the other polyol to be used in combination, any known polyol having a hydroxyl value of 40 to 80 mgKOH / g may be used, and it is particularly preferable if it is a polyol sold for hot molding. For example, Actol MF-26, MF-53, MF-6 manufactured by Takeda
It is 7 mag. The hydroxyl value of the mixed polyol is 4
About 5 to 75 mg KOH / g is preferable, and primary terminal OH%
Is preferably about 55% or less, and more preferably 30% or more. If the hydroxyl value is too high, foaming stability will be poor and a good foam will be difficult to obtain, and if it is too low, the physical properties of the resulting foam, particularly the wet heat permanent set, will be poor. On the other hand, terminal 1
If the grade OH% is too high, it tends to become closed cells. On the other hand, if it is too low, the curability of the foam deteriorates, but the foam itself can be obtained. However, considering the productivity, the terminal primary OH% is more preferably 30% or more.

The organic polyisocyanate used in the above method of the present invention includes tolylene diisocyanate (hereinafter referred to as T
(Referred to as DI), and more preferably TDI-
80 (manufactured by Takeda, Takenate-80: 2; 4TDI /
2; 6 TDI = 80/20) is suitable. In the method of the present invention, the above-mentioned polyol and organic polyisocyanate are used so that the isocyanate index is in the range of 80 to 120. Isocyanate index is 80
If it is smaller than the above range, the physical properties of the foam may be deteriorated, for example, the wet-heat compression set of the obtained foam becomes large. On the other hand, when the isocyanate index is larger than 120, the curability is deteriorated, and the hardness of the obtained foam is also increased.

In the method of the present invention, only water is used as the foaming agent, and the amount thereof is in the range of 4 to 6 parts by weight based on 100 parts by weight of the polyol used. When the amount of water used as a foaming agent is less than 4 parts by weight, the density of the obtained foam increases and the low density foam aimed at by the present invention cannot be obtained. However, when the amount exceeds 6 parts by weight, the hardness of the obtained foam increases, and similarly, the low-hardness flexible foam intended by the present invention cannot be obtained. The amine catalyst used in the present invention may be substantially absent, but a small amount of commonly used amine catalyst may be used. For example, triethylenediamine (TEDA),
Examples include pentamethyldiethylenetriamine and N-ethylmorpholine. It is also desirable to use a tin catalyst such as stanos octoate in combination. However, the catalyst that can be used in the present invention is not limited to the above examples.

As the foam stabilizer used in the present invention, any foam stabilizer used for a slab foam or a hot mold can be used. Examples of such foam stabilizers include B-8017 and B-237.
0 (made by Gold Schmidt), L-582, L-57
40M, L-5740S (manufactured by Nippon Unicar Co., Ltd.), S
H-190, SRX-293 (manufactured by Toray Silicone Co., Ltd.)
Etc. can be mentioned. Such foam stabilizers are usually
It is in the range of 0.5 to 2 parts by weight per 100 parts by weight of the polyol. Furthermore, in the present invention, depending on the required properties and application of the obtained flexible foam, for example, tris (2,3-dichloropropyl) phosphate, halogen-containing condensed organic phosphate ester (for example, CR5 manufactured by Daihachi Chemical Co., Ltd.)
Flame retardants such as 05), colorants, antioxidants, viscosity reducing agents such as propylene carbonate and the like, and any conventionally known additives can be used in combination. When the flexible urethane foam is produced by the hot cure method in this manner, it is preferably cured at 100 ° C or higher, preferably 100 ° C to 200 ° C.

Further, as a production method particularly suitable for producing the HR foam as described above, specifically, (i) an ethylene oxide adduct of aminoethylpiperazine is used as an initiator, and an alkylene oxide is addition-polymerized to give a hydroxyl value of 23.
Using a polyol containing a polyether polyol component having an APE structure of ˜50 mg KOH / g, (ii) polyol 100
A method of producing a flexible urethane foam by using 2.5 parts by weight or more and 5.0 parts by weight or less of water per part by weight as a foaming agent and reacting it with an organic isocyanate. The polyol that can be used in this method is a polyether polyol having the above APE structure and a hydroxyl value of 23 to 50 mg.
It is preferable to use KOH / g. Hydroxyl value 50
In the case of the above, it is easy to form closed cells during foam production, and a good HR foam cannot be obtained. On the other hand, it is difficult to produce an APE polyol having a hydroxyl value of 23 or less by a general production method. The amount of APE polyol used is preferably 30% or more. If it is less than 30%, the effect is not always sufficient.

In the present method, the specific APE polyol may be used in combination with a commercially available polyol, and any commercially available polyol may be used as the polyol to be used in combination, but the hydroxyl value of the polyol after mixing with the APE polyol is It is preferable to use it so as to be 23 to 45 mg KOH / g. It is difficult to obtain a polyol having a hydroxyl value of 23 or less, and a good foam cannot be obtained if it has a hydroxyl value of 45 or more. Specific examples of suitable polyols to be used in combination include Actol GE-3412 (hydroxyl value 34, viscosity 950 mPa · s), MF-81 (35, 1100), and M manufactured by Takeda Pharmaceutical Co., Ltd.
F-83 (35, 950), MF-85 (28,
1400), POP-28 (polymer polyol, OH
No. 28, viscosity 2800), POP-18 (polymer polyol, OH number 30, viscosity 2000).
The APE polyol used is preferably one in which the alkylene oxide to be addition polymerized is propylene oxide and / or ethylene oxide, and the ethylene oxide content is preferably 5% or more and 25% or less. An APE polyol having a terminal ethylene oxide content of 5 to 20% is preferable. If the ethylene oxide content is too high, it is difficult to obtain an HR foam having good open cell cushioning properties, and if the ethylene oxide content is too low, the foam cannot be formed well in many cases.

The amount of water used as the foaming agent in the present invention is 2.5 parts by weight or more and 5.0 parts by weight or less. If it is 2.5 parts by weight or less, there is no need for a low-density foam, and it is meaningless to purposely use this polyol. On the other hand, if it is 5.0 parts by weight or more, the density is too low to obtain a foam having suitable physical properties. Water alone is sufficient as the foaming agent, but as a supplementary agent, CFC-11, HCFC-141
It does not prevent the combined use of low boiling point organic substances such as b. The foam stabilizer used in the above production method of the present invention is HR
Any foam stabilizer used for foams can be used. Specific examples of such a foam stabilizer include B-4113, B-4690, B-8650 (manufactured by Gold Schmidt) L-5305, L-3600,
SZ-1313 (manufactured by Nippon Unicar), SRX-274
C, SF-2962 (manufactured by Toray Dow Corning Co., Ltd.) and the like. The amount of foam stabilizer used is polyol 10
Generally, 0.5 to 2 parts is used per 0 part by weight.

As the catalyst used in the present invention, any catalyst generally sold as a catalyst for urethane foam can be used. For example, triethylenediamine (T
EDA) Tetramethylhexanediamine (TMHDA)
Although a tertiary amine such as, for example, can be used, it may not be used depending on the reactivity. A cross-linking agent may be used in the production of HR foam. It is possible to use low molecular weight compounds such as ethylene glycol and glycerin, amino alcohols such as monoethanolamine and diethanolamine, polyether polyols having a hydroxyl value of 400 or more, such as PO adducts of ethylenediamine. In addition, a flame retardant, a coloring agent, etc. may be added and used as needed. As the organic polyisocyanate used in the method of the present invention, tolylene diisocyanate (hereinafter TDI), 2,
It is possible to use 4'and / or 4,4'-diphenylmethane diisocyanate (MDI) and prepolymers thereof with modified substances and polyols, polyphenylpolymethylene polyisocyanate (hereinafter referred to as "polymeric MDI") and mixtures thereof.

Also in the method of the present invention, the above-mentioned polyol, the H ₂ O used and the organic polyisocyanate have an isocyanate index (hereinafter referred to as NCO).
It is called an index. ) Is used in the range of 80 to 120. When the isocyanate index is less than 80, the physical properties of the foam may be deteriorated, such as the wet heat compression set of the resulting foam becoming large. On the other hand, when the isocyanate index is larger than 120, scorch is likely to occur, and the hardness of the obtained foam also becomes high. In the above-mentioned method, a product other than the organic isocyanate is mixed in advance (referred to as a premix), and the premix and the isocyanate are mixed and stirred for several seconds with a high-speed mixer for production. In industrial production, it is convenient to mix and produce foam in a machine called a foaming machine. Also, when HR foam is manufactured by the cold cure method, 30 to 80 ° C
It is preferable to cure at 50 to 70 ° C. The present invention will be described below with reference to Examples, Comparative Examples and Reference Examples, but the present invention is not limited to these Examples.

Example 1 Aminoethylpiperazine was placed in a reaction kettle equipped with a heating and stirring device.

[Chemical 9] 2.7 kg (20.9 mol) was charged, and the inside of the reaction vessel was replaced with N ₂ gas. Then it is heated to 120 ° C. and 2.76 kg (62.7 mol) of ethylene oxide are added. In this reaction, 3EO form of aminoethylpiperazine (structure of the present application)
Is obtained. Next, add 150 g of KOH flakes and add N ₂
After bubbling and dehydration to adjust the water content to 0.1% or less, 57.0 kg of propylene oxide was reacted at 105 ° to 115 °, and then 3.3 kg (5% in polyol) of ethylene oxide was reacted. After completion of the reaction, a small amount of water and synthetic magnesium silicate (Kyowad 600 (trade name), manufactured by Kyowa Kagaku Co., Ltd.) were added, potassium hydroxide was adsorbed, insoluble materials were removed by filtration, and then water was removed. 0.05%
After dehydration to the following, BHT (2,6-ditertiarybutyl 4-methylphenol: manufactured by Yoshitomi Pharmaceutical Co., Ltd.) (65 g) was added. The polyol A thus synthesized had a hydroxyl value of 63.5 mgKOH / g and a viscosity of 610 mPa · s (25 ° C.). The polyol contains 5% oxyethylene units in the molecule and 8.3% (% by weight) of APE structure.

Example 2 Separately Synthesized Aminoethylpiperazine 3EO Form 2.7
2 kg was charged into the same reaction kettle as in Example 1 and 150 g of KOH
Add flakes and dehydrate. Then propylene oxide 52.
3 kg is reacted, and further 7.5 kg ethylene oxide is reacted. Neutralization and purification were performed in the same manner as in Example 1, and 63 g of BHT was added to obtain Polyol B. This polyol B
Has a hydroxyl value of 35.8 mg KOH / g and a viscosity of 930 mPa · s (2
5 ° C.), oxyethylene unit content 12%, AEP structure content 4.3%.

Example 3 750 polyol B in a 5 liter autoclave
g After charging in advance and repeating depressurization and nitrogen substitution, polyol B3250g, acrylonitrile 50
A mixture of 0 g, 500 g of styrene monomer and 30 g of AIBN was introduced at 120 ° C. for 3 hours with predetermined stirring. Unreacted monomers were removed under reduced pressure to obtain the target polymer polyol. The polymer polyol obtained had an OH number of 27.5 mg KOH / g and a viscosity of 244.
It was 0 mPa · s (25 ° C). (Polyol C)

Comparative Example 1 Polyol D was produced in the same reaction vessel as in Example 1 and in the same manner as in Example 1. That is, aminoethylpiperazine 2.
77 kg (21.5 mol) were admixed with 3.76 kg (64.5 mol) propylene oxide, then 150 g KOH flakes were added and after dehydration 0.58 kg (10 mol) propylene oxide was added. By this PO, all units of oxypropylene are added to -NH of aminoethylpiperazine, and the APE polyol does not have a structure.
(Thus, it is not the polyol of the present invention.) Next, 1.89 kg of ethylene oxide was added, 51.0 kg of propylene oxide was further added, and 3.2 kg of ethylene oxide was further added.
(Terminal oxyethylene unit 5.1%) was added.
KOH was treated with synthetic magnesium silicate, filtered and purified, and 63 g of BHT was added. The obtained polyol D has a hydroxyl value of 62.4 mgKOH / g and a viscosity of 560 mPa · s (25
℃). The APE content was 0%, the oxyethylene unit content was 5.1% at the terminal, and the total was 8.1%.

Comparative Example 2 As in Example 1, K was added to 3.17 kg of triethanolamine.
Charge OH flakes 150g, ethylene oxide 2.7kg
Was reacted. Then, dehydration was performed, and KOH in the system was converted to alcoholate, and then 52.0 kg of propylene oxide was added.
After adding 3 kg of ethylene oxide, neutralization-purification,
Further, 61 g of BHT was added to obtain polyol E.
Polyol E has a hydroxyl value of 56.3 mg KOH / g and a viscosity of 4
80mPa ・ s, ethylene oxide unit content terminal 4.9
%, For a total of 9.3%. Of course, the APE content is 0%.

Examples 4 to 5 and Comparative Examples 3 to 8 Flexible urethane foams were produced by the hand mixing method according to the formulations shown in [Table 1]. In addition, in the table below,
The ratio 1 etc. shows Example 1 and Comparative Example 1 etc., respectively. Ie 2
A foam stabilizer, a catalyst, a foaming agent and other additives were mixed in advance with 00 g of a polyol, and stanos octoate (manufactured by Yoshitomi Pharmaceutical Co., Ltd.) was added to this mixed solution, and then immediately mixed with TDI-80 (manufactured by Takeda Pharmaceutical Co., Ltd.). , Takenate 80) was added and mixed by stirring for 5 seconds with a mixer. 40 this mixture
The mixture was poured into an aluminum mold of 320 × 320 × 70 mm whose mold temperature was adjusted to ± 1 ° C. and foamed. After the foaming was completed, after-curing was performed for 12 minutes in a curing oven at 180 ° C. The physical properties of the obtained foam are shown in [Table 1]. The method is a hot cure method and the production of so-called mold foams. Among the mold foams of Example 4, Comparative Examples 3, 4 and 6 using the same amount of water, the density is much lower in Example 4. Further, in order to obtain a foam having the same density as that of Example 4, 5.7 parts or more of H ₂ O is required as in Comparative Example 7. To obtain the same density as in Comparative Example 3 using the polyol of Example 1, H
₂ O is less than 4.7 parts. The influence of the polyol of Example 1 on the density is remarkable. On the other hand, the hardness of each of Examples 4 and 5 (25% ILD) is 10.0 kg or less, which is a sufficiently low value. In such hand mixing foaming, it is extremely difficult to maintain a wet heat permanent set of 15% or less and manufacture a foam having a hardness of 10 kg or less. However, by using the polyol of the present application, it can be easily achieved as in Example 3. Actcol MF-5, which is currently on the market as a soft polyol for CFC protection
3, the density of the same blowing agent is 35.4 kg / m ³ , 25%
The ILD is 13.5 kg and it is clear how excellent the example is. In order to obtain a density of about 35 kg / m ³ , the polyol of Example 1 had H ₂ as shown in Example 5.
The amount of O used is only 4.7 parts, and the 25% ILD can be cut to 10 kg. The effect of this Example 2 is also clear.

Comparative Examples 4 and 5 use the polyol of Comparative Example 1. The polyol of Comparative Example 1 has a structure similar to that of the polyol of Example 1, but does not use the EO adduct of aminoethylpiperazine as an initiator. [Table 1]
As is clear from the results of 1., the difference between Example 4 and Comparative Example 4 is clear. Comparative Example 8 is a low hardness, low density flexible foam using the conventional CFC-11. Many chlorofluorocarbon countermeasures have been studied in search of the physical properties shown here. Comparing this physical property with Examples 4 and 5, there is no inferiority. According to the present invention, the reduction of CFCs in hot-molded foam has been completely achieved. From these results, the flexible urethane foam obtained by using the polyol of the present invention has excellent properties, and the usefulness of the polyol of the present invention is clear.

[0034]

[Table 1] (1) Takeda Yakuhin OH number 70.0 mg KOH / g, viscosity 4
50 mPa · s (2) Flame retardant manufactured by Daihachi Chemical Co., Ltd. (3) Catalyst manufactured by Tosoh (4) Nihon Unicar: Silicon foam stabilizer Example 6-1 to 6-3, 7-1, 7-2 and Comparative Example 9 −
1 to 9-3 [Table 2] shows a comparison as a polyol for HR foam. HR foam was produced by the hand mixing method with the formulation shown in [Table 2]. That is, a polyol catalyst, a foam stabilizer, a cross-linking agent, and water are used as a premix in advance, and an appropriate amount is taken out so that the isocyanate index becomes 100 (Examples, Examples 6 and 7 and Comparative Example 8, premix in the formulation. /TM-20=100/43.5),
Stir in mixer for 5 seconds. This was poured into a 400 × 400 × 100 mm aluminum mold whose mold temperature was adjusted to 60 ° to 70 °, cured at the same temperature for 7 minutes, demolded, and crushed. The physical properties were measured after standing for 1 day or more. Foam was made by adding the injection amount, and the foam was made by changing the density. The hardness of HR foam depends on the foam density. FIG. 1 shows the relationship between the density and 25% ILD. The formulation of Comparative Example 9 does not show a density of 37 kg / m ³ or less, which means that the polyol of Comparative Example cannot reduce the density. The effect of lowering the density and the effect of lowering the hardness of the polyols of Examples 2 and 3 are clear. Also, the permanent set of moist heat is 20
% Or less, which is a clear difference from the comparative example.

[0035]

[Table 2] Reference Example 1 Ruplanate MI (BA
18.5 kg of SF-made MDI) and 34.5 kg of luplanate M (BASF-made MDI) are added at 70 ° -80 °.
Takerac P-21 (Takeda Yakuhin OH number 56 diol) 17.0 kg was added in 1 hr, and 2 to 3 hr 70 ° C to 80 ° C.
Keep at ℃. Then, 30 kg of Luplanate M-20 (Polymeric MDI made by Takeda Birdish Urethane) was added and mixed to obtain an amine equivalent of 159.5 and a viscosity of 102 mPa · s (250
C.) modified MDI was obtained. This MDI is called isocyanate-C.

Examples 8 and 9 and Comparative Examples 10 and 11 [Table 3] shows an example of a so-called all-MDI formulation. Example 8 and Comparative Example 10 are almost the same in terms of prescription. Also, the free foam density does not change so much. However, when a mold foam is used as in Example 6-1 and the like, the density changes greatly. As a matter of course, the density of HR foam changes depending on the filling amount of foam, but Comparative Example 1
When the injection amount is reduced with the prescription of 0, the foam is not completely filled and it is not possible to obtain a foam of 53 kg / m ³ or less. In practice, a foam having the same density as that of Comparative Example 10 can be obtained by reducing H ₂ O to 3.0 parts as in Example 9. The obtained physical properties are also shown in [Table 3]. That is, low density and low hardness are obtained, the permanent set is sufficiently small, and the wet heat permanent set is less than 10%. Also in this example, the excellent effect of this manufacturing method is clear.

[Table 3]

[0037]

The present invention has the following effects. That is, when the polyol of the present invention is used (including the case where it is used as a part of the polyol), the following surprising effects are exhibited. 25% ILD (compression hardness according to JIS-K6401)
Can be reduced by 2 kg or more, and permanent distortion and the like are not reduced. It is possible to suppress the amount of water used in the production of mold foam. That is, when the same water is used for foaming, the polyol of the present invention can be used to obtain a low-density foam. That is, the foaming efficiency becomes extremely high. It is possible to reduce the amount of the amine catalyst used during foam production or substantially eliminate the need for use. The amine catalyst used in foam production is necessary for foam production, but it is well known that the amine catalyst present in the foam causes discoloration, deterioration and the like. Also in this respect, the present polyol has a very specific advantage. Further, the foam produced by the present invention has the following features. (1) It is not necessary to use a specific chlorofluorocarbon such as CFC-11, which causes environmental problems. (2) The hardness can be lowered without lowering other physical properties (particularly, wet heat permanent set). (3) The amount of H ₂ O used in foam production is small. As a result, not only can the foam be manufactured more economically, but the problems (feel, hardness, permanent set, etc.) due to the use of a large amount of H ₂ O can be solved.

[Brief description of drawings]

FIG. 1 is an HR obtained in Examples 6 and 7 and Comparative Example 9.
The relationship between foam density and hardness is shown.

[Explanation of symbols]

● indicates the foam of Example 6, ◆ indicates the foam of Example 7, and × indicates the foam of Comparative Example 9.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Office reference number FI technical display area C08G 101: 00)

Claims (13)

[Claims] 1. A polyether polyol having a molecular weight of about 2000 to 7,000 obtained by addition-polymerizing an alkylene oxide using an ethylene oxide adduct of N-aminoethylpiperidine as an initiator. 2. The polyether polyol according to claim 1, which has a hydroxyl value of 23 to 100 mgKOH / g. 3. The polyether polyol according to claim 1, wherein the alkylene oxide which undergoes addition polymerization is ethylene oxide and / or propylene oxide. 4. The polyether polyol according to claim 1, wherein the content of ethylene oxide for addition polymerization is 20% or less in the polyether polyol. 5. The polyether polyol according to claim 1, wherein the content of ethylene oxide directly linked to the terminal hydrogen atom of the molecule is 15% or less. 6. A polyol containing a polymer component of an ethylenically unsaturated bond monomer and the polyether polyol component of claim 1. 7. A method for producing a flexible urethane foam, which comprises reacting a polyol containing the polyether polyol component according to claim 1 with an organic polyisocyanate in the presence of a foam stabilizer and a foaming agent. 8. A polyol containing (i) a polyether polyol component having a hydroxyl value of 40 to 80 mg KOH / g, and (ii) 4.0 to 6.0 per 100 parts by weight of the polyol.
The manufacturing method according to claim 7, characterized in that a part by weight of water is used as a foaming agent. 9. The alkylene oxide to be addition-polymerized with a polyether polyol component is propylene oxide and ethylene oxide, and the ethylene oxide content is 2
The production method according to claim 8, wherein the content is 0% or less and the content of terminal ethylene oxide is 10% or less. 10. The process according to claim 8, wherein the polyether polyol component according to claim 1 is used in an amount of 5% or more and 40% or less based on the total polyol. 11. The method according to claim 8, wherein the organic polyisocyanate is tolylene diisocyanate. 12. (i) Hydroxyl value is 23 to 50 mg KOH / g
8. A polyol containing a polyether polyol component which is said, and (ii) 2.5 parts by weight or more and 5.0 parts by weight or less of water per 100 parts by weight of polyol is used as a foaming agent. Manufacturing method. 13. The alkylene oxide to be addition-polymerized with the polyether polyol component is propylene oxide and ethylene oxide, the ethylene oxide content is 25% or less and 5% or more, and the terminal ethylene oxide content is 5 to 20%. 12. The method according to item 12.