JP2003231747A - Polyol, method for producing the same, and method for producing flexible polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a low hydroxy number and high molecular weight polyol as a starting material for flexible polyurethane foams, to provide a method for producing the polyol within a short time, and to provide a method for producing a flexible polyurethane foam produced by using the polyol. <P>SOLUTION: A polyol having a hydroxyl number of at most 15 mgKOH/g, a hydroxyl functionality of 2-8 and ethylene oxide/3C or higher alkylene oxide oxyalkylene random chains is provided, in which proportion of ethylene groups is 1-60 mass%; a method for producing the polyol by obtaining the oxyalkylene random chains by using a mixture of ethylene oxide and a 3C or higher alkylene oxide as alkylene oxides; and a method for producing a flexible polyurethane foam in an open state by reacting the polyol with a polyisocyanate compound in the presence of a catalyst, a blowing agent, and a foam stabilizer. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

TECHNICAL FIELD The present invention relates to a high molecular weight polyol having an oxyalkylene random chain and a low hydroxyl value, a method for producing the same, and a method for producing a flexible polyurethane foam produced by using the polyol.

[0002]

2. Description of the Related Art Conventionally, a flexible polyurethane foam is manufactured from a polyol as a raw material by an open manufacturing method such as a slab molding method or a closed manufacturing method using a closed mold. As the slab foam produced by the open-type production method, a polyol having a molecular weight of about 3,000 to 5,000 as a raw material is generally used.

Generally, the polyol used as a raw material for the flexible polyurethane foam is a sodium-based catalyst such as sodium hydroxide or a potassium-based catalyst such as potassium hydroxide, and propylene oxide or the like using a polyhydric alcohol or the like as an initiator. Is produced by subjecting the alkylene oxide of ## STR3 ## to ring-opening addition polymerization. In this production method, a monool having an unsaturated bond (unsaturated monool) is produced as a by-product, and the production amount of this unsaturated monool increases with a decrease in the hydroxyl value of the polyol (an increase in the molecular weight).

When a flexible polyurethane foam is produced using a polyol having a high degree of unsaturation, there arise problems such as a decrease in hardness, deterioration of compression set, and a decrease in cure property during molding. Further, when trying to produce a polyol having a low hydroxyl value using a sodium-based catalyst or a potassium-based catalyst,
The degree of unsaturation becomes extremely high, which makes production very difficult.

On the other hand, as a method for producing a polyol having a low hydroxyl value and a low unsaturation degree, a method of ring-opening addition polymerization of alkylene oxide using a double metal cyanide complex catalyst is known.

Although a polyol having a low unsaturation degree can be produced by using a double metal cyanide complex catalyst, foam stability tends to be deteriorated when producing a foam. When a high-molecular-weight polyol having a hydroxyl value of 15 mgKOH / g or less is used as a raw material, the tendency is further strengthened, and it has been speculated that the production of flexible polyurethane foam is difficult.

In order to improve the above-mentioned problem of moldability, in JP-A-8-231676, a polyol produced by using a complex metal cyanide complex catalyst and a sodium hydroxide catalyst or a potassium hydroxide catalyst are produced. A method for producing a flexible polyurethane foam using a polyol mixture with the above polyol has been proposed. However, this publication relates to a mold foam, and does not describe a production example using a high molecular weight polyol.

Further, in US Pat. No. 6,028,230 and US Pat. No. 6,066,683, a slab is prepared by using a polyol having a hydroxyl value of 10 to 80 mgKOH / g, which is produced by using a complex metal cyanide complex catalyst. A method of making a foam is disclosed. But,
In the examples of these publications, only an example of producing a flexible foam with a polyol having a molecular weight of 5000 is described, and an example of production using a higher polymer polyol is not described.

Further, in Japanese Patent Laid-Open No. 2-286707, mechanical properties such as tensile strength and elongation are considered as essential components of polyoxyalkylene diol having an average molecular weight of 1500 or more and polyoxyalkylene diol having an average molecular weight of 150 to 350. A method for producing a flexible polyurethane foam having excellent properties is disclosed. The publication describes an example in which the mechanical properties are insufficient when the two components are not essential, particularly when a polyoxyalkylene diol having 2 functional groups is not used. However, this publication does not describe any production example of a flexible polyurethane foam using a polyol having a molecular weight of 5000 or more as a raw material.

[0010]

The polyol, which is a raw material of the above-mentioned flexible polyurethane foam, removes the catalyst used during its synthesis. Therefore, an adsorbent is added to the reaction product to adsorb the catalyst and by-products. Furthermore, there is a problem that an operation for separating the adsorbent from the polyol is required, which requires time and labor for its production. In addition, since a high molecular weight polyol having a low hydroxyl value generally has a high viscosity, it is difficult to remove the adsorbent.

The present invention provides a method for producing a polyol capable of producing a high molecular weight polyol having a low hydroxyl value, which is a raw material of a flexible polyurethane foam, in a short time without using an adsorbent, and a method for producing the polyol. It is an object of the present invention to provide a high molecular weight polyol having a low hydroxyl value, and a method for producing a flexible polyurethane foam produced by using the polyol.

[0012]

The present invention has a hydroxyl value of 1
5 mgKOH / g or less, the number of hydroxyl groups is 2 to 8, has an oxyalkylene random chain of ethylene oxide and an alkylene oxide having 3 or more carbon atoms, and the proportion of oxyethylene groups in the oxyalkylene random chain is 1 to 60 mass. % Polyoxyalkylene polyol is provided. Below, this specific polyoxyalkylene polyol is referred to as polyol (1). This polyol (1)
When used, a low-resilience flexible polyurethane foam excellent in durability and mechanical properties can be obtained.

The present invention is also a method for producing a polyoxyalkylene polyol by subjecting an initiator to ring-opening addition polymerization of alkylene oxide in the presence of a catalyst, wherein ethylene oxide and alkylene oxide having 3 or more carbon atoms are used as the alkylene oxide. There is provided a method for producing a polyoxyalkylene polyol, which comprises producing an oxyalkylene random chain using a mixture to produce the polyol (1). Here, the catalyst is preferably a double metal cyanide complex catalyst. According to this production method, the polyol (1) can be stably produced.

The present invention also provides a method for producing a flexible polyurethane foam in an open state by reacting a polyol and a polyisocyanate compound in the presence of a catalyst, a foaming agent and a foam stabilizer, and the above polyol (1) is used as the polyol. The present invention provides a method for producing a flexible polyurethane foam, which comprises using Below, flexible polyurethane foam is abbreviated as flexible foam. According to this production method, it is possible to obtain a low-resilience flexible foam having excellent durability and mechanical properties and having a characteristic that hardness change due to temperature change is small.

[0015]

BEST MODE FOR CARRYING OUT THE INVENTION The polyol according to the present invention has a hydroxyl value of 15 mgKOH / g or less, a hydroxyl group number of 2 to 8, and an oxyalkylene random chain of ethylene oxide and an alkylene oxide having 3 or more carbon atoms, The ratio of oxyethylene groups in the oxyalkylene random chain is 1
It is characterized by being ~ 60 mass%. Further, the method for producing a polyoxyalkylene polyol according to the present invention,
A method for producing a polyoxyalkylene polyol by ring-opening addition polymerization of an alkylene oxide as an initiator in the presence of a catalyst, which comprises using a mixture of ethylene oxide and an alkylene oxide having 3 or more carbon atoms as the alkylene oxide. To obtain the polyol (1). Furthermore, the method for producing a flexible foam according to the present invention is a method for producing a flexible polyurethane foam in an open state by reacting a polyol and a polyisocyanate compound in the presence of a catalyst, a foaming agent and a foam stabilizer, wherein the above-mentioned polyol is used. It is characterized by using a polyol (1).

Polyol used in the present invention (1)
Is a high-molecular-weight polyol having a hydroxyl value of 15 mgKOH / g or less. As the polyol (1) having a low hydroxyl value, a polyoxyalkylene polyol obtained by subjecting an alkylene oxide to an initiator as a ring-opening addition polymerization reaction is preferable. As the ring-opening addition polymerization catalyst, a double metal cyanide complex catalyst, a phosphazene compound catalyst,
Any catalyst capable of obtaining a low degree of unsaturation such as a cesium hydroxide catalyst may be used, but a double metal cyanide complex catalyst is particularly preferable. That is, the polyol (1) preferably has a polyoxyalkylene chain obtained by ring-opening addition polymerization of alkylene oxide using a double metal cyanide complex catalyst. By using the double metal cyanide complex catalyst, a polyol having a low hydroxyl value and a narrow molecular weight distribution can be produced. A polyol having a narrow molecular weight distribution has a lower viscosity than a polyol having a wide molecular weight distribution in a similar molecular weight region, and therefore foam stability during the production of a flexible foam is improved, which is preferable. In addition, by using a complex metal cyanide complex catalyst, it is possible to use a small amount of catalyst, and it is possible to omit the addition of an absorbent for adsorbing and removing the catalyst and the like after the synthesis of the polyol, and the separation operation thereof, and to produce in a short time. can do.

As the above-mentioned complex metal cyanide complex catalyst, for example, those described in JP-B-46-27250 can be used. Specific examples include a complex containing zinc hexacyanocobaltate as a main component, and an ether and / or alcohol complex thereof is preferable. As the ether, ethylene glycol dimethyl ether (glyme), diethylene glycol dimethyl ether (diglyme), ethylene glycol mono-tert-
Butyl ether (METB), ethylene glycol mono-tert-pentyl ether (METP), diethylene glycol mono-tert-butyl ether (DET)
B), tripropylene glycol monomethyl ether (TPME) and the like are preferable. Further, as the alcohol, tert-butyl alcohol or the like is preferable.

The initiator is preferably a compound having 2-8 active hydrogen atoms in the molecule, for example, ethylene glycol, propylene glycol, 1,4-butanediol, glycerin, trimethylolpropane, pentaerythritol, diglycerin. , Polysodium alcohols such as meso-erythritol, methyl glucoside, glucose, sorbitol, sucrose; phenols such as bisphenol A; ethylenediamine, diethylenetriamine,
Examples include amines such as piperazine, aminoethylpiperazine, diaminodiphenylmethane, and monoethanolamine; condensed compounds such as phenol resin and novolac resin. Among the above initiators, polyhydric alcohols are preferable. Two or more kinds of these initiators may be used in combination.
Further, a relatively high molecular compound obtained by ring-opening addition of an alkylene oxide to the above compound may be used as an initiator. That is, a particularly preferable compound as an initiator is a relatively high molecular compound obtained by ring-opening addition of an alkylene oxide to the above polyhydric alcohols, and its hydroxyl value is 200 mgK.
OH / g or less is preferable.

The polyol (1) in the present invention has an oxyalkylene random chain. The oxyalkylene random chain is a structure obtained by supplying ethylene oxide and an alkylene oxide having 3 or more carbon atoms in a predetermined ratio into the reaction system and randomly performing ring-opening addition polymerization. The formation of the oxyalkylene random chain is ¹³ C-
It can be confirmed by NMR. For example, in the case of an oxyalkylene random chain of ethylene oxide and propylene oxide, a peak derived from the oxyalkylene random chain is observed at 69.7 ppm with TMS as the standard. The catalyst used for the formation of the oxyalkylene random chain may be a catalyst capable of obtaining a low degree of unsaturation such as a complex metal cyanide complex catalyst, a phosphazene compound catalyst, and a cesium hydroxide catalyst, but particularly a complex metal cyanide. Complex catalysts are preferred. Further, the proportion of the oxyalkylene random chain in the polyol (1) is preferably 30 to 99% by mass, more preferably 50 to 90% by mass. The carbon number 3
Propylene oxide is preferable as the above alkylene oxide. The content of the oxyethylene group in the oxyalkylene random chain is preferably 3 to 50% by mass, more preferably 5 to 35% by mass, and particularly preferably 15 to 30% by mass based on the oxyalkylene random chain. The proportion of all oxyethylene groups (including the oxyethylene groups in the oxyalkylene random chain) in the polyol (1) is preferably 2 to 50% by mass, and 5 to 45% by mass with respect to the entire polyol (1). Is more preferable. The polyol (1) preferably has the oxyalkylene random chain at the end.

The number of hydroxyl groups of the polyol (1) in the present invention is preferably 2-8, more preferably 2-6.
8-5.2 are especially preferable. However, the number of hydroxyl groups means the average value of the number of active hydrogens of the initiator. By setting the number of hydroxyl groups to 2 or more, it is possible to avoid the drawback that the flexible foam becomes soft and the compression set deteriorates. By setting the number of hydroxyl groups to 8 or less, it is possible to avoid the drawback that the obtained flexible foam becomes hard and the mechanical properties such as elongation are deteriorated.

The hydroxyl value of the polyol (1) in the present invention is 15 mgKOH / g or less and 5 mgKOH / g.
g or more and 15 mgKOH / g or less are preferable, and 5 mgKO
It is preferably H / g or more and less than 10 mgKOH / g. By using a polyol having a hydroxyl value of 15 mgKOH / g or less, mechanical properties such as tensile strength and tear strength are excellent,
Moreover, a flexible foam having a characteristic that the change in physical properties with temperature is small can be produced. Also, the hydroxyl value is 5 mgK
When it is less than OH / g, the viscosity of the polyol becomes high, which makes it substantially difficult to produce a flexible foam.

The unsaturation degree of the polyol (1) in the present invention is preferably 0.05 meq / g or less. By setting the degree of unsaturation to 0.05 meq / g or less, it is possible to avoid the drawback that the durability of the produced flexible foam deteriorates. More preferably, the unsaturation of the polyol is 0.04
It is not more than meq / g.

As the polyol (1) in the present invention, a polymer-dispersed polyol in which polymer particles are stably dispersed may be used. Here, the polymer-dispersed polyol is a dispersion system in which polymer particles (dispersoids) are stably dispersed in a base polyol (dispersion medium). Examples of the polymer of the polymer particles include addition polymerization type polymers or condensation polymerization type polymers. The addition-polymerization polymer is obtained, for example, by homopolymerization or copolymerization of monomers such as acrylonitrile, styrene, methacrylic acid ester, and acrylic acid ester. Examples of the polycondensation polymer include polyester, polyurea, polyurethane, melamine and the like. The presence of polymer particles in the polyol suppresses the hydroxyl value of the polyol to a low level, and is effective in improving the physical properties such as air permeability of the flexible foam. The content of polymer particles in the polymer-dispersed polyol is not particularly limited, but is preferably 50% by mass or less, more preferably 3 to 40% by mass. When the mass of the polyol is used for calculation, the mass of the polymer particles is not included.

In the method for producing a flexible foam of the present invention, a polyol, which comprises the above-mentioned polyol (1) or a polyol mixture containing the polyol (1) as a main component, and a polyisocyanate compound are used as a catalyst, a foaming agent and a foam stabilizer. To produce a flexible foam. In the production of this flexible foam, the proportion of the polyol (1) in the total amount of the polyol compound used is preferably 90% by mass or more, more preferably 95% by mass or more, and particularly preferably 100% by mass. That is, the polyol compound may contain other polyols other than the polyol (1), but the proportion thereof is preferably 10% by mass or less in the polyol compound, and 5% by mass.
The following are more preferable, and it is particularly preferable that they are not included. However, the crosslinking agent described below is not considered as a polyol. The total unsaturation of the polyol mixture is 0.05 m
eq / g or less is preferable, and 0.04 meq / g or less is more preferable.

The polyisocyanate compound used in the present invention is not particularly limited, and is an aromatic, alicyclic or aliphatic polyisocyanate having two or more isocyanate groups; two or more kinds of the above polyisocyanates. Mixtures; examples include modified polyisocyanates obtained by modifying these. Specific examples include tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (common name: crude MDI), xylylene diisocyanate (XDI), isophorone diisocyanate (IPDI), hexamethylene diisocyanate (HM).
Examples thereof include polyisocyanates such as DI) or prepolymer-type modified products thereof, nurate modified products, urea modified products, carbodiimide modified products, and the like. Among these, TD
I, MDI, crude MDI, or modified forms thereof are preferred.

The amount of the polyisocyanate compound used is usually represented by an isocyanate index (a number represented by 100 times the number of isocyanate groups with respect to the total number of all active hydrogens such as polyol, crosslinking agent and water). The amount of the polyisocyanate compound used is preferably in the range of 40 to 120 in terms of isocyanate index, and 5
The range of 0 to 110 is more preferable.

As the catalyst for reacting the polyol with the polyisocyanate compound, all catalysts that accelerate the urethanization reaction can be used, and examples thereof include triethylenediamine, bis (2-dimethylaminoethyl) ether,
Tertiary amines such as N, N, N ′, N′-tetramethylhexamethylenediamine; carboxylic acid metal salts such as potassium acetate and potassium 2-ethylhexanoate; organometallic compounds such as stannas octoate and dibutyltin dilaurate Is mentioned.

As the above-mentioned foam stabilizer, those used in the usual production of polyurethane foam can be used, and examples thereof include a silicone-based foam stabilizer and a fluorine-based foam stabilizer. Particularly preferred. By using these foam stabilizers, uniform bubbles can be formed. The foaming agent is not particularly limited, and a known foaming agent such as hydrogen fluoride can be used, but at least one selected from water and an inert gas is preferable. Specific examples of the inert gas include air, nitrogen, carbon dioxide gas and the like. Of these, water is preferred. The amount of the foaming agent used is not particularly limited, but when water is used, it is preferably 10 parts by mass or less, more preferably 0.1 to 8 parts by mass, and 0.5 to 4 parts by mass with respect to 100 parts by mass of the polyol. Particularly preferred.

In the present invention, a cross-linking agent can also be used if necessary. As the cross-linking agent, a compound having two or more functional groups having active hydrogen such as a hydroxyl group, a primary amino group or a secondary amino group is preferable. However, when a polyol compound is used as the cross-linking agent, it is considered as follows. That is, a polyol compound having a hydroxyl value of 50 mgKOH / g or more and a functional group number of 4 or more is considered to be a cross-linking agent, and a polyol not corresponding to this is any one of the above-mentioned polyol mixtures (polyol (1) or other polyols). ) Think as. Furthermore, two or more crosslinking agents may be used in combination. Specific examples include polyhydric alcohols such as pentaerythritol, diglycerin, dextrose, sorbitol, sucrose; polyols obtained by adding alkylene oxide to the polyhydric alcohols; monoethanolamine, diethanolamine, ethylenediamine, 3,5- Diethyl-2,4 (or 2,6) -diaminotoluene (DETDA), 2-chloro-p-phenylenediamine (CPA), 3,5-bis (methylthio) -2,4 (or 2,6) -diamino Toluene, 1-trifluoromethyl-4-chloro-3,5
-Diaminobenzene, 2,4-toluenediamine, 2,
6-toluenediamine, bis (3,5-dimethyl-4-
Examples thereof include amine compounds such as aminophenyl) methane, 4,4′-diaminodiphenylmethane, m-xylylenediamine, 1,4-diaminohexane, 1,3-bis (aminomethyl) cyclohexane, and isophoronediamine.

In the method for producing a flexible foam of the present invention, desired additives may be used in addition to the above-mentioned catalyst, foaming agent, foam stabilizer and cross-linking agent. As additives, fillers such as potassium carbonate and barium sulfate; surfactants such as emulsifiers and foam stabilizers; antioxidants such as antioxidants and ultraviolet absorbers; flame retardants, colorants, antifungal agents, Examples include foam breakers, dispersants, discoloration inhibitors, and the like.

As the method for producing the flexible foam of the present invention, a method (slab method) in which a reactive mixture is injected into an open mold and foam molding is employed. As a specific reaction method, a known method such as a one-shot method, a semi-prepolymer method or a prepolymer method can be adopted. For the production of polyurethane, commonly used production equipment can be used.

The flexible foam according to the present invention is used for bedding, mats, cushions, seats and the like.

[0033]

EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited thereto. In addition, the numerical value of the foaming prescription column in the following Examples 1-11 represents a mass part.

The number of hydroxyl groups, the hydroxyl value (mgKOH / g), the degree of unsaturation (meq / g) of the polyols used in Examples 1 to 11 below, and the time required from the start of the reaction to the production of the product (hr) are shown in the table. Shown in 1. The unsaturated degree was measured by a method according to JIS K1557. Also, the formation of oxyalkylene random chains can be confirmed by ¹³ C-
It was performed by NMR. The measurement is JNM-A manufactured by JEOL Ltd.
L300 was used.

(1) Production of polyol A: A compound having a hydroxyl value of 56 mgKOH / g obtained by adding propylene oxide to glycerin was used as an initiator. In the presence of 3000 g of this initiator, zinc hexacyanocobaltate-
Using a glyme complex catalyst (hereinafter referred to as DMC-glyme catalyst), propylene oxide: ethylene oxide =
75:25 wt% alkylene oxide mixture 2500
0 g was reacted at about 120 ° C. to complete the polymerization, and a polyol A having a hydroxyl value of 6.9 mgKOH / g having an oxyalkylene random chain of ethylene oxide and propylene oxide was produced.

(2) Production of Polyol B: Propylene oxide: ethylene oxide = 85.000 using DMC-Glyme catalyst in the presence of 3000 g of the same initiator as in (1).
7: 14.7 wt% alkylene oxide mixture 200
Polymerization was completed by reacting 00 g at about 120 ° C. to produce a polyol B having a hydroxyl value of 8.6 mgKOH / g having an oxyalkylene random chain of ethylene oxide and propylene oxide.

(3) Production of Polyol C: In the presence of 3000 g of the same initiator as in (1), 21,700 g of propylene oxide was reacted with DMC-glyme catalyst at about 120 ° C., and then ethylene oxide was used with potassium hydroxide catalyst. 1300 g was reacted at 120 ° C. to complete the polymerization,
A hydroxyl value of 8.4 mg KOH polyol C was obtained.

(4) Production of Polyol D: In the presence of 3000 g of the same initiator as in (1), 21,700 g of propylene oxide was reacted with DMC-glyme catalyst at about 120 ° C., and then ethylene oxide was used with potassium hydroxide catalyst. Polymerization was completed by reacting 1300 g at 120 ° C. After reaction, treatment with adsorbent (synthetic magnesium silicate),
Filtration was performed to obtain a polyol D having a hydroxyl value of 9.1 mgKOH / g.

(5) Production of polyol E: In the presence of 1000 g of glycerin as an initiator, 2300 g of a mixture of ethylene oxide and propylene oxide containing 10% of ethylene oxide was reacted at 110 ° C. using a KOH catalyst to complete the production. After the reaction, treatment with an adsorbent (synthetic magnesium silicate) and filtration were performed to obtain a polyol E having a hydroxyl value of 56.1 mgKOH / g having an oxyalkylene random chain of ethylene oxide and propylene oxide.

(6) Production of Polyol F: Polyol E
A polymer-dispersed polyol in which (60% by mass) is used as a dispersion medium and acrylonitrile and styrene copolymer particles (40% by mass) are dispersed.

Crosslinking agent: sorbitol 182 as an initiator
Propylene oxide 6 with KOH catalyst in the presence of g
345g, then 300g of ethylene oxide about 100
The reaction was carried out at ° C. After the reaction, treatment with an adsorbent and filtration were performed to obtain a polyol having a hydroxyl value of 56.0 mgKOH / g.

[0042]

[Table 1]

Flexible foams were produced by using the raw materials shown in Table 2 in the blending amounts shown in Tables 3 and 4 (the numbers indicate parts by mass). In Examples 1 to 8 and Examples 10 to 11, among these raw materials and compounding agents, the liquid temperature of a mixture of all raw materials other than polyisocyanate was adjusted to 50 ° C. ± 1 ° C., and the polyisocyanate compound solution was heated to a liquid temperature of 20 ±. The temperature was adjusted to 1 ° C., a predetermined amount of the polyisocyanate compound was added to the polyol-containing mixture, and the total amount of 1 kg was mixed with a high-speed mixer for 5 seconds.
It was poured into a 0 mm wooden box. The polyurethane foam was taken out and allowed to stand in a room whose temperature and humidity were adjusted to room temperature (20 ° C.) and humidity of 50% for 24 hours or more, and then various physical properties were measured. Regarding Example 9, a polyurethane foam was produced in the same manner as in Examples 1 to 9 except that the mixture of all raw materials other than polyisocyanate and the polyisocyanate compound solution were respectively adjusted to 25 ° C ± 1 ° C. Example 8
No sufficient foaming occurred, molding was not possible, and physical properties could not be measured.

The measurement results are shown in Tables 3 and 4. The foam physical properties are measured in accordance with the following. Regarding the core density and the core impact resilience, the foam is cut out from the center of the foam to 100 mm in length and width and 50 mm in height for measurement. I was there.

The standards used for measuring the physical properties of flexible foams are shown below. Core density (unit: kg / m ³ ), 25% hardness (ILD)
(23 ° C.) (unit: N / 314 cm ² ), CLD hardness (unit: N / cm ² ), breathability (unit: ft ³ / min)
(SI conversion: 28.3 L / min)), core impact resilience (unit:%), tear strength (unit: N / cm), tensile strength (unit: kPa), elongation (unit:%), dry heat Compression set (unit:%), hysteresis loss (unit:
%) Is a method based on JISK6400. CLD hardness 1 is CLD measured at room temperature (23 ° C)
Hardness, CLD hardness 2 is CLD hardness measured at a low temperature (−25 ° C.), and the hardness ratio is the value of CLD hardness 2 of CLD.
It is a value divided by the value of LD hardness 1. If this hardness ratio is close to 1, it can be said that the hardness change with respect to the temperature change is small.

[0046]

[Table 2]

[0047]

[Table 3]

[0048]

[Table 4]

From the results shown in Table 1, alkylene oxide was subjected to ring-opening addition polymerization in the presence of a double metal cyanide complex catalyst to have an oxyalkylene random chain of ethylene oxide and propylene oxide and a hydroxyl value of 15
Compared with the polyol D, the polyols A and B according to the present invention having a mgKOH / g or less do not require much time to convert the catalyst, and the steps of adding an adsorbent for removing the converted catalyst and removing the adsorbent are not required. Since it can be omitted, it was possible to manufacture in a short time.

Further, from the results shown in Tables 3 and 4,
Examples 1 to 1 produced using the polyols A and B according to the present invention
The flexible foam of No. 7 was able to produce a flexible foam, while the hydroxyl value of 8.4 m having no oxyalkylene random chain of ethylene oxide and propylene oxide.
In Example 8 in which gKOH / g of polyol C was used as a raw material, the foam was poorly formed. Further, in comparison with the flexible foams of Examples 9 and 10 using Polyol D having a hydroxyl value of 9.1 mgKOH / g having no oxyalkylene random chain of ethylene oxide and propylene oxide as raw materials and Example 11 using Polyol E as raw material, It was found that the flexible foams of Examples 1 to 7 produced by using the polyols A and B according to the present invention had a 25% hardness and a low core impact resilience, and a low resilience flexible foam was obtained. That is,
It was found that by using the polyol according to the present invention, a flexible foam having the same or lower resilience as that of the polyol D having no oxyalkylene random chain can be obtained and the production time of the polyol can be shortened.

[0051]

According to the method for producing a polyol of the present invention, a high molecular weight polyol having a random addition structure of ethylene oxide and propylene oxide, which is a raw material for a flexible polyurethane foam, and having a hydroxyl value of 15 mgKOH / g or less, It can be manufactured in a short time without using an adsorbent. The method for producing a flexible polyurethane foam according to the present invention can produce a flexible polyurethane foam having excellent mechanical properties, particularly low rebound, using the polyol according to the present invention as a raw material.

Continued front page    (72) Inventor Yuji Kimura             25 Asahi, Towada, Kazasu-machi, Kashima-gun, Ibaraki             Glass Urethane Co., Ltd. F-term (reference) 4J005 AA04 BB02                 4J034 BA03 DB04 DB05 DC50 DE04                       DG02 DG03 DG04 DG05 DG06                       DG10 HA07 HA11 HB08 HC12                       HC17 HC22 HC35 HC52 HC63                       HC64 HC67 HC71 HC73 KA01                       KA04 KC02 KC17 KD02 KD12                       KE01 KE02 NA01 NA02 NA03                       NA08 QA02 QC01 QD03 RA03

Claims (4)

[Claims] 1. A hydroxy group value of 15 mgKOH / g or less, a hydroxyl group number of 2 to 8, an oxyalkylene random chain of ethylene oxide and an alkylene oxide having 3 or more carbon atoms, and oxyethylene in the oxyalkylene random chain. A polyoxyalkylene polyol having a group ratio of 1 to 60% by mass. 2. A method for producing a polyoxyalkylene polyol by ring-opening addition polymerization of an alkylene oxide with an initiator in the presence of a catalyst, wherein ethylene oxide and C 3 are used as the alkylene oxide.
An oxyalkylene random chain is obtained by using a mixture with the above alkylene oxide to produce the polyoxyalkylene polyol according to claim 1.
Method for producing polyoxyalkylene polyol. 3. The method for producing a polyol according to claim 2, wherein the catalyst is a double metal cyanide complex catalyst. 4. In the method for producing a flexible polyurethane foam in an open state by reacting a polyol and a polyisocyanate compound in the presence of a catalyst, a foaming agent and a foam stabilizer, the polyol according to claim 1 is used as the polyol. A method for producing a flexible polyurethane foam, comprising: