JP2007186557A - Foam stabilizer for polyurethane foam and method for producing polyurethane foam - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a foam stabilizer for polyurethane foams which extremely reduces the amount of aldehydes generated with time even when incorporated into a polyurethane foam and a method for producing a polyurethanr foam by using this foam stabilizer. <P>SOLUTION: The foam stabilizer for polyurethane foams comprises a polyether-modified silicone compound synthesized by the hydrosilylation reaction between at least an organohydrogenpolysiloxane and an allyl group-containing polyoxyalkylene compound, and the polyether-modified silicone compound has an amount of aldehydes generated on heat aging at 50°C for 0.5 hour in 0.23 N hydrochloric acid of not more than 100 ppm based on the mass of the polyether-modified silicone compound. The method for producing a polyurethane foam comprises foaming a mixture containing a polyol, an isocyanate compound, a blowing agent, a catalyst, and the above foam stabilizer. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a foam stabilizer for polyurethane foams, and more particularly to a foam stabilizer for polyurethane foams that has a very small amount of harmful aldehydes that are generated over time even when blended in polyurethane foams. Moreover, this invention relates to the manufacturing method of the polyurethane foam using this foam stabilizer.

  With the recent increase in interest in environmental problems, there are concerns about the adverse effects that volatile organic substances generated from building materials, automobile interior materials, etc. have on the human body. Polyurethane foams used in these building materials, automobile interior materials, and the like often contain the volatile organic substances, and there is an increasing demand for reducing the content thereof as much as possible.

  By the way, a polyurethane foam is obtained by foaming by mixing and reacting a polyol, an isocyanate compound, a foaming agent, a catalyst, and a foam stabilizer. Conventionally, many foam stabilizers are compositions containing a polyether-modified silicone compound and, optionally, other polyether compounds and diluents such as dipropylene glycol. The polyether-modified silicone compound is usually produced by an addition reaction between an organohydrogensiloxane and a polyether compound having a double bond at the molecular chain terminal in the presence of a noble metal catalyst such as chloroplatinic acid.

  In the polyether-modified silicone compound thus obtained, for example, when an allyl etherified polyether is used as a polyether compound having a double bond at the molecular chain end, this is added with an organohydrogensiloxane under a noble metal catalyst. During the reaction, the allyl group undergoes internal rearrangement as a side reaction, resulting in a propenyl etherified polyether. Since this propenyl etherified polyether does not react with the organohydrogensiloxane, it remains as an impurity together with the polyether-modified silicone compound produced by the desired addition reaction, and unreacted allyl etherified polyether is also present as an impurity in the polyether-modified polyether. It remains with the silicone compound. Further, the unreacted allyl etherified polyether is gradually isomerized by the remaining platinum catalyst to become a propenyl etherified polyether. When water acts on the polyether-modified silicone compound containing the propenyl etherified polyether, it is considered that the propenyl ether site is cleaved to generate volatile propionaldehyde. This series of reactions is accelerated by the presence of acid, and the reaction rate increases as the pH decreases.

  Due to this series of reactions, cosmetics in which the polyether-modified silicone compound is used may generate an unpleasant odor over time. Therefore, in order to reduce such an odor from cosmetics, for example, the polyether-modified silicone compound is used by using water and an aqueous solution having a pH of 7 or less under a specific condition, so A method has been proposed in which propionaldehyde is generated by treatment until the degree of unsaturation derived from the bond-containing polyether is 0.002 or less, and then removed (Patent Document 1). This makes it difficult for the polyether-modified silicone compound to generate propionaldehyde over time. In addition, a method has been proposed in which residual double bond-containing polyether is alkylated by a hydrogenation reaction to reduce the generation of propionaldehyde (Patent Document 2). Furthermore, a method has been proposed in which both the above-described acid treatment and hydrogenation are used in combination to remarkably suppress the generation of volatile aldehydes (Patent Document 3).

  However, a method for reducing volatile organic compounds generated over time from a polyether-modified silicone compound contained in a foam stabilizer for polyurethane foam used in building materials, the automobile industry (for example, automobile interior materials), etc. It has not yet been proposed and is eagerly developed.

Japanese Patent No. 2137062 JP-A-7-330907 International Publication No. 02/055588 Pamphlet

  Accordingly, an object of the present invention is to provide a foam stabilizer for polyurethane foam that has a very small amount of harmful aldehydes that are generated with time even when blended with polyurethane foam.

The present invention firstly includes a polyurethane containing a polyether-modified silicone compound synthesized by addition reaction of at least an organohydrogenpolysiloxane and an allyl group-containing polyoxyalkylene compound in the presence of a platinum-based catalyst. A foam stabilizer,
The foam stabilizing agent, wherein the amount of aldehyde generated when the polyether-modified silicone compound is heat-aged in 0.23 normal hydrochloric acid at 50 ° C. for 0.5 hours is 100 ppm or less based on mass relative to the polyether-modified silicone compound. Agent.

  The present invention secondly provides a method for producing a polyurethane foam, which comprises foaming a mixture containing a polyol, an isocyanate compound, a foaming agent, a catalyst and the foam stabilizer for polyurethane foam.

  The foam stabilizer of the present invention is useful for the production of polyurethane foam as a foam stabilizer for polyurethane foam because the amount of harmful aldehydes generated over time is extremely small even when blended in polyurethane foam. . Since the generation of harmful aldehydes causing unpleasant odors is reduced, the foam stabilizer of the present invention is particularly useful for building materials, automobile industry (for example, automobile interior materials), furniture such as beds and sofas, It is preferably used for the production of polyurethane foam applied to bedding, clothing and the like.

  Hereinafter, the present invention will be described in more detail.

<Foam stabilizer for polyurethane foam>
-Polyether-modified silicone compound-
The foam stabilizer of the present invention contains a specific polyether-modified silicone compound. This polyether-modified silicone compound has an aldehyde generation amount of 100 ppm or less, particularly 20 ppm or less, particularly 10 ppm, based on the weight of the polyether-modified silicone compound, when heated and aged at 50 ° C. for 0.5 hours in 0.23 normal hydrochloric acid. It is as follows.

  Examples of the polyether-modified silicone compound include the following general formula (1):

（１）

(1)

[In general formula (1),
R ¹ may be the same or different and is a monovalent organic group having 1 to 30 carbon atoms;
R ² may be the same or different and is represented by the general formula (2):
_{-C 3 H 6 -O- (C 2} H 4 O) a (C 3 H 6 O) b R 4 (2)
(Wherein R ⁴ is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 30 carbon atoms, or an acyl group, a is an integer of 0 to 50, and b is an integer of 0 to 50. Yes, but a + b> 1.)
A monovalent group represented by:
R ³ may be the same or different and is a group represented by R ¹ or R ² ;
x is an integer of 1 to 500, preferably 5 to 100;
y is an integer of 0-50, preferably 2-20.
However, when y = 0, R ^{3 at} both ends is a group represented by R ² . ]
It is represented by

In the general formula (1), examples of the monovalent organic group represented by R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, and a nonyl group. A monovalent hydrocarbon group such as an alkyl group such as a decyl group, a cycloalkyl group such as a cyclopentyl group or a cyclohexyl group, an aryl group such as a phenyl group or a tolyl group, an aralkyl group such as a benzyl group or a phenethyl group; A monovalent hydrocarbon group obtained by substituting at least a part of the hydrogen atoms of the hydrogen group with a halogen atom, a cyano group, or the like, for example, a fluorine-substituted alkyl group such as a trifluoropropyl group or a heptadecafluorodecyl group.

In the general formula (2) representing the R ^2, 1 a monovalent hydrocarbon group of R ⁴ in the represented may unsubstituted or substituted having 1 to 30 carbon atoms is preferably of 1 to 10 carbon atoms, Specific examples include alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl and decyl; acyl such as formyl, acetyl and propionyl. A cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; an alkenyl group such as a vinyl group and an allyl group; an aryl group such as a phenyl group and a tolyl group; and an aralkyl group such as a benzyl group and a phenethyl group.

  The polyether-modified silicone compound is synthesized by addition reaction of at least an organohydrogenpolysiloxane and an allyl group-containing polyoxyalkylene compound in the presence of a platinum-based catalyst.

Organohydrogenpolysiloxane The organohydrogenpolysiloxane is not particularly limited, but is a diorganohydrogenpolysiloxane having a molecular chain non-terminal (that is, molecular chain side chain) and / or a hydrosilyl group at the molecular chain terminal, particularly Dimethyl hydrogen polysiloxane is preferred.

  The hydrosilyl group that the organohydrogenpolysiloxane has in one molecule is usually in such an amount that the hydrogen gas generation amount is 10 to 200 ml / g, preferably 10 to 150 ml / g. “Hydrogen gas generation amount” was determined by reacting a solution of a sample in n-butyl alcohol with a 10% by mass aqueous sodium hydroxide solution at room temperature, collecting the generated hydrogen gas in a burette, and measuring its volume. The amount of hydrogen gas generated per gram of organohydrogenpolysiloxane (ml).

  Examples of the organohydrogenpolysiloxane include those represented by the general formula (3) corresponding to the general formula (1).

（３）
〔式中、Ｒ^１、ｘおよびｙは一般式（１）について定義の通りであり、Ｘは同一または異なり、水素原子またはＲ^１で表される基を示す。但し、ｙ＝０の場合、両末端のＸは水素原子である。〕

(3)
[Wherein, R ¹ , x and y are as defined for general formula (1), and X is the same or different and represents a hydrogen atom or a group represented by R ¹ . However, when y = 0, Xs at both ends are hydrogen atoms. ]

  Organohydrogenpolysiloxanes may be used alone or in combination of two or more.

-Allyl group-containing polyoxyalkylene compound The allyl group-containing polyoxyalkylene compound is not particularly limited. For example, the following general formula (4):
_{CH 2 = CHCH 2 O (C} 2 H 4 O) a C 3 H 6 O) b R 4 (4)
(In the formula, R ⁴ , a and b are as defined in the general formula (1).)
Represented by

  The amount of the allyl group-containing polyoxyalkylene compound used is 0.9 to 2.0 moles, preferably 1.0 to 1 moles of allyl groups per mole of silicon-bonded hydrogen atoms (Si—H) of the organohydrogenpolysiloxane. .5 moles.

  An allyl group containing polyoxyalkylene compound may be used individually by 1 type, or may use 2 or more types together.

Platinum-based catalyst The platinum-based catalyst is used to promote an addition reaction between an organohydrogenpolysiloxane and an allyl group-containing polyoxyalkylene compound. The platinum-based catalyst is not particularly limited, and examples thereof include neutral platinum complexes such as chloroplatinic acid, alcohol-modified chloroplatinic acid, and platinum-alkenylsiloxane complexes.

  The amount of the platinum-based catalyst used may be an effective amount as a catalyst, but is usually 1 to 100 ppm, particularly 1 to 20 ppm in terms of platinum atom mass relative to the organohydrogenpolysiloxane. A platinum-type catalyst may be used individually by 1 type, or may use 2 or more types together.

Other components In addition, in order to further promote the addition reaction, carboxylic acid alkali metal salts such as potassium acetate and potassium propionate can be added. Furthermore, the addition reaction can be carried out in the presence of a solvent such as ethanol, isopropyl alcohol, or toluene.

Purification method An unpurified polyether-modified silicone compound (hereinafter referred to as “unpurified product”) can be obtained by mixing the above components and subjecting them to an addition reaction. This unpurified product is usually obtained in the form of a reaction solution. The purification method applied to this unpurified product is, for example,
(i) removing the remaining aldehydes by treating the unpurified product obtained after the addition reaction with a solution having a pH of 7 or less (purification method 1), or
(ii) alkylating the allyl group-containing ether compound contained in the unpurified product obtained after the addition reaction by a hydrogenation reaction (purification method 2);
Or by doing both of these. Since it is possible to purify with high purity, it is more preferable to perform both of these, and it is particularly preferable to perform both by performing the purification method 1 after performing the purification method 2.

  These purifications may be performed using the unpurified product (or reaction solution) obtained after the addition reaction as it is, or when the addition reaction is performed in the presence of a solvent, the solvent is previously removed by stripping. It may be done after that.

-Purification method 1-
The solution having a pH of 7 or less used in the purification method 1 is not particularly limited, and examples thereof include aqueous solutions of strong acids such as hydrochloric acid, sulfuric acid, and nitric acid; weak acids such as carbonic acid, acetic acid, and citric acid. Hereinafter, treatment with an aqueous solution of an acid which is a preferred embodiment will be described as an example.

  The acid concentration in the aqueous solution of the acid is preferably 0.001 to 0.5% by mass for a strong acid and 0.01 to 1% by mass for a weak acid. When the acid concentration is too high, the siloxane bond in the polyether-modified silicone compound is cleaved during the acid treatment, and the performance of the resulting polyether-modified silicone compound as a foam stabilizer may be reduced. If the acid concentration is too low, the remaining aldehydes may not be sufficiently removed.

  The amount of the aqueous solution of the acid added to the unpurified product (or reaction solution) is not particularly limited, but is usually about 1 to 50% by mass, preferably about 5 to 20% by mass based on the amount of the unpurified product.

  After adding an acid aqueous solution to generate aldehydes from an unpurified product (or reaction solution), as a post-treatment, the solution is neutralized with a basic compound (or an aqueous solution thereof), heated to a solvent, Aldehydes are distilled off with water. A purified product is thus obtained.

-Purification method 2-
The hydrogenation method used for the hydrogenation reaction of the purification method 2 includes (a) a method using hydrogen and (b) a method using metal hydride, and further includes a homogeneous reaction and a heterogeneous reaction. These can be performed alone or in combination. Considering the advantage that the used catalyst does not remain in the purified product, the heterogeneous catalytic hydrogenation reaction using a solid catalyst is most preferable.

  Examples of the solid catalyst include simple substances such as nickel, palladium, platinum, rhodium, cobalt, chromium, copper, and iron, or compounds thereof. If necessary, a catalyst carrier such as activated carbon, silica, silica alumina, alumina, or zeolite may be used. These catalysts may be used alone or in combination. Most preferred is Raney nickel, which is economically superior. Since Raney nickel is usually used after being developed in an alkali, it is particularly necessary to carefully measure the pH of the reaction solution. Further, since the inside of the reaction system becomes weakly alkaline, a hydrolysis reaction with an acidic aqueous solution is particularly effective for deodorization.

  The hydrogenation reaction is generally desirably performed at 1 to 100 MPa and 50 to 200 ° C. The hydrogenation reaction may be batch or continuous. For example, in the case of a batch system, the reaction time depends on the amount of catalyst, temperature, etc., but is generally 3 to 12 hours. The hydrogen pressure can be adjusted to a constant pressure as appropriate, but the end point of the hydrogenation reaction can be judged as a point where the hydrogen pressure has stopped changing by carefully observing the pressure gauge. After the hydrogenation reaction, the reaction solution is filtered and the solvent is distilled off. A purified product is thus obtained.

<Polyurethane foam>
The foam stabilizer is used for producing polyurethane foam. There are hard and soft polyurethane foams. Polyurethane foams can usually be produced by a process that includes mixing and foaming a polyol, an isocyanate compound, a blowing agent, a catalyst and a foam stabilizer, and optionally other components. Hereinafter, each component will be described.

-Polyol Examples of the polyol include polyether polyol and polyester polyol. Polyether polyol is obtained by adding alkylene oxide to polyhydric alcohol, saccharide, phenol, phenol derivative, aromatic amine, etc., for example, glycerin, propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol. , Trimethylolpropane, pentaerythritol, sucrose, sorbitol, novolak, nonylphenol, bisphenol A, bisphenol F, tolylenediamine, diphenylmethanediamine, and the like obtained by adding alkylene oxide to one or more of them. . Polyester polyols are polycondensation of polyfunctional carboxylic acids such as adipic acid, phthalic acid and succinic acid with polyfunctional hydroxyl compounds such as glycerin, propylene glycol, dipropylene glycol, ethylene glycol, diethylene glycol, trimethylolpropane and pentaerythritol. The polyol which has a hydroxyl group at the terminal manufactured by is mentioned. A polyol may be used individually by 1 type, or may use 2 or more types together.

-Isocyanate compound As the isocyanate compound, all known organic polyisocyanates can be used, but the most common ones are tolylene diisocyanate (hereinafter abbreviated as "TDI") and diphenylmethane diisocyanate (hereinafter referred to as "MDI"). Abbreviated.) TDI is a mixture of isomers, that is, 100% of 2,4-isomer, 2,4-isomer / 2,6-isomer = 80/20, 65/35 (respectively mass ratio), etc. Crude TDI containing polyfunctional tar known as TDI-TRC manufactured by Takeda Chemical Co., Ltd. can also be used. As MDI, in addition to pure products mainly composed of 4,4'-diphenylmethane diisocyanate, there are so-called polymeric MDIs such as MDI-CR manufactured by Mitsui Toatsu Chemical Co., Ltd., which contains polynuclear compounds of 3 or more nuclei. Can be used.

  Of these isocyanate compounds, MDI is usually used for producing rigid polyurethane foam, and TDI is usually used for producing flexible polyurethane foam.

-Foam stabilizer The foam stabilizer of this invention can be used as a suitable foam stabilizer with respect to both a rigid polyurethane foam and a flexible polyurethane foam. The compounding quantity is 0.5-3.0 mass parts normally with respect to 100 mass parts of polyols, Preferably it is 1.0-2.0 mass parts. A foam stabilizer may be used individually by 1 type, or may use 2 or more types together.

-Foaming agent As a foaming agent, hydrocarbons, such as cyclopentane, a methylene chloride, a carbon dioxide gas, water, etc. can be used, for example.

  Among these foaming agents, cyclopentane and water are preferable for the production of rigid polyurethane foam, and methylene chloride and carbon dioxide gas are preferable for the production of flexible polyurethane foam.

  The blending amount is appropriately determined according to the desired density of the polyurethane foam.

・ Catalyst Examples of the catalyst include triethylamine, tripropylamine, N-methylmorpholine, N-ethylmorpholine, triethylenediamine, tetramethylenediamine, tetramethylhexanediamine, N, N, N ', N'', N An amine catalyst such as ''-pentamethyldiethylenetriamine; a tin catalyst such as bis (2-ethylhexanoate) tin can be used.

  Among these catalysts, amine-based catalysts are preferable for the production of rigid polyurethane foams, and combined use of amine-based catalysts and tin-based catalysts is preferable for the production of flexible polyurethane foams.

Other components In addition to these components, a polyurethane foam may be prepared by adding a flame retardant, a plasticizer, a stabilizer, a colorant and the like as necessary.

-Manufacturing method In order to manufacture a rigid polyurethane foam, the above-mentioned polyol, foaming agent, catalyst and foam stabilizer, and optionally other components are mixed into a resin liquid, and this resin liquid and the isocyanate compound are in a certain ratio. What is necessary is just to make it foam by mixing by. For this mixing, a commonly used apparatus such as a low pressure foaming machine, a high pressure foaming machine, or a spray foaming machine may be used. The mixture of the respective components is molded by being injected into a suitable mold or sprayed by a commonly used apparatus according to a production method generally used for producing a rigid polyurethane foam. Specific methods for producing such rigid polyurethane foam include, specifically, slabstock foam production method, lamination board / panel continuous production method, multi-stage press / discontinuous injection foam production method, mold foam production method, spray Examples include foam manufacturing methods.

  In order to produce a flexible polyurethane foam, the above-mentioned polyol, foaming agent, catalyst, foam stabilizer and isocyanate compound, and in some cases other components, may be produced by a conventionally known production method such as a one-shot method or a prepolymer method. And may be foamed by mixing. In the prepolymer method, a polyol and an isocyanate compound are mixed in advance to obtain a kind of urethane prepolymer, which is then mixed with a foaming agent, a catalyst and a foam stabilizer and optionally other components, and if necessary, further polyol Are mixed and reacted (foamed). In the one-shot method, an isocyanate compound and a polyol are mixed and reacted (foamed) in the presence of a foaming agent, a catalyst and a foam stabilizer, and optionally other components.

  EXAMPLES Hereinafter, the present invention will be specifically described with reference to examples, but the present invention is not limited to these examples.

<Synthesis Example 1 (Comparative Example 1)>
-Normal foam stabilizer for rigid polyurethane foam-
In a glass reaction vessel, hydrogen gas generation amount is 56.0 ml / g, weight average molecular weight 2,900 molecular chain both ends trimethylsilyl group-blocked methyl hydrogen polysiloxane compound 750 g, average structural formula: CH ₂ = CHCH ₂ O 1,600 g of polyoxyalkylene allyl ether represented by (C ₂ H ₄ O) ₁₂ (C ₃ H ₆ O) ₃ H and 700 g of isopropyl alcohol are charged, and 1,3-divinyl-1,1,3,3-tetra A neutral platinum complex toluene solution (platinum content: 0.5 mass%) containing methyldisiloxane as a ligand was added, and an addition reaction was carried out at 80 ° C. for 5 hours. The reaction solution was distilled off under reduced pressure at 110 ° C. or lower and 400 Pa, and then filtered to obtain an average structural formula:

（式中、Ｍｅはメチル基を表す。以下、同じである。）
で表される、25℃における粘度が880mm²/sであり、比重が1.055のポリエーテル変性シリコーン化合物Ｃ１からなる硬質ポリウレタンフォーム用整泡剤2280gを得た。

(In the formula, Me represents a methyl group. The same shall apply hereinafter.)
Thus, 2280 g of a foam stabilizer for a rigid polyurethane foam comprising a polyether-modified silicone compound C1 having a viscosity at 25 ° C. of 880 mm ² / s and a specific gravity of 1.055 is obtained.

<Example 1>
-Removal of volatile organic compounds by acid treatment of foam stabilizer for rigid polyurethane foam-
A glass reaction vessel was charged with 100 g of the polyether-modified silicone compound C1 obtained in Synthesis Example 1, 10 g of a 0.005N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours. Distilled under reduced pressure at 110 ° C. or lower and 400 Pa, to obtain 95 g of a foam stabilizer for a rigid polyurethane foam comprising the polyether-modified silicone compound 1 having a viscosity at 25 ° C. of 880 mm ² / s and a specific gravity of 1.055.

<Example 2>
-Hydrogenation reaction of foam stabilizer for rigid polyurethane foam-
The autoclave was charged with 100 g of the polyether-modified silicone compound C1 obtained in Synthesis Example 1, 2.5 g of Raney nickel was added, hydrogen gas was introduced, and a hydrogenation reaction was performed at 100 ° C. for 3 hours. During the reaction, the hydrogen pressure was maintained at 1 MPa. Thereafter, the catalyst was recovered by filtration to obtain 85 g of a foam stabilizer for a rigid polyurethane foam comprising the polyether-modified silicone compound 2 having a viscosity at 25 ° C. of 865 mm ² / s and a specific gravity of 1.054.

<Example 3>
-Removal of volatile organic compounds by hydrogenation reaction and acid treatment of foam stabilizer for rigid polyurethane foam-
100 g of the polyether-modified silicone compound C1 obtained in Synthesis Example 1 was charged into an autoclave, 2.5 g of Raney nickel was added, hydrogen gas was introduced, and a hydrogenation reaction was performed at 100 ° C. for 3 hours. During the reaction, the hydrogen pressure was maintained at 1 MPa. Thereafter, the catalyst was recovered by filtration. The reaction product obtained after the hydrogenation reaction was again charged into a glass reaction vessel, 10 g of 0.005N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours. Then, the mixture was distilled off under reduced pressure at 400 Pa, to obtain 76 g of a foam stabilizer for a rigid polyurethane foam comprising the polyether-modified silicone compound 3 having a viscosity at 25 ° C. of 870 mm ² / s and a specific gravity of 1.054.

<Synthesis Example 2 (Comparative Example 2)>
-Normal foam stabilizer for flexible polyurethane foam-
In a glass reaction vessel, hydrogen gas generation amount is 28.5 ml / g, weight average molecular weight is 2,500 molecular chain both ends trimethylsilyl group-blocked methylhydrogenpolysiloxane compound, average structural formula: CH ₂ = CHCH ₂ O Charged 1,300 g of polyoxyalkylene allyl butyl ether represented by (C ₂ H ₄ O) ₂₂ (C ₃ H ₆ O) ₂₂ C ₄ H ₉ and 800 g of isopropyl alcohol, 1,3-divinyl-1,1,3, A neutral platinum complex toluene solution (platinum content: 0.5 mass%) containing 3-tetramethyldisiloxane as a ligand was added, and an addition reaction was performed at 80 ° C. for 5 hours. The reaction solution was distilled off under reduced pressure at 110 ° C. or lower and 400 Pa, and then filtered to obtain an average structural formula:

で表される、25℃における粘度が1810mm²/sであり、比重が1.030のポリエーテル変性シリコーン化合物Ｃ２からなる軟質ポリウレタンフォーム用整泡剤1560gを得た。

Thus, 1560 g of a foam stabilizer for a flexible polyurethane foam comprising a polyether-modified silicone compound C2 having a viscosity at 25 ° C. of 1810 mm ² / s and a specific gravity of 1.030 was obtained.

<Example 4>
-Removal of volatile organic compounds by acid treatment of foam stabilizers for flexible polyurethane foams-
A glass reaction vessel was charged with 100 g of the polyether-modified silicone compound C2 obtained in Synthesis Example 2, 10 g of 0.005N HCl aqueous solution was added, and the mixture was hydrolyzed at 60 ° C. for 3 hours. Under reduced pressure at 400 ° C. or lower and 95 Pa, a foam stabilizer 95 g for a flexible polyurethane foam comprising a polyether-modified silicone compound 4 having a viscosity at 25 ° C. of 1790 mm ² / s and a specific gravity of 1.030 was obtained.

<Example 5>
-Hydrogenation reaction of foam stabilizer for flexible polyurethane foam-
The autoclave was charged with 100 g of the polyether-modified silicone compound C2 obtained in Synthesis Example 2, 2.5 g of Raney nickel was added, hydrogen gas was introduced, and a hydrogenation reaction was performed at 100 ° C. for 3 hours. During the reaction, the hydrogen pressure was maintained at 1 MPa. Thereafter, the catalyst was recovered by filtration to obtain 85 g of a foam stabilizer for a flexible polyurethane foam comprising a polyether-modified silicone compound 5 having a viscosity at 25 ° C. of 1805 mm ² / s and a specific gravity of 1.030.

<Example 6>
-Removal of volatile organic compounds by hydrogenation reaction and acid treatment of foam stabilizers for flexible polyurethane foams-
The autoclave was charged with 100 g of the polyether-modified silicone compound C2 obtained in Synthesis Example 2, 2.5 g of Raney nickel was added, hydrogen gas was introduced, and a hydrogenation reaction was performed at 100 ° C. for 3 hours. During the reaction, the hydrogen pressure was maintained at 1 MPa. Thereafter, the catalyst was recovered by filtration. The reaction product obtained in this way after the hydrogenation reaction was again charged into a glass reaction vessel, 10 g of 0.005N HCl aqueous solution was added, and hydrolysis was performed at 60 ° C. for 3 hours. Under reduced pressure at 400 Pa, 71 g of a foam stabilizer for a flexible polyurethane foam comprising a polyether-modified silicone compound 6 having a viscosity at 25 ° C. of 1770 mm ² / s and a specific gravity of 1.029 was obtained.

<Measurement method>
The unsaturation degree and aldehyde content of the polyether-modified silicone compounds obtained in Synthesis Examples 1 and 2 (Comparative Examples 1 and 2) and Examples 1 to 6 were measured by the following methods. The obtained results are shown in Table 1.

-1. Measurement of unsaturation (meq / g)
Calculated from the ¹ H signal of unsaturated double bond hydrogen by ¹ H-NMR using heavy acetone as solvent. The allyl group used was 5.1 to 5.3 ppm d, d (2H), and the propenyl group used 6.1 to 6.3 ppm d (1H).

-2. Determination of aldehydes
1 g of a polyether-modified silicone compound was dissolved in 10 ml of special grade ethanol, and this was dissolved in a solution obtained by adding 90 ml of special grade ethanol to 50 mg of 2,4-DNPH (2,4-dinitrophenylhydrazine) to obtain a test solution. Next, purified water was added to 2 ml of concentrated hydrochloric acid (36%) to make 50 ml, and the reaction solution was used [the hydrochloric acid concentration of the reaction solution was 1.44% (0.47 N)]. 1.0 ml of the reaction solution is added to 1.0 ml of the test solution [at this time, the hydrochloric acid concentration of the reaction solution becomes 0.72% (0.23 N)], and after heating at 50 ° C. for 30 minutes, CH ₃ CN / H ₂ O (50/50) was used as an eluent, and HPLC analysis was performed using 365 nm ultraviolet rays.

<Production and evaluation of polyurethane foam>
-Production and evaluation of foam stabilizer for rigid polyurethane foam-
Using the rigid foam stabilizers obtained in Synthesis Example 1 (Comparative Example 1) and Examples 1 to 3, rigid polyurethane foams were produced at the blending ratios shown in Table 2, and the foaming test was performed. Specifically, a polyol (100 g), a foam stabilizer, a foaming agent, and a catalyst are put in a 200 cc polyethylene container, mixed, stirred for 10 seconds, MDI is added, and further stirred for 3 seconds. (200 mm × 200 mm × 200 mm) was added to obtain urethane foam. For stirring, a homodisper (2000 rpm) was used.
As a result, even when the foam stabilizer of Synthesis Example 1 (Comparative Example 1) was used, even when the foam stabilizers of Examples 1 to 3 were used, no difference in appearance was seen in the polyurethane foam, and all appearances were It was good.

（質量部）
＊アクトコールNT-630は、多官能ＰＰＧ（ＯＨ価４７０ＫＯＨｍｇ／ｇ）である。
＊コスモネートＭ−２００は、ポリメリックＭＤＩ（イソシアネート３１質量％含有）である。

(Parts by mass)
* Actocol NT-630 is a polyfunctional PPG (OH number 470 KOHmg / g).
* Cosmonate M-200 is polymeric MDI (containing 31% by mass of isocyanate).

-Production and evaluation of foam stabilizer for flexible polyurethane foam-
Using the soft foam stabilizers obtained in Synthesis Example 2 (Comparative Example 2) and Examples 4 to 6, flexible polyurethane foams were produced with the blending ratios shown in Table 3, and the foaming test was performed. Specifically, a polyol (592 g) and a foam stabilizer were mixed in a 1 L polyethylene container, and after stirring for 30 seconds, a tin catalyst was added and further stirred for 20 seconds. An amine catalyst and a foaming agent were added to this, and after stirring for 5 seconds, TDI was added. After further stirring for 7 seconds, the mixture was quickly charged into a container (350 mm × 350 mm × 350 mm) to obtain a urethane foam. For stirring, a homodisper (2000 rpm) was used.

  As a result, even when the foam stabilizer of Synthesis Example 2 (Comparative Example 2) was used or when the foam stabilizers of Examples 4 to 6 were used, there was no difference in the appearance of the polyurethane foam, and all the appearance was It was good.

（質量部）
＊MN-3050Kは、軟質スラブ発泡用（ＯＨ価５６ＫＯＨｍｇ／ｇ）である。
＊コスモネートT-80は、ＴＤＩ「２，４−体」と「２，６−体」の８０：２０の混合物である。

(Parts by mass)
* MN-3050K is for soft slab foaming (OH value 56KOHmg / g).
* Cosmonate T-80 is a 80:20 mixture of TDI “2,4-form” and “2,6-form”.

<Evaluation>
As can be seen from Table 1, the polyether-modified silicone compounds of Examples 1 to 6 not only produce a small amount of aldehydes that are volatile organic compounds, but also the amount of unsaturated compounds that cause the formation of aldehydes. is decreasing. And it does not adversely affect the production of polyurethane foam. Further, the appearance is of the same level as the conventional one. From the above points, it can be evaluated that it is very useful as a foam stabilizer for polyurethane foam.

Claims (4)

A foam stabilizer for polyurethane foam comprising a polyether-modified silicone compound synthesized by addition reaction of at least an organohydrogenpolysiloxane and an allyl group-containing polyoxyalkylene compound in the presence of a platinum-based catalyst. And
The foam stabilizing agent, wherein the amount of aldehyde generated when the polyether-modified silicone compound is heat-aged in 0.23 normal hydrochloric acid at 50 ° C. for 0.5 hours is 100 ppm or less based on mass relative to the polyether-modified silicone compound. Agent. The polyether-modified silicone compound is
(i) removing the remaining aldehydes by treating the polyether-modified silicone compound obtained after the addition reaction with a solution having a pH of 7 or less, or
(ii) alkylating the allyl group-containing ether compound contained in the polyether-modified silicone compound obtained after the addition reaction by a hydrogenation reaction;
Alternatively, the foam stabilizer according to claim 1, wherein the foam stabilizer is purified by performing both of them. The allyl group-containing polyoxyalkylene compound is represented by the following general formula (4):
_{CH 2 = CHCH 2 O (C} 2 H 4 O) a C 3 H 6 O) b R 4 (4)
[Wherein, R ⁴ is a hydrogen atom, an unsubstituted or substituted monovalent hydrocarbon group having 1 to 30 carbon atoms, or an acyl group, a is an integer of 0 to 50, and b is an integer of 0 to 50. Yes, but a + b> 1. )
The foam stabilizer according to claim 1 or 2 represented by:   The manufacturing method of a polyurethane foam including foaming the mixture containing a polyol, an isocyanate compound, a foaming agent, a catalyst, and the foam stabilizer for polyurethane foam as described in any one of Claims 1-3.