JP2007321119A - Polyurethane foam and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyurethane foam, that can be produced by foaming a mixture prepared from a polyisocyanate component, a polyol component, a catalyst, a foam stabilizer and a foaming agent, and is excellent in view of cost and the environment when an amine compound is used as a catalyst, and to provide a method for producing the same. <P>SOLUTION: The a polyurethane foam is produced by foaming a mixture of a polyisocyanate component, a polyol component, a catalyst, and further, a foam controlling agent and a foaming agent, wherein the catalyst comprises at least one amine compound selected from the compounds represented by the general formula, where R<SP>1</SP>and R<SP>2</SP>are each a 1-6C alkyl group, and R<SP>3</SP>is a 10C alkyl group. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  TECHNICAL FIELD The present invention relates to a polyurethane foam used for various molded articles such as automobile parts and indoor products and a method for producing the same. In particular, the present invention relates to a polyurethane foam suitably used for a seat pad and a method for producing the same.

  Polyurethane foam is used in various applications such as automotive seats, cushioning materials such as bedding and furniture, heat insulating materials such as refrigerators, vending machines, showcases and container ships, and in the building field, heat insulating panels and cushioning materials for flooring. It is used.

  In its production, in addition to the main raw materials such as polyols and isocyanates, catalysts, foam stabilizers, foaming agents and other auxiliary agents (colorants, chain extenders, crosslinking agents, fillers, flame retardants, antioxidants) UV absorbers, light stabilizers, conductive substances, antibacterial agents, etc.) are used as necessary.

  Particularly recently, chlorofluorocarbons (CFCs, commonly called chlorofluorocarbons) that have been used as blowing agents are required to be reduced because they cause ozone layer destruction. In addition to the development of main raw materials, Improvements have been attempted. On the other hand, the method of reducing CFCs and increasing the amount of water was taken, but there were problems that the foam curing speed, foaming efficiency, moldability, adhesiveness, dimensional stability, thermal conductivity, etc. deteriorated remarkably. . Therefore, development of a catalyst suitable for a formulation with an increased amount of water and an alternative blowing agent has been desired.

  Conventionally, organometallic catalysts and amine catalysts have been used as catalysts for polyurethane production. Among them, it is well known that amine catalysts are excellent catalysts for polyurethane production. However, the amine catalyst has a strong amine odor and has problems such as leaving a bad odor in the polyurethane foam product itself.

  Under such circumstances, Japanese Patent Application Laid-Open No. 7-173242 (Patent Document 1) describes carbon having improved curing speed, moldability and generation of odor in a formulation in which CFCs are reduced as a blowing agent and the amount of water is increased. A method for producing a flexible polyurethane foam using an amine catalyst of several 11 to 14 has been proposed.

  However, when aiming to improve productivity, it is effective to increase the amount of the catalyst added in order to increase the curing rate, etc., but this not only causes further odors in the foaming process, but also causes deterioration of the working environment. It is also disadvantageous in terms of cost. Further, when the catalyst does not completely evaporate and remains in the product in the manufacturing process, a bad odor remains in the product itself, and further, it is scattered from the product to the outside during use. In particular, the fogging phenomenon of the window glass that occurs when a flexible polyurethane foam is used as an automobile interior material is a problem.

  Therefore, in the production of polyurethane foam, from the viewpoint of cost and environment, improvement in productivity and reduction in the amount of catalyst added are required, and development of a more advantageous polyurethane foam has been desired.

Japanese Patent Laid-Open No. 7-173242

  The present invention has been considered in view of the above circumstances, and in a polyurethane foam obtained by mixing and foaming a polyisocyanate component and a blended liquid obtained by mixing a polyol component, a catalyst, a foam stabilizer and a foaming agent, It is characterized by using a specific amine compound, and an object is to provide a polyurethane foam excellent in cost and environment, particularly a polyurethane foam that can be suitably used as a seat pad, and a method for producing the same.

（式中、Ｒ¹、Ｒ²は炭素数１〜６のアルキル基、Ｒ³は炭素数１０のアルキル基を表す。）
で表されるアミン化合物が、ポリウレタンフォームの製造において、触媒として従来使用されていたアミン化合物よりも高い活性を示すことから、生産性を著しく向上させられること、及び生産性を維持しながら触媒の添加量を削減することが可能であることを見出し、本発明をなすに至った。 As a result of intensive studies to solve the above problems, the present inventor has found that the following general formula

(In the formula, R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 10 carbon atoms.)
In the production of polyurethane foam, the amine compound represented by the formula shows higher activity than the amine compound conventionally used as a catalyst, so that productivity can be remarkably improved and the productivity of the catalyst can be maintained while maintaining productivity. The present inventors have found that it is possible to reduce the addition amount, and have reached the present invention.

（式中、Ｒ¹、Ｒ²は炭素数１〜６のアルキル基、Ｒ³は炭素数１０のアルキル基を表す。）
で表されるアミン化合物より選ばれる１種以上を用いることを特徴とするポリウレタンフォーム。
〔２〕 前記アミン化合物がＮ，Ｎ−ジメチルデシルアミンであることを特徴とする〔１〕記載のポリウレタンフォーム。
〔３〕 前記発泡剤が水であることを特徴とする〔１〕又は〔２〕記載のポリウレタンフォーム。
〔４〕 シートパッド用として用いることを特徴とする〔１〕，〔２〕又は〔３〕記載のポリウレタンフォーム。
〔５〕 ポリイソシアネート成分と、ポリオール成分、触媒、整泡剤及び発泡剤を含む配合液とを混合し、発泡させて得られるポリウレタンフォームの製造方法において、触媒として下記一般式

（式中、Ｒ¹、Ｒ²は炭素数１〜６のアルキル基、Ｒ³は炭素数１０のアルキル基を表す。）
で表されるアミン化合物より選ばれる１種以上を用いることを特徴とするポリウレタンフォームの製造方法。 That is, this invention provides the following polyurethane foam and its manufacturing method.
[1] A polyurethane foam obtained by mixing and foaming a polyisocyanate component and a blending solution containing a polyol component, a catalyst, a foam stabilizer and a foaming agent.

(In the formula, R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 10 carbon atoms.)
A polyurethane foam characterized by using one or more selected from amine compounds represented by the formula:
[2] The polyurethane foam according to [1], wherein the amine compound is N, N-dimethyldecylamine.
[3] The polyurethane foam according to [1] or [2], wherein the foaming agent is water.
[4] The polyurethane foam according to [1], [2] or [3], which is used for a seat pad.
[5] In a method for producing a polyurethane foam obtained by mixing and foaming a polyisocyanate component and a blending solution containing a polyol component, a catalyst, a foam stabilizer and a foaming agent, the following general formula is used as a catalyst.

(In the formula, R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 10 carbon atoms.)
1 or more types chosen from the amine compounds represented by these are used, The manufacturing method of the polyurethane foam characterized by the above-mentioned.

  According to the present invention, in the production of polyurethane foam, the use of a specific amine compound with higher activity as a catalyst can significantly improve productivity, and the amount of catalyst added while maintaining productivity. Therefore, it is possible to provide a polyurethane foam more advantageous in terms of cost and environment and a method for producing the same.

Hereinafter, the present invention will be described in more detail.
First, the polyurethane foam of the present invention is mainly composed of isocyanate and polyol as in the case of ordinary polyurethane foam.

  The urethane foam stock solution used in the present invention includes (A) a polyisocyanate that supplies an isocyanate group, and (B) a polyol that supplies a hydroxyl group, and (B) the viscosity of the polyol that supplies the hydroxyl group. However, it is preferably 3,000 mPa · s or less at a liquid temperature of 25 ° C. In the present invention, “viscosity” means the viscosity measured using a capillary viscometer at a liquid temperature of 25 ° C. in accordance with JIS Z 8803-1991.

(A) Polyisocyanate (A) A known polyisocyanate can be used. For example, tolylene diisocyanate (TDI), diphenylmethane diisocyanate (MDI), triphenyl diisocyanate, xylene diisocyanate, polymethylene polyphenylene polyisocyanate, Examples include hexamethylene diisocyanate and isophorone diisocyanate. In the present invention, it is preferable to contain tolylene diisocyanate (TDI) and / or diphenylmethane diisocyanate (MDI) from the viewpoint of the molding density region.
Here, the TDI is not particularly limited, but is a mixture having a blending ratio (mass ratio) of 2,4-TDI and 2,6-TDI of 80/20 to 50/50. A mixture of 80/20 to 65/35 is particularly preferable.

  On the other hand, the MDI is not particularly limited and can be used regardless of whether the molecular weight distribution is wide or narrow. For example, pure MDI (4,4-MDI), polymeric MDI, and crude MDI. Etc. are suitable.

As such TDI and MDI, commercially available products can be used. As TDI, for example, TDI-80 (manufactured by Sumika Bayer Urethane Co., Ltd.), and as MDI, 44V20 (manufactured by Sumika Bayer Urethane Co., Ltd.). , Crude MDI) and the like can be suitably used.
When the TDI and MDI are used in combination, the blending ratio (mass ratio) of the two is usually 20/80 to 80/20, preferably 50/50 to 80/20 as the value of TDI / MDI.

  The proportion of the polyisocyanate supplying the isocyanate group (A) (when two or more isocyanates are used in combination, the total amount thereof) in the polyurethane foam stock solution is not particularly limited. Isocyanate equivalent as a standard (equivalent (molar) ratio of isocyanate group when the amount of active hydrogen (mole) in the polyurethane foam stock solution is 100) is usually 60 or more, preferably 70 or more, and the upper limit is usually 120 or less. , Preferably 115 or less. When the isocyanate equivalent is less than 60, poor stirring may occur, and when it exceeds 120, foam-down may occur.

  (A) It is recommended that the compounding quantity of a component is 20-100 mass parts normally with respect to 100 mass parts of the following (B) polyol component.

(B) Polyol As the polyol for supplying the hydroxyl group (B) in the present invention, polyether polyol or a mixture of polyether polyol and polymer polyol is preferably used.

  As the polyether polyol, a polyether polyol obtained by ring-opening polymerization of alkylene oxide is preferable from the viewpoint of reactivity. Examples of such alkylene oxides include propylene oxide (PO) and ethylene oxide (EO). These may be used alone or in combination of two or more.

  Among these, as the polyether polyol, a polyether polyol obtained by using the PO and EO in combination is preferably used from the viewpoint of raw material activity. The compounding ratio (molar ratio) of PO and EO is not particularly limited, but is usually 8/92 to 25/75, preferably 13/87 to 20/80 as EO / PO (molar ratio). is there. When EO / PO (molar ratio) is out of the above range, it may be difficult to produce a polyether polyol.

  The number of hydroxyl groups contained in one molecule of the polyether polyol preferably used in the present invention is usually 2 to 4, particularly preferably 3. If the number of hydroxyl groups is too large, the raw material viscosity may increase, and if it is too small, the physical properties may decrease.

  The number average molecular weight of the polyether polyol is usually less than 8,000, preferably 6,000 or less, and the lower limit is usually 3,000 or more, preferably 4,000 or more. When the number average molecular weight of the polyether polyol is 8,000 or more, the viscosity of the component (B) becomes too large, and the stirring efficiency of the polyurethane foam stock solution may be inferior. On the other hand, if the number average molecular weight of the polyether polyol is less than 3,000, the resilience may be greatly reduced. In the present invention, the number average molecular weight is a value calculated as a polystyrene equivalent value by gel permeation chromatography (GPC method).

  On the other hand, as the component (B) in the present invention, as a polymer polyol used in combination with the polyether polyol as necessary, a general-purpose polymer polyol can be used for a polyurethane foam molded article. More specifically, for example, a polyether polyol composed of polyalkylene oxide and preferably having an average molecular weight of 3,000 or more and 8,000 or less, more preferably 4,000 or more and 7,000 or less is combined with polyacrylonitrile or acrylonitrile-styrene. Examples include polymer polyols obtained by graft copolymerization of polymer components such as polymers. The alkylene oxide used as the raw material for the polyalkylene oxide preferably includes propylene oxide, and particularly preferably includes propylene oxide alone or includes both propylene oxide and ethylene oxide. Moreover, as a ratio of the above polymer components in the said polymer polyol, it is 25-50 mass% normally.

  When a polyether polyol or a mixture of a polyether polyol and a polymer polyol is used as the component (B) in the present invention, the blending ratio of both is usually 30/70 as a polyether polyol / polymer polyol (mass ratio). -100/0, preferably 40 / 60-80 / 20. When the blending ratio of both deviates from the above range, the physical properties may be deteriorated or a reaction failure may occur.

  In the present invention, the polyol (B) for supplying a hydroxyl group has a viscosity (viscosity of the whole mixed polyol in the case of using a mixture of plural kinds of polyols as the component (B)) at a liquid temperature of 25 ° C. The viscosity range is preferably 3,000 mPa · s or less, particularly 1,800 mPa · s or less. By using a polymer polyol in such a viscosity range, it is possible to suppress the viscosity increase rate of the polyurethane foam stock solution, increase the stirring efficiency, and allow the isocyanate groups and hydroxyl groups to react more uniformly. Therefore, not only the generation efficiency of the generated gas is increased compared to the conventional case, but also the generated gas is generated uniformly in the polyurethane foam stock solution, and a lightweight and homogeneous polyurethane foam molded product is obtained. Can be obtained.

（式中、Ｒ¹、Ｒ²は炭素数１〜６のアルキル基、Ｒ³は炭素数１０のアルキル基を表す。）
で表される。本発明においては、上記の構造を満たしていれば特に限定されないが、Ｎ，Ｎ−ジメチルデシルアミンを好適に用いることができる。 (C) Catalyst (C) The amine catalyst of the present invention has the following general formula:

(In the formula, R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 10 carbon atoms.)
It is represented by In the present invention, there is no particular limitation as long as the above structure is satisfied, but N, N-dimethyldecylamine can be suitably used.

  Further, the amine catalyst of the present invention may be used by mixing with any other amine-based or tin-based catalyst. As the other catalyst used in combination with the catalyst of the present invention, a normal catalyst used for the production of polyurethane foam can be used, and one or two or more kinds can be used in combination according to the use and demand. . Specifically, as the amine catalyst, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, dimethylcyclohexylamine, bis- (dimethylaminoethyl) ether, tetramethylpropylenediamine, trimethylaminoethylpiperazine, tetramethylethylenediamine, dimethylbenzyl Examples of tin-based catalysts such as amine, methylmorpholine, ethylmorpholine, triethylenediamine, and diethanolamine include stannous octate and dibutyltin dilaurate. In the present invention, triethylenediamine and diethanolamine can be suitably used.

  The compounding amount of the catalyst (the total amount when two or more types are used in combination) is usually 0.1 to 5.0 parts by mass, preferably 0.5 to 4.0, with respect to 100 parts by mass of the total polyol. Part by mass, particularly preferably 1.0 to 3.0 parts by mass. Moreover, when using together the amine catalyst of this invention, and another catalyst, the ratio of the amine catalyst of this invention is 1-100 mass% of the whole catalyst addition amount, Preferably it is 20-80 mass%, More preferably 30 to 60% by mass.

(D) Foam stabilizer (D) Examples of the foam stabilizer include organopolysiloxanes, alkyl carboxylates, and alkylbenzene sulfonates. Particularly preferred are organopolysiloxanes. The blending amount is preferably 0.5 to 5 parts by mass, particularly 0.5 to 2 parts by mass with respect to 100 parts by mass of the total polyol.

(E) Foaming agent (E) The foaming agent can use water suitably in this invention. A compounding quantity is 0.1-8.0 mass parts normally, Preferably it is 1.0-6.0 mass parts, More preferably, it is 2.0-5.0 mass parts.

  Furthermore, various additives can be added to the polyurethane foam formulation of the present invention as necessary, for example, colorants such as pigments, chain extenders, crosslinking agents, fillers such as calcium carbonate, A flame retardant, an antioxidant, an ultraviolet absorber, a light stabilizer, a conductive material such as carbon black, an antibacterial agent, and the like can be blended. In this case, the blending amount may be in the range normally used.

  Since the polyurethane foam of the present invention can improve productivity and reduce the amount of catalyst added, it is superior in cost and environment compared to the conventional one, and can be suitably used as a seat pad. is there.

  EXAMPLES Hereinafter, although an Example and a comparative example are given and this invention is demonstrated in detail, this invention is not restrict | limited to the following Example. In addition, in the following example, a part and% show a mass part and mass%.

[Examples 1 and 2 and Comparative Example 1]
Each of the isocyanate and polyol mixtures having the composition shown in Table 1 was previously stirred and mixed, and then both components were mixed to prepare a polyurethane foam stock solution. At this time, the temperature of the polyurethane foam stock solution is usually 10 to 40 ° C, preferably 15 to 35 ° C, and more preferably 20 to 30 ° C. Next, immediately after preparation of the stock solution, it was injected into a cavity of a mold capable of reducing the pressure in the cavity under atmospheric pressure, and pressure reduction was started immediately after the injection was completed. Then, it was made to foam and harden | cure in a metal mold | die, was demolded, and it was set as the product of this invention. The mold temperature is usually 30 to 80 ° C, preferably 50 to 75 ° C, more preferably 60 to 70 ° C.

"Evaluation methods"
The product of the present invention was measured for OA density based on JIS K 7222, 25% hardness based on JIS K 6400-2, and fogging value based on ISO 6452. The rise time and gel time were measured by the following methods. The results are shown in Table 1.
-Rise time 250 g of a polyol / isocyanate mixed solution was put into a cylindrical bucket having a diameter of 20 cm and a depth of 25 cm, and the time until the growing foam passed 20 cm from the bottom was measured.
Gel time In the same manner as the rise time measurement, when a polyol / isocyanate mixed solution was put in a bucket, pachinko balls were put into the growing foam from a height of 5 cm from the liquid level. At that time, the time until the hardening of the foam progressed and the pachinko ball became hard enough to not reach the bottom surface of the bucket was measured.

１）ＴＤＩ：ＴＤＩ−８０（住化バイエルウレタン（株）製）
２）ＭＤＩ：４４Ｖ２０（住化バイエルウレタン（株）製、クルードＭＤＩ）
３）ポリエーテルポリオール：平均分子量５，０００、官能基数３、ＥＯ１５モル％，ＰＯ８５モル％、粘度９００ｍＰａ・ｓ（液温２５℃）（三洋化成（株）製）
４）ポリマーポリオール：ベース平均分子量５，０００、官能基数３、固形分３３％、ＡＮ／ＳＴ＝１５／８５（モル比）（三洋化成（株）製）
５）触媒Ａ：トリエチレンジアミン（花王（株）製）
６）触媒Ｂ：ジエタノールアミン（（株）日本触媒製）
７）触媒Ｃ：Ｎ，Ｎ−ジメチルドデシルアミン
８）触媒Ｄ：Ｎ，Ｎ−ジメチルデシルアミン
９）整泡剤：Ｌ５３０９（東レ・ダウコーニング（株）製）
１０）発泡剤：水

1) TDI: TDI-80 (manufactured by Sumika Bayer Urethane Co., Ltd.)
2) MDI: 44V20 (manufactured by Sumika Bayer Urethane Co., Ltd., Crude MDI)
3) Polyether polyol: average molecular weight 5,000, functional group number 3, EO 15 mol%, PO 85 mol%, viscosity 900 mPa · s (liquid temperature 25 ° C.) (manufactured by Sanyo Chemical Co., Ltd.)
4) Polymer polyol: base average molecular weight 5,000, functional group number 3, solid content 33%, AN / ST = 15/85 (molar ratio) (manufactured by Sanyo Chemical Co., Ltd.)
5) Catalyst A: Triethylenediamine (manufactured by Kao Corporation)
6) Catalyst B: Diethanolamine (manufactured by Nippon Shokubai Co., Ltd.)
7) Catalyst C: N, N-dimethyldodecylamine 8) Catalyst D: N, N-dimethyldecylamine 9) Foam stabilizer: L5309 (manufactured by Dow Corning Toray)
10) Foaming agent: water

  From the results in Table 1, it can be confirmed that the polyurethane foam using the catalyst of the present invention is excellent in rise time and gel time. Therefore, according to the present invention, it is possible to remarkably improve the productivity in the production of polyurethane foam, and it is possible to reduce the amount of the catalyst added while maintaining the productivity, which is more advantageous in terms of cost and environment. It became possible to provide forms.

Claims (5)

A polyurethane foam obtained by mixing and foaming a polyisocyanate component and a blending solution containing a polyol component, a catalyst, a foam stabilizer and a foaming agent.

(In the formula, R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 10 carbon atoms.)
A polyurethane foam characterized by using one or more selected from amine compounds represented by the formula:   The polyurethane foam according to claim 1, wherein the amine compound is N, N-dimethyldecylamine.   The polyurethane foam according to claim 1 or 2, wherein the foaming agent is water.   The polyurethane foam according to claim 1, 2 or 3, wherein the polyurethane foam is used for a seat pad. In the process for producing a polyurethane foam obtained by mixing and foaming a polyisocyanate component and a blending solution containing a polyol component, a catalyst, a foam stabilizer and a foaming agent, the following general formula is used as a catalyst.

(In the formula, R ¹ and R ² represent an alkyl group having 1 to 6 carbon atoms, and R ³ represents an alkyl group having 10 carbon atoms.)
1 or more types chosen from the amine compounds represented by these are used, The manufacturing method of the polyurethane foam characterized by the above-mentioned.