JPS6033130B2 - Foam stabilizer for polyurethane foam - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organic poppy or elementary compound foam stabilizer for polyurethane foams, particularly for cold cure type polyurethane foams.

Various methods for producing polyurethane foam are already known, and the polyurethane foam, which is usually called a cold cure type, has at least two active hydrogen atoms, and more than 20% of its hydroxyl groups are primary hydrogen atoms. Polyable polyol, which is a water base, is converted into isocyanate,
It is also known that it can be obtained by reaction in the presence of water and/or an organic blowing agent, catalyst or other auxiliary agent.

This cold cure type polyurethane foam is highly reactive because its polyether polyol contains a large amount of primary hydroxyl groups.
The cross-linking reaction progresses and cures at a relatively low temperature compared to general flexible polyurethane foams, so even with almost no heating, this foam is attracting attention from an energy-saving perspective. It is called a high-elastic foam because it exhibits excellent anti-twill elasticity and high load-bearing performance, and is widely used as a cushioning material in automobiles, furniture, etc. On the other hand, when producing this urethane foam, it is common to add polysiloxane-polyoxyalkylene copolymer as a foam stabilizer in order to make the cell structure uniform and smooth. If this polysiloxane-polyoxyalkylene copolymer is not added, the cell structure will become coarse and in some cases the foam itself will collapse, but if this polysiloxane-polyoxyalkylene copolymer is added during the production of the cold cure type polyurethane foam described above, The closed cell ratio of the foam increases, causing it to show a marked shrinkage tendency, resulting in poor compression set.Furthermore, in mold foaming, in which raw materials are injected during molding and foamed, the surface skin layer becomes voided. There is a drawback that a so-called loose skin occurs, which separates from the foam body due to generation or the like.

The present invention relates to a foam stabilizer for cold-cure polyurethane foams that can solve these disadvantages, and has the following general formula: where R is an alkyl group having 4 or less carbon atoms;
Alternatively, the RI group, R3, and R4 represent an alkyl group, an alkanol group, or a phenyl group having 4 or less carbon atoms, and m and n each represent a positive number represented by the following formula.

It is characterized by containing an organic poppy compound represented by the following formulas as the main ingredient:

To explain this, the present inventors conducted various studies on the manufacturing method of cold cure type polyurethane foam, and found that
When a polysiloxane represented by the above general formula which does not contain a polyoxyalkylene group but contains a tertiary amino group is used as the foam stabilizer in place of the conventionally known polysiloxane-polyoxyalkylene copolymer, This problem has been solved, and the closed cell ratio is not high, so it is possible to produce a foam with a fine cell structure and a high resiliency rate, and the obtained foam does not shrink even without crushing, and this tendency has been reduced. The present invention was completed by confirming that the occurrence of loose skin, which is noticeable even in a closed metal mold, is further suppressed in this case.

That is, the tertiary amino group-containing polysiloxane as the main ingredient of the foaming agent for polyurethane foam according to the present invention is represented by the above general formula, and R in this formula is a methyl group, a propyl group, or a butyl group, R3 and R4 are groups selected from those to which a methanol group, an ethanol group, a propanol group, a butanol group, or a phenyl group is added, and this RI is represented by, and R2 is selected from this RI. be.

Note that m and n in this formula are each a number of 30 or less, and may be 0, but for this n, RI
Since the presence of a tertiary amino group represented by is an essential condition, it may be 0 only when R2 is R. This third
A polysiloxane containing amino groups can be synthesized by a conventionally known method, for example, by adding allyl glycidyl ether to a polysiloxane having SiH groups capped at both ends in the presence of a platinum catalyst. It can then be produced by ring-opening addition of a secondary amine group to the epoxy ring.

In addition, when producing polyurethane foam using this foam stabilizer, conventionally known methods may be used, except that this foam stabilizer is used in place of the conventionally known polysiloxane-polyoxyalkylene copolymer. , Specifically, a hydroxyl group-containing polyether polyol having at least two, but not less than 20% of, primary hydroxyl groups in one molecule, a polyisocyanate having at least two isocyanate groups in one molecule, a catalyst, After uniformly mixing water, a foam forming agent, and the foam stabilizer, foaming may be carried out naturally or forcibly, and by this method, the desired urethane foam can be easily obtained.

In this case, the foam stabilizer according to the present invention may include various compounds that are blended in conventional foam stabilizer compositions, such as amine compounds such as pentamethyldiethylenetriamine and tetramethylhexamethylenediamine, tolylene diisocyanate, and difluoride. There is no problem in adding and mixing isocyanate compounds such as enylmethane diisocyanate, methane compounds such as monofluoromethane, monofluorotrichloromethane, etc., but the amount of the foam stabilizer itself to be added is limited to the polyether polyol. The amount may range from 0.01 to 2 parts by weight, preferably from 0.03 to 1 part by weight. In summary, the present invention relates to a foam stabilizer for polyurethane foams, particularly cold cure type polyurethane foams, whose main ingredient is polysiloxane containing tertiary amino groups. The industrial advantage is that it is possible to easily obtain polyurethane foam that has a high elasticity, excellent rebound resilience and compression set, and has a good appearance without cell roughness or loose skin. It will be given to you.

Next, reference examples and examples of the present invention will be given.

In the examples, Me is a methyl group, Et is an ethyl group, and P
r is a propyl group, Bu is a butyl group, Ph is a phenyl group, and parts indicate parts by weight, and the polyether polyols A, B and isocyanate C used in the examples each have the following compositions. be. Polyether polyol A: 75% of hydroxyl groups are primary hydroxyl groups, hydroxyl value is 3.
12 of 9KOH/Polyether Polyol B: Graft polymerized with 2% by weight of acrylonitrile, 75% of hydroxyl groups are primary hydroxyl groups, hydroxyl value is 28.
8 of 9 KOH/Yu no Polyether Polyol Isocyanate C: Tolylene diisocyanate TDI-80 (80:2 Madarao mixture of 2,6-tolylene diisocyanate and 2,4-tolylene diisocyanate) with 8 Togeto , Crude MD
1 (Crude diphenylmethane diisocyanate) 2 Reference example of mixture with anchor part (Production of tertiary amino group-containing polysiloxane) Reflux condenser, thermometer, pestle, dropping.

In a four-piece flask equipped with a gasket, allyl glycidyl ether 114 (1 mol), toluene 100, and an inpropyl alcohol solution of chloroplatinic acid (Pt concentration 0.
2%) 0.5 liters was added and heated to 100°C, and the methylhydrogenpolysiloxane 40 represented by the following formula was added.
09 (0.93 mol) was gradually added dropwise, and the reaction was allowed to proceed for 4 hours after the completion of the dropwise addition under toluene reflux. After the reaction was completed, toluene and the polysiloxane resulting from the reaction were removed under reduced pressure and filtered through a furnace to obtain an intermediate product 468 represented by the following formula.

Next, 272 moles (0.5 moles) of this intermediate product and 53.5 moles (0.5 moles) of methylaniline were placed in the same Yotsuro flask as above and reacted at 800C ± 1000 for 5 hours. Almost all of the methyl amines reacted,
The product was stripped under reduced pressure and filtered through an oven.
A product 318 having the following formula was obtained.

In addition, in the same manner as above, by changing the type of methyl hydrogen polysiloxane and using various secondary amines in place of methylaniline, various tertiary amino group-containing polys as shown in Table 1 below were prepared. Siloxane was produced.

Table 1 (Note) The above R, R1, R2, R3, R4, m, and n all mean the respective groups or numbers in the following general formula.

Example 1 Polyether polyol A7 anchor part, polyether polyol B3 base part, water 3 part, tetramethylhexamethylene diamine 0.4 part, DABC03 Maru V (catalyst manufactured by Handley Process Co., Ltd., trade name) 0 After mixing 3 parts of the foam stabilizer obtained in the reference example to make it homogeneous, 39.5 parts of isocyanate C was added thereto, and the mixture was heated for 5 seconds, and then placed in an aluminum mold held at 40 mm. , heated to 70°C for 10 minutes, then demolded the obtained foam material, flashed it, and then heated it in a dryer at 70 qo for another 10 minutes.The appearance was observed and the physical properties were tested. The results shown in Table 2 were obtained.

Table 2 (Note) D: Dimethyl poly.

Xane oil (5 ratio S) P: polyether modified silicone Example 2 Polyether polyol A8 part, part of polyether polyol B2, water 3. 2.
parts, 0.4 parts of tetramethylhexamethylene diamine,
0.3 part of DABC03 Maru V (mentioned above) and various foam stabilizers obtained in the reference examples were mixed uniformly, and to this was added isocyanate C43.5 ml, stirred for 5 seconds, and maintained at 48 oz. When the product was placed in an aluminum metal mold and foamed, and treated in the same manner as in the previous example, the results shown in Table 3 were obtained.

Table 3

Claims (1)

[Claims] 1 General formula ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [R is an alkyl group having 4 or less carbon atoms, R^1 is ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ A group represented by R ^2 is R or R^1 group, R^3, R
^4 represents an alkyl group, alkanol group, or phenyl group having 4 or less carbon atoms, and m and n each represent a positive number represented by the following formula; 0≦m≦30, 0≦n≦30] A foam stabilizer for polyurethane foam that uses a basic compound as the main ingredient.