JPS5825320A - Foam stabilizer for polyurethane foam - Google Patents

Abstract

PURPOSE:To obtain a foam having a fine cell structure and a high open cell content, by employing a specified organosilicon compound as a foam stabilizer for cold-curing polyurethane foams. CONSTITUTION:Use is made of a foam stabilizer containing an organosilicon compound represented by formulaI, wherein R is 4C or lower alkyl, R<1> is a group of formula II (R<3> and R<4> are each 4C or lower alkyl, an alkaryl or phenyl), R<2> is R or R<1>, 0<=m<=30 and 0<=n<=30. Thus it becomes possible to obtain a polyurethane foam which is low in closed cell content, does not shrink without crushing, is excellent also in resilience and compression set and has a cell disturbance-free, loose skin-free, excellent appearance.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to an organosilicon foam stabilizer g for polyurethane foams, particularly for pooled cured polyurethane foams.

As for the production method of polyurethane foam, various methods are known and are commonly referred to as cold cure. It is also known that polyether polyols having 20% or more of primary hydroxyl groups can be obtained by reacting polyether polyols in the presence of isocyanates, water and/or organic blowing agents, catalysts and other auxiliaries. The pool-cured polyurethane foam used in the lever is highly reactive because its polyether volume contains a large amount of primary hydroxyl.
Since the crosslinking reaction progresses and cures at a relatively low temperature compared to general flexible polyurethane foam, and therefore hardly any heating is required, this is attracting attention from the perspective of energy saving. Because the foam exhibits excellent rebound resilience and high load-bearing performance, it is called a high-elastic foam, and it has come to be widely used as a material for shoes, automobiles, furniture, etc. ing.

On the other hand, in the production of this urethane foam, it has become common to perform fI7JD using a polysiloxypolyoxyalkylene co-bicarbonate as a foam stabilizer in order to make the cell structure uniform and open. In fact, if it is not added, the cell structure becomes rough and in some cases the foam itself collapses, but when manufacturing the cold cure type polyurethane foam mentioned above, this polyV lokitin When an alkylene copolymer is added, the closed cell ratio of the foam becomes high and the foam shows a remarkable shrinkage tendency, and the compression set becomes worse, which is disadvantageous.
Furthermore, mold foaming, in which raw materials are injected into a molding frame and foamed, has the disadvantage that the surface skin layer separates from the foam body due to the generation of voids, ie, so-called loose skin.

The present invention relates to a foam stabilizer for cold-cure polyurethane foams that can overcome these disadvantages, and has the following formula: where R is an alkyl group having 4 or less carbon atoms.

H R1 is R or R1 group, R", R' is an alkyl group having 4 or less carbon atoms, an alkanol group or a phenyl group, m and n are positive numbers shown by the following formula, respectively 01, m130. Ojn, (30) It is characterized by being made of an organosilicon compound represented by (30) as a main ingredient.

To explain this, 1. As a result of extensive research into the manufacturing method of gold cure type polyurethane foam, the present inventors found that
As this foam stabilizer, instead of the conventionally known polysiloxinacypolyoxyalkylene co-baking carbonate, a botanyl quinane, which does not contain a polyoxyalkylene group but does contain a tertiary amino group, is used as shown in the general formula: As a result, the above-mentioned problems are solved, and it is possible to produce a foam with a small closed cell ratio and a fine cell structure with a high communication rate, and the obtained foam does not shrink even without crushing. The present invention was completed by confirming that this tendency is noticeable even in a closed metal mold, and that the occurrence of loose skin is further suppressed in this case.

That is, the tertiary amino group-containing polysilokitiy as the main ingredient of the foam stabilizer for polyurethane foams according to the present invention is represented by the general formula Jingki, in which R is a methyl group, a propyl group, or a butyl group. R%R is a group that is separated from the following by adding a methanol group, an ethanol group, a propatool group, a butanol group, or a phenyl group.1. R is H and R1 is selected from R or R1.

In addition, m%n in this formula is a number of 30 or less, and these may be 0, but since the presence of a tertiary amino grave represented by R is an essential requirement for this n, R3 may be 0 only when R1. This tertiary amino acid-containing polyV lokitin can be processed by a conventionally known method, for example, by
It can be produced by subjecting polysilochitin having an s1a group to an addition reaction with Aturu jφ diele ether in the presence of a platinum-based catalyst, and then ring-opening and adding a secondary amine group to the epoxy ring.

In addition, when producing polyurethane foam using this foam stabilizer, this foam stabilizer may be replaced with a conventionally known polysiloxitin-polyoxyalkylene copolymer (: except that it is used in place of the conventionally known method). Specifically, polyether polyols containing hydroxyl radicals have at least two, but not less than 20% of, primary hydroxyl groups in one molecule, and polyisocyanates having a small number (both have two isocyanate groups) in one molecule. After homogeneously mixing the catalyst, water, the foam forming agent, and the foam stabilizer, natural ζ or forced ζ foaming can be carried out. According to this method, the desired urethane foam can be easily obtained. can.

In this case, 1. The invention 2. Related arrangements? ! The J agent includes various compounds that are present in conventional foam stabilizer compositions, such as aminated compounds such as bentamether dietherene triamine, tetramethel hequinamethylene cyano, tolylene diisocyanate, and diphenylmethane. There is no problem in adding and mixing inocyanate compounds such as diisocyanates, methane compounds such as monofluoromethane, monofluorotrichloromethane, etc., but the amount of addition of this foam stabilizer itself is 0.01 to the polyether polyol. The amount may range from 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 cool-cured polyurethane foams, whose main ingredient is polysilochitin containing tertiary amino groups. The industrial advantage is that it is possible to easily obtain polyurethane foam that has a high elasticity, excellent rebound properties, and compression set, and has a good appearance without cell roughness or loose skin. It will be done.

Next, reference examples and examples of the present invention will be given. In addition, M in steel is a methyl group, %Et is 4% propyl, Bu is a butyl group, Ph is a tool group, and parts are parts by weight. The polyether polyols A, B and isoνane)0 each have the following compositions.

Polyether polyol A: 75% of hydroxyl groups are primary hydroxyl groups, hydroxyl value is 3.
12 qKOH/,! Polyether polyol of /Polyether polyol B: Graft polymerized with 20% by weight of acrylonitrile, 75% of the hydroxyl straw is primary hydroxyl group, hydroxyl monovalence is 2
8.8m9KOH/Ii of polyether polyol isocyanate O: 80 parts of TDI-80 (2,6-)tolylenediisoνanate and 2,4-tolylenediisoνanate in an 80:20 ratio) , Crude M
DI (Crew V diphenylmethane diisocyanate) 2
Reference example of a mixture with 0 parts (manufacture of tertiary amino acid-containing polysilochitin) 1j equipped with a reflux condenser, thermometer, stirrer, dropping funnel
Yozuro flask (:, Allyl Gly V Dyl Ether 11
4Ii (1 mol), toluene 100p.

Isopropyl alcohol solution of chloroplatinic acid (pt concentrated 1
F0.2%) 0.5II was added and heated to 100°C, and then methyl octohydrodienebosiloxane 40010.93 mol) represented by the following formula was gradually added dropwise. reacted to. - After the reaction is complete, toluene and unreacted vorinurokinav are removed under reduced pressure and filtered to produce an intermediate product of the following formula: $468
．． I got a 9.

Next, ζ2, this intermediate product 272j (0.5 mol) and metheranili ν53.5JF (0.5 mol) were placed in a four-way flask similar to that used in Boki, and reacted for 5 hours at BO℃±lθ℃. Substantially all of the methylaniline was reacted, and the product was filtered under reduced pressure to give the product @318I shown in the following formula.

In the same manner as above, the methylhydrodiene polyvrokina y may be varied, and various secondary amines may be used in place of mesolaniline to prepare the above 1f.
i (=various types of #I tertiary A) group-containing polysilochitins were produced.

Table 1 (Note) Above R%R'', R'', R'', R',
II and n both mean the respective groups or numbers in the following general formula.

Example 1 70 parts of polyether polyol A, 30 parts of polyether polyol B, 3.0 parts of water, 0.4 part of tetramethyl hequinamethylene diamine, DABOO33L"t/
(Catalyst manufactured by Hendley Process Co., trade name) 0.3 parts,
After mixing and stirring the foam stabilizer obtained in the reference example to make it homogeneous, add this (= 039.5 parts of isocyanate) and stir for 5 seconds, then put it into an aluminum mold maintained at 40'CH, and ℃ 4: Heated for 10 minutes, then demolded the obtained foam material, flubbed it, and then heated it in a dryer at 70℃ for another 210 minutes. As a result, the result of the second fiζ: 1 was obtained.

2nd fi (Note) Dl: Dimethylpolysilochitin song (500B
JP = Polyether-modified silibone Example 2 80 parts of polyether polyol A, 20 parts of polyether polyol B, 3.0 parts of water, 2.0 parts of triethanolamine, Tetramethane Lzy971y
0.4 part, DABOO33LV (@ listed) 0.3 part and each of the foam stabilizers obtained in the reference examples were uniformly mixed and stirred, and 43.5 g of isoνane) 0 was added thereto and stirred for 5 seconds. This was placed in an aluminum moxibustion mold kept at 48°C and foamed, and treated as in the previous example. I
The results shown are obtained.

Part 3 s

Claims (1)

[Claims] 1. General formula [R1 is a group represented by, R2 is R or R1 group, R3 and R4 are an alkyl group having 4 or less carbon atoms, an alkanol group or a phenyl group, m and n are each A foam stabilizer for polyurethane foams, which is made of an organosiliconized metal compound represented by the following formula: 0≦m≦30, 0≦n≦30, which is a positive number expressed by the following formula: