JPH0485316A - Production of flexible polyurethane foam - Google Patents

Abstract

PURPOSE:To produce the title foam of improved flexibility without using any halohydrocarbon by reacting a polyol with an organic polyisocyanate in the presence of a specified compound, a catalyst, a foam stabilizer and a blowing agent. CONSTITUTION:A mixture of 100 pts.wt. polyol of a hydroxyl value of 20-150 mgKoH/g (e.g. ethylene glycol) with 0.5-5 pts.wt. at least one compound selected from among compounds of formulas I-III (wherein R1 to R9 are each H or 1-5C alkyl; R10 is 2-5 C alkylene) is reacted with an organic polyisocyanate (e.g. 2,4-tolylene diisocyanate) in an amount to give an equivalent ratio of the isocyanate groups to the active hydrogen atoms of 0.7-1.4:1.0 in the presence of a catalyst (e.g. triethylamine), a foam stabilizer and a blowing agent.

Description

[Detailed description of the invention]

(Industrial Field of Application) The present invention relates to the production of flexible polyurethane foam. More specifically, the present invention relates to a method for producing flexible polyurethane foam that does not require a halogenated hydrocarbon as a blowing agent. (Prior Art) Conventionally, water and halogenated hydrocarbons have been mainly used as blowing agents in the production of urethane foam. In this case, water alone cannot soften the polymer because it reacts and increases the number of hard segments in the polymer, so halogenated hydrocarbons, which do not participate in the reaction, are used in combination to reduce density and hardness. Ta. However, halogenated hydrocarbons are widely regarded as substances that destroy the ozone layer, and their release has become a major problem in terms of environmental conservation. In order to manufacture it, following the conventionally known concept, A. Lower the NGO index, B. Lower the density by increasing the amount of water.
This is a possible method. However, in the case of A, the effect is small because the density increases,
In addition, the curing of the foam surface becomes worse, and in the case of B, there are many hard segments and the effect of lowering the hardness is small.
There were drawbacks such as poor moldability due to increased reactivity. (Problems to be Solved by the Invention) An object of the present invention is to provide a method for producing flexible polyurethane foam that does not use halogenated hydrocarbons and overcomes the drawbacks of these conventional methods. . (Means for Solving the Problems) In order to solve the above problems, the present inventors have conducted extensive studies and found that the reaction is carried out in the presence of an amide compound or urea compound as shown in formulas a, b, and c below. It has been discovered that the above object can be achieved by doing so, and based on this knowledge, the present invention has been achieved. That is, in the present invention, when manufacturing a flexible polyurethane foam by reacting a polyol with an organic polyisocyanate in the presence of a catalyst, a foam stabilizer, and a blowing agent, the reaction is carried out by the following formula a, b, or C / (in the formula , R, , Re and R, are hydrogen atoms or have 1 carbon number
-5 alkyl groups, and R1, R2 and R3 may be the same or different from each other. ) (wherein, R4, Rs
, Re and R? represents a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R4, R5, R6 and R2 may be the same or different from each other. ) (~R1゜) (In the formula, R8 and R9 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, sRI and R11 may be the same or different from each other, and R1゜ is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms. Provided is a method for producing a flexible polyurethane foam, characterized in that at least one compound represented by ) representing an alkylene group is used in an amount of 0.5 to 5 parts by weight based on 100 parts by weight of the bodiol. It is something. In the compound represented by the formula a used in the present invention, R3
, Re, and Rs are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, and more preferably a methyl group or an ethyl group. In the compound represented by formula b used in the present invention, R4
, Rs, Re, and Rt are preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group. In the compound represented by the formula C used in the present invention, Re
, Re is preferably a hydrogen atom or a linear or branched alkyl group having 1 to 5 carbon atoms, more preferably a methyl group or an ethyl group. R1° is an alkylene group having 2 to 5 carbon atoms, preferably an ethylene group. The total amount of compounds a, b, and c used in the present invention is 0.5 to 5.0% by weight, preferably 1.0% by weight, based on the total amount of polyol components.
0 to 4.0% by weight. When this amount is less than 0.5% by weight, there is no softening effect, and when it is more than 5% by weight, the air resistance during foam production becomes poor. The polyol components used in the present invention include ethylene glycol, propylene glycol, diethylene glycol,
Monomeric polyols such as triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and 1,4-butanediol, triethanolamine,
Alkanolamines such as jetanolamine, water, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol,
1.3- and 1.4-butanediol, 1.5-pentadiol, 1.2-hexylene glycol, 1. lO-
Decanediol, 1,2-cyclohexanediol, 2
-butene-1,4-dyl, 3-cyclohexane-1
, 1-dimetatool, 4-methyl-3-cyclohexane-1,I-dimetatool, 3-methylene-1°5-pentadiol, (2-hydroxyethoxy)-1-propanol-4-(2-hydroxyethoxy) -1-butanol, 5-(2-hydroxypropoxy)-1-pentanol, 1-(2-hydroxypropoxy)-2-octatool, 3-allyloxy-1,5-pentadiol,
2-allyloxymethyl-2-methyl-1,3-pentadiol, ((4,4-bentroxy)-methyl]-1,
3-propanediol, 3-(o-propenylphenoxy)-1,2-propanediol, 2,2'-diisobrobyldene bis(p-phenyleneoxy)jetanol, glycerin, 1,2,6-hexandriol, 1.
1.1-trimethylolethane, 1. l, 1-)limethylolpropane, 3-(2-hydroxyethoxy)-1
, 2-propanediol, 3-(2-hydroxypropyl)-1,2-propanediol, 2,4-dimethyl-
2-(2-hydroxyethoxy)-methylpentanedio-1,5°1.1.1-tris

[(2-hydroxy)methyl] ethane, l, 1.1-)lis [(2-hydroxypropyl)-methyl 1-propane, pentaerythritol, sorbitol, sucrose, lactose, α-methyl glycoside, α-hydroxyalkyl Glycosides, novolac resins, phenol-aniline-formaldehyde three-dimensional condensation products, aniline-formaldehyde condensation products, caprolactones. Aliphatic polyamines such as ethylenediamine, diethylenetriamine, triethylenetetramine, methylene orthochloroaniline, 4,4'-diphenylmethanediamine,
Aromatic polyamines such as aniline, 2.4-tolylene diamine, and 2.64 lylene diamine, alkanolamines such as triethanolamine and jetanolamine, and 1 such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, and styrene oxide. Polyether polyols obtained by adding a species or two or more species, or polytetramethanelene ether glycol, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1.3- and 1,4-butanediol, tetramethylene glycol, neopentyl glycol, hexamethylene glycol, decamethylene glycol, glycerin,
One or more compounds having at least two hydroxyl groups such as trimethylolpropane, pentaerythritol, and sorbitol; and malonic acid, maleic acid, succinic acid, adipine acid, tartaric acid, pimelic acid, sebacic acid,
Oxalic acid, phthalic acid, terephthalic acid, trimellitic acid,
Polyester polyols made from one or more compounds having a small amount (both have two carboxyl groups) such as hemimellitic acid, or ring-opening polymers of cyclic esters such as polycaprolactone, and also Japanese Patent Publication No. 39-24734 , Special Publication No. 41-3'473, Special Publication No. 43-22108,
Special Publication No. 44-8230, Special Publication No. 47-47597,
JP 47-47999, JP 48-34991, JP 51-50398, JP 51-70286
No., JP-A-52-11249, JP-A-53-4092
No., JP-A-53-13700, JP-A-54-6426
No. 4, JP-A-53-78297, JP-A-54-133
No. 599, obtained by graft polymerization of an ethylenically unsaturated compound in a polyether polyol and/or polyester polyol described in JP-A No. 55-5988.
There are so-called polymer polyol compositions, and suitable ethylenically unsaturated compounds for preparing such compositions include acrylonitrile, styrene, and the like. Furthermore, 1.2-polybutadiene polyol, 1.4-
A polybutadiene polyol is used. The preferred range of the hydroxyl value of the various polyols mentioned above is 20 to 150 mgKOH/g,
These polyols may be used alone or in combination. The incyanate component used in the present invention is not particularly limited and can be those commonly used for urethane foams, but examples include 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, The isomer ratio of 2.4-tolylene diisocyanate and 2.6-tolylene diisocyanate is 80/20 (TDI-80), 6
5/35 mixture of (TDI-65), crude tolylene diisocyanate, diphenylmethane-4,4'-diisocyanate, polyphenylmethylene polyisocyanate (
It is known as crude MDI, and its manufacturing method does not matter. )
, various known modified diphenylmethane-4°4'-diisocyanates modified with carbodiimide groups, dianisidine diisocyanate, toluidine diisocyanate, xylylene diisocyanate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl) fumarate, (2-isocyanatoethyl) carbonate, 1.6-hexamethylene diisocyanate, 1.4-tetramethylene diisocyanate, 1.
10-decamethylene diisocyanate, cumene-2,4
-diisocyanate, 4-methoxy-1,3-phenylene diisocyanate, 4-bromo-1,3-phenylene diisocyanate, 4-ethoxy-1,3-phenylene diisocyanate, 2,4'-diisocyanate Isocyanato diphenyl ether, 5,6-dimethyl-1,3-phenylene diisocyanate, 2,4-dimethyl 1,3-phenylene diisocyanate, 44゛diisocyanato diphenyl ether, bis-5,6-(2- isocyanatoethyl)bicyclo[2,2,13hept-2-ene, benzidine diisocyanate, 4,6-dimethyl-1,3-phenylene diisocyanate, 9,20-anthracene diisocyanate, 4,4'- Diisocyanato dibenzyl, 3.
3'-dimethyl-4,4'-diisocyanatodiphenylmethane, 2,6-dimethyl-4,4'-diisocyanatodiphenyl, 2,4-diisocyanatostilbene, 3.
3'dimethyl-4,4'-diisocyanatodiphenyl,
1.4-anthracene diisocyanate, 2.5-fluorene diisocyanate, 1.8-naphthalene diisocyanate, 2,6-diisocyanatobenzfuran, 2,
NG from 4.6-trientry isocyanate, dimers and trimers of these isocyanates, these organic incyanate compounds, and the above-mentioned active hydrogen-containing compounds
O-terminated prepolymers, which can be used alone or in combination. The amount of isocyanate component used (including the amount used for preparing the urethane prepolymer) is not particularly limited, but in addition to the polyol component, it is based on the amount of active hydrogen compounds including amine compounds that are appropriately used as crosslinking agents in urethane foams. Equivalent ratio of incyanate groups (NGO/H equivalent ratio)
A suitable range is 0.70 to 40, preferably 0.8 to 1.1. Catalysts that can be used in the present invention are not particularly limited and include those commonly used in the production of urethane foams, but examples include riboviramine, triisopropanolamine, trioctylamine, Tributylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, jetanolamine, triethanolamine, N-methyljetanolamine, N,N-dimethyljetanolamine , diethylenetriamine, N,N,N'N'-tetramethylethylenediamine, N,N. N', N'-tetramethylpropylene diamine, N, N
, N', N'-tetramethylbutanediamine, N, N,
N', N'-tetramethyl-1,3-butanediamine,
N,N,N',N'-tetramethylhexamethylenediamine, bis[2-(N,N-dimethylamino)ethyl]
Ether, N, N-dimethylbenzylamine, N, N-
Dimethylcyclohexylamine, N, N, N'N', N
'-Pentamethyldiethylenetriamine, triethylenediamine, formate and other salts of triethylenediamine, oxyalkylene adducts of primary and secondary amines, N
, N-dialkylpiperazines, various N. N',N'-trialkylaminoalkylhexahydroxytriazines, β-aminocarbonyl catalyst of Japanese Patent Publication No. 52-43517, β- of Japanese Patent Publication No. 14279/1983
Aminonitrile catalyst, JP-A-59-191743-1
amine carbonates, etc.), organometallic urethanation catalysts (tin acetate, tin octylate, silver oleate, silver laurate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, etc.). In the present invention, the blowing agent basically only needs to be water, but if necessary, other blowing agents may be used in combination. Among these blowing agents, trichloromonofluoromethane, dichlorodifluoromethane, methylene Chloride, trichlorotrifluoroethane, dibromotetraoloethane, trichloroethane, pentane, n-hexane, dichlorotrifluoroethane, dichlorofluoroethane, 1,1-
1 dichloro 1-fluoroethane, 2.2 dichloro 1.1.
This includes l-trifluoroethane, etc., but it is preferable to prevent halogenated hydrocarbon-based substances from being released to the outside as they are. The foam stabilizer in the present invention is a conventionally known organosilicon surfactant, such as L-520 manufactured by Nippon Unicar Co., Ltd.
L-532, L-540, L-544, L-550, L
-355, L-5305, L-5307, L-5309
, L-5710, L-5720, L-5740M%L-
6202, etc., and 5H-1 manufactured by Tomu Silicone Co., Ltd.
90,5H-192, SH-194,5H-200,5
RX-253,5RX=274c,5F-2961,5
F-2962, 5RX-280A, 5RX-294A, etc., and F-114, F-121 manufactured by Shin-Etsu Silicone Co., Ltd.
, F-122, F-220, F-230% F-258,
F-260B etc., and Goldschmidt's B
-4113 etc. The amount of these foam stabilizers used is 0.1 to 1000 parts, preferably 0.1 to 5 parts, per 100 parts of the polyol component. In the present invention, paints, colorants, flame retardants, fillers, etc. can be contained as necessary. The polyurethane foam manufacturing process in the present invention can be carried out in the same manner as a conventional method, and is not particularly limited. The polyurethane foam obtained by the present invention has excellent flexibility. (Examples) Next, the present invention will be explained in more detail based on Examples, but this does not limit the scope of the present invention.
In the examples, parts indicate parts by weight. The meanings of the abbreviations used in the examples are as follows: Voit = 25 J. Hydroxyl group value 54 kg obtained by addition polymerizing propylene oxide and ethylene oxide to glycerin
KOH/g polyether polyol. TEDA Triethylenediamine DMEA N, N-dimethylethanolamine L-5740S Silicone blowing agent manufactured by Konica Japan MIN, N'-dimethylimidazolidinone MU N, N'-dimethylurea MA N, N'-dimethylacetamide DMF N , N''-dimethylformamide DI-80 2,4-)lylene diisocyaner) 80% by weight and 2,6
- Comparative Example 1 of a mixture of 20% by weight of tolylene diisocyanate: 280 parts of polyol A, 14 parts of water, 0 parts of TEDA
0.196 parts, DMEA 0.28 parts, L-5740
4.2 parts of S are mixed in advance, 0.42 parts of Stanus octoate is added thereto, and immediately after high-speed mixing, TDI-80
150.8 parts of the mixture was added, mixed at high speed, poured into a mold with internal dimensions of 400 x 400 x 70 mm and adjusted to 40°C in advance, and the mixture was covered with a lid and foamed. After heating and curing in an oven at 160° C. for 12 minutes, the foam was taken out from the mold. The physical properties and curing properties of the obtained foam were measured and the results are shown in Table 1. Comparative Example 2, Examples 1 to 4, Comparative Example 3 The same process as Comparative Example 1 was performed except that DMI was added to the polyol side in the amount shown in Table 1. The physical properties and curing properties of the obtained foam were measured and the results are shown in Table 1. It can be seen from Comparative Examples 1 to 3 and Examples 1 to 4 that by adding DMI, the 25% ILD decreases and becomes softer. However, if the DMI exceeds 5 parts, the curing performance deteriorates. Example 5.6 The same process as in Comparative Example 1 was carried out except that DMU was added to the polyol side in the amount shown in Table 1. The physical properties and curing properties of the obtained foam were measured and the results are shown in Table 1. It can be seen that by adding DMU, the ILD decreases by 25%, making it softer. Example 7.8 The same process as in Comparative Example 1 was carried out except that DMA was added to the polyol side in the amount shown in Table 1. The physical properties and curing properties of the obtained foam were measured and the results are shown in Table 1. It can be seen that by adding DMA, the ILD decreases by 25% and becomes softer. Example 9.10 The same process as in Comparative Example 1 was carried out except that DMF was added to the polyol side in the amount shown in Table 1. The physical properties and curing properties of the obtained foam were measured and the results are shown in Table 1. It can be seen that by adding DMF, the ILD decreases by 25% and becomes softer. Comparative Example 4 350 parts of polyol, 14 parts of water, 121 parts of TEDAO,
0.35 parts of DMEA and 4.2 parts of L-5740S were mixed in advance, 0.455 parts of Stanus octoate was added thereto, 8 parts of TDI-80150 was added immediately after high speed mixing, and 40 parts of L-5740S were mixed in advance. Inner dimension adjusted to ℃ 40
The mixture was poured into a mold of 0 x 400 x 70 mm, covered with a lid, and foamed. After heating and curing in an oven at 160° C. for 12 minutes, the foam was taken out from the mold. The physical properties and curing properties of the obtained foam were measured, and the results are shown in Table 2. Comparative Example 5, Examples 11 to 13, Comparative Example 6 DMI is shown in Table-2
Comparative Example 4 except that the amount shown in was added to the polyol side.
processed in the same way. The physical properties and curing properties of the obtained foam were measured and the results are shown in Table 2. From Comparative Examples 4 to 6 and Examples 11 to 13, it can be seen that by adding DMI, the ILD decreases by 25% and becomes softer. However, if DMI exceeds 5 parts, the curing property deteriorates. (Effect of the invention) In the method of the present invention, without using halogenated hydrocarbons by adding compounds of formulas B, b, c,
It has the excellent effect of producing a flexible polyurethane foam.

Claims (6)

[Claims] (1) When producing flexible polyurethane foam by reacting a polyol with an organic polyisocyanate in the presence of a catalyst, a foam stabilizer, and a blowing agent, the reaction is carried out using the following formula a, b, or c a: ▲ Numerical formula, chemical formula , tables, etc. ▼ (In the formula, R_1, R_2 and R_3 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R_1, R_2 and R
_3 may be the same or different. )b:▲There are mathematical formulas, chemical formulas, tables, etc.▼ (In the formula, R_4, R_5, R_6 and R_7 represent a hydrogen atom or an alkyl group having 1 to 5 carbon atoms,
5, R_6 and R_7 may be the same or different. ) c: ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, R_8 and R_9 are hydrogen atoms or carbon atoms from 1 to
5 shows the alkyl group. R_8 and R_9 may be the same or different. R_1_0 represents an alkylene group having 2 to 5 carbon atoms. ) A method for producing a flexible polyurethane foam, characterized in that at least one compound represented by the following formula is used in an amount of 0.5 to 5 parts by weight per 100 parts by weight of the polyol. (2) The method for producing a flexible polyurethane foam according to claim 1, wherein the polyol is selected from the group consisting of polyether polyols, polymer polyols, polyester polyols, ring-opened polymers of cyclic esters, and mixtures thereof. . (3) The method for producing a flexible polyurethane foam according to claim 1, wherein the polyol has a hydroxyl value of 20 to 150 mgKOH/g. (4) The method for producing a flexible polyurethane foam according to claim 1, wherein the organic polyisocyanate is selected from the group consisting of tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenylisocyanate, and mixtures thereof. (5) The equivalent ratio of isocyanate groups to active hydrogen of the organic polyisocyanate in the reaction solution is 0.7:1.0 to 1.4:
1. The method for producing a flexible polyurethane foam according to claim 1. (6) The method for producing flexible polyurethane foam according to claim 1, wherein the catalyst is selected from the group consisting of amine catalysts and organometallic urethanization catalysts.