JPS6375021A - Non-rigid high, high-elasticity foam - Google Patents

Abstract

PURPOSE:To produce the titled polyurethane foam having especially improved resistance to wet heat-aging exposure without lowering physical properties such as hardness, etc., by blending a specific crosslinking agent with polyol, etc., in a specific ratio and reacting the blend with a polyisocyanate. CONSTITUTION:A crosslinking agent obtained by adding 2-10mol ethylene oxide to 1mol non-amine tetrafunctional compound (e.g. pentaerythritol, diglycerin, etc.) containing an active hydrogen at the end is mixed with polyol, a catalyst (e.g. triethylamine, etc.), a foam stabilizer, a blowing agent (e.g. trichloro-monofluoromethane, etc.) and other auxiliaries and the mixture is reacted with a polyisocyanate to give the aimed foam. The amount of the crosslinking agent added is 1-10pts.wt. based on total amount of the polyol.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a flexible polyurethane foam with improved quality, and more particularly to a flexible, highly elastic polyurethane foam with improved moist heat aging resistance.

(Prior Art) Flexible polyurethane foam has moderate elasticity and excellent shock absorption performance, and is therefore widely used in bedding, car seats, clivia for furniture, and the like. Flexible polyurethane foam is usually produced by slab foaming or hot mold foaming, both of which require considerable energy to heat in a furnace, and are less pliable and less elastic than foams made from rubber latex. The downside was that the L2 was not comfortable enough to sit on the rubber latex foam because it was so low.

High modulus polyurethane foams were developed to improve this drawback. This foam uses a polymer polyol obtained by polymerizing ethylene-based polymers such as acrylonitrile and styrene in a highly active polyol as a part of the polyol, and reacts with polyisocyanate to form a chamber IJ after foaming.
It is manufactured by leaving it at a temperature of L to 100° C. for a short period of time to perform a so-called cold cure.

This highly elastic polyurethane foam has a very good tactile feel when sitting on it, so it is widely used in passenger car clivias.

(Problems to be Solved by the Invention) Since high-elastic polyurethane foam is often used in passenger car cushions, it needs to have stiffness, that is, hardness and mechanical strength.
@t) is inferior. Jetanolamine and triethanolamine are usually used as crosslinking agents for soft and highly elastic foams, but no improvement in moist heat aging resistance has been observed.

(Means for Solving the Problems) In order to improve the heat aging resistance of soft, highly elastic foams, we have conducted various studies on crosslinking agents, and as a result, we have arrived at the present invention.

That is, the present invention provides a soft, highly elastic polyurethane foam obtained by reacting a mixture of a polyol, a crosslinking agent, a foam stabilizer, a blowing agent, and other auxiliary agents with a polyisocyanate.
A soft polyurethane obtained by adding 1 to 10 parts of a crosslinking agent made by adding 2 to 10 moles of ethylene oxide to 1 mole of a non-amine type tetrafunctional compound having active hydrogen at the end per 10 parts of the total amount of polyol. It is an elastic form.

Examples of the non-amine type tetrafunctional compound having active hydrogen at the end used in the present invention include 1,2,3.4-butanetetrol, 1,2,3.5-pentanetetrol,
Penquerystol, diglycerin, 112.5.6-
Hexanetetrol, 2.3,4.5-hexanetetrol, 1.3,4.5-hexanetetrol, etc. The amount of ethylene oxide added is 2 to 10 moles per mole of the tetrafunctional compound. Appropriate.

If the amount added is out of this range, it will have a negative effect on the hardness, mechanical strength, etc. of the high elastic foam. These crosslinking agents may be used alone or in combination of two or more. may be mixed after adding ethylene oxide, or may be mixed after adding ethylene oxide, or may be added after mixing a tetrafunctional compound.

When mixed, a combination suitable for the present invention is a mixture of pentaerythritol and diglycerin.

The mixing ratio is preferably 100:0 to 20:80, and if mixed within this range, the temperature and heat aging resistance can be improved.
Other physical properties such as hardness and mechanical strength also do not deteriorate.

The appropriate amount of the crosslinking agent according to the present invention is 1 to 10 parts by weight per 100 parts by weight of the polyol. If the amount used is less than this range, the thermal aging resistance will be improved, and if the amount used is more than this range, it will have a negative effect on mechanical strength.

The crosslinking agent of the present invention can be used with other crosslinking agents such as ethylene glycol, propylene glycol, diethylene glycol,
．． Compounds with active hydrogen such as 3- and 1,4-butanediol, jetanolamine, triethanolamine, ethylenediamine, diphenylmethanediamine, tolylenediamine, and hydroxyl value 200mtKOH obtained by adding ethylene oxide to these compounds /
It can also be used in combination with a compound of more than 100 g.

The polyols used in the present invention include water, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and 1,4-butanediol, 1,5-pentanediol, 1 .2-hexylene glycol, l, 10-decanediol, 1,2-cyclohexanediol, 2-butene-1,4-diol, 3
-Cyclohexane-1,1-dimetatool, 4-methyl-3-cyclohexane-1,1-dimetatool, 3-methylene-1,5-bentanediol, (2-hydroxyethoxy)-1-propanol-4-(2 -Hydroxyethoxy)-1-butanol, 5-(2-hydroxypropoxy)-1-pentanol, 1-(2-hydroxypropoxy)-2-octatool, 3-Ori Waxy 1
．． 5-bentanediol, 2-allyloxymethyl-2-
Methyl-1,3-bentanediol ((4,4-pentyloxy)-methyl]-1,3-propanediol, 3-
(O-propenylphenoxy) -1,2-propanediol, 2,2'-diisopropylidenebis(p-phenyleneoxy)jetanol, glycerin, 1.2.6
-hexanetetrol, 1. Ll-trimethylolethane, 1.1.1-trimethylolpropane, 3-(2-
hydroxyethoxy)-1,2-propanediol,
3-(2-hydroxypropyl)-1,2-propanediol, pentaerythritol, sorbitol, cy! ! Sugar, lactose, α-methyl glucoside, α-hydroxyalkyl glucoside, novolanc resin, phosphoric acid, polyhydric hydroxy compounds such as benzene phosphate, polyphosphoric acid (e.g. tripolyphosphate and tetrapolyphosphate), phenol-
Aniline-formaldehyde ternary condensation product, aniline-formaldehyde condensation product, ethylenediamine, diethylenetriamine, triethylenetetramine, methylenebisorthochloroaniline, 4,4゛-and hy2゜4゛-diphenylmethanediamine, 2.4-1 Polyamines such as lylene diamine, 2.6-tolylene diamine,
Polyether polyols or polytetramethylene ether glycol obtained by adding one or more of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, etc. to alkanolamines such as triethanolamine and jetanolamine, or polytetramethylene ether glycol It is. Also, ethylene glycol,
Diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,3- and l,4-butanediol, tetramethylene gelyl, neopentyl glycol,
hexamethylene glycol, decamethylene glycol,
One or more compounds having at least two hydroxyl groups such as glycerin, trimethylolpropane, pentaerythritol, and sorbitol, and malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, pimelic acid,
A polyester polyol obtained from one or more compounds having at least two carboxyl groups, such as sebacic acid, sheracic acid, phthalic acid, terephthalic acid, trimellitic acid, and hemimellitic acid, or a cyclic ester such as polycaprolactone. Ring-opened polymers of can also be used. Furthermore, JP 39-24737, JP 41-3473, JP 43-22108, JP 44-8230, JP 47-47597, JP 47-47999, JP 4
8-34991. JP-A-51-50398, JP-A-51
-70286, JP-A-52-11249, JP-A-53-
4092, JP-A-53.13700, JP-A-54-6
4264, JP-A-53-78297, JP-A-54-13
A so-called polymer polyol composition obtained by graft polymerizing an ethylenically unsaturated compound in a polyether polyol and/or polyester polyol described in No. 3599 and JP-A-55-5988 is used. Ethylenically unsaturated compounds suitable for preparing such compositions include acrylonitrile, styrene, and the like. Furthermore, 1
．． 2-polybutadiene polyol and 1,4-polybutadiene polyol are also used.

The preferred range of the hydroxyl value of the various polyols mentioned above is 20 to 150 mgKOH/g, and these polyols may be used alone or in combination.

The polyisocyanates used in the present invention are known ones, and are not particularly limited, but examples include 2.4-)lylene diisocyanate, 2,6-tolylene diisocyanate, and 2.4-)lylene diisocyanate.
- The isomer ratio of tolylene diisocyanate and 2,6-tolylene diisocyanate is 80720 (TDI-80)
, 65/35 (TDI-65), crude tolylene diisocyanate, 4.4'-diphenylmethane diisocyanate (4,4'-MDI), 2.4'-diphenylmethane diisocyanate (2,4'-MDI)
and mixtures thereof, such as diphenylmethane diisocyanate (MDI), polymethylene polyphenylisocyanate (known as crude MDI, regardless of its manufacturing method), various known modified diphenylmethane diisocyanates modified with carbodiimide groups, and dianisidine. diisocyanate, toluidine diisocyanate,
Xylylene diisocyanate, bis(2-isocyanatoethyl) fumarate, bis(2-isocyanatoethyl)
maleate, bis(2-isocyanatoethyl) carbonate, bis(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-L3- phenylene diisocyanate,
4-ethoxy-1,3-phenylene diisocyanate,
2.4'-diisocyanatodiphenyl ether, 5.6
-Simethyl-1,3-phenylene diisocyanate, 2
, 4-dimethyl-1,3-phenylene diisocyanate)
, 4.4”-diisocyanatodiphenyl ether, bis5.6-(2-isocyanatoethyl)bicyclo(2,2
, 1) hept-2-ene, benzine diisocyanate,
4.6-dimethyl-1,3-phenylene diisocyanate, 9.10-anthracene diisocyanate, 4,4
°-diisocyanatodibenzyl, 3,3°-dimethyl-
4,4゛-diisocyanatodiphenylmethane, 2.6-
Dimethyl-4.4'-diisocyanatodiphenyl, 2.
4-diisocyanatostilbene, 3゜3゜-dimethyl-
4,41-diisocyanatodiphenyl, 3.3'-dimethyl-4,4°-diisocyanatodiphenyl, 1.4-
Anthracene diisocyanate, 2.5-fluorene diisocyanate, 1.8-naphthalene diisocyanate, 2.6-diisocyanatobenzfuran, 2.4.6-
) Luentilisocyanate Also, carbodiimide modified products, billet modified products, dimers, trimers of these organic polyisocyanates, NGO group-terminated prepolymers made from these organic polyisocyanate compounds and the above-mentioned active hydrogen-containing compounds, These may be used alone or in combination.

Catalysts that can be used in the present invention are conventionally known catalysts and are not particularly limited, but examples of amine catalysts include triethylamine, tripropylamine, triisopropanolamine,
Tributylamine, trioctylamine, hexadecyldimethylamine, N-methylmorpholine, N-ethylmorpholine, N-octadecylmorpholine, monoethanolamine, jetanolamine, triethanolamine, N-methyljetanolamine, N, N- Dimethylethanolamine, diethylenetriamine, NIN, N'
, N'-tetramethylethylenediamine, N, N, N'
, N'-tetramethylpropylenediamine, N, N, N
', N'-Tetramethylbutanediamine, N, N, N'
.

No-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,
and oxyalkylene adducts of amino groups of secondary amines,
Azacyclic compounds such as N,N-dialkylpiperazines, various N,N',N"-trialkylaminoalkylhexahydrotriazines, β-aminocarbonyl catalysts of Japanese Patent Publication No. 52-43517, Japanese Patent Publication No. 53-14279 Organometallic urethanization catalysts such as β-aminonitrile catalysts (
tin acid, octyl all, tin oleate, tin laurate, dibutyltin diacetate, diptyltin dilaurate, diptyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, etc.). These catalysts are used alone or in combination, and the amount used is 100f! of a compound with active hydrogen! 0.0001 to 100 per part (hereinafter in the present invention, parts indicate parts by weight)
It is 0 copies.

The blowing agent in the present invention is a mixture of one or more of water, trichloromonofluoromethane, dichlorodifluoromethane, methylene chloride, trichlorofluoroethane, dibromotetrafluoroethane, trichloroethane, pentane, n-hexane, and the like.

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
.

3550, L-5305, L-3600, L-3601
, L-5305, L-5307, L-5309, L-5
710, L-5720, L-5740M, L-620
2, etc., and 5R-190 manufactured by Toray Silicone Co., Ltd.
, 5R-192, 5H-194, 5H-200, SRχ
-253,5RX-274C,5F-2961,5F-
2962, 5RX-28OA, 5RX-294A, etc., F-114, F-121, manufactured by Shin-Etsu Silicone Co., Ltd.
F-122, F-220, F-230, F-258, F
-2608, F-317, F-341, F-601, F
-606, X-20-200,
A-4202, etc.

The amount of these foam stabilizers used is 0.1 to 20 per 100 kg of the compound with active hydrogen and organic polyisocyanate.
Department.

In the present invention, dyes, coloring agents, etc. can be included as necessary.

To carry out the present invention, a polyol, a crosslinking agent, a catalyst, a blowing agent, a foam stabilizer, and other auxiliary agents are mixed to form a resin liquid. A resin liquid and a polyisocyanate are mixed at a predetermined ratio, and the mixture is injected into a mold and foamed. The mixing ratio is the equivalent ratio of NGO groups in the polyisocyanate to active hydrogen in the resin liquid (NG
O/H) is 0.8 to 1.4 After foaming is complete, leave it in an atmosphere at room temperature to 100°C for 5 to 30 minutes, allow it to harden, and then remove it from the mold to create a soft, highly elastic foam. .

(Functions and Effects) The crosslinking agent of the present invention can improve the moist heat aging resistance of the soft, highly elastic foam without deteriorating its physical properties such as hardness and mechanical strength.

(Example) Examples of the present invention will be described below.

The following raw materials were used in the examples. The following parts indicate parts by weight.

Polyol P----A polyether polyol with a hydroxyl value of 34+mgKOH/g obtained by addition polymerizing pentaerythritol with propylene oxide and ethylene oxide.

Polyol R - Graft polyol with a hydroxyl value of 2hgKOH/g obtained by graft polymerizing acrylonitrile to a polyether polyol with a hydroxyl value of 34-gKOH/g obtained by addition polymerization of propylene oxide and ethylene oxide to glycerin. (polymer polyol).

Crosslinking agent - Crosslinking agent obtained by adding the following amount of ethylene oxide to 1 mol of a mixture of pentaerythritol and diglycerin (tJt combined ratio is the weight mixing ratio of pentaerythritol and diglycerin) ) Crosslinking agent Mixing ratio Ethylene oxide Hydroxyside addition amount Ru value (mol) (+sgKOH/*)A 100
10 9.32 400B 80/2
0 5.84 550C501503,8
5700 D 20/80 2.57
850E 50150 1
3.57 300F 50150
1.00 1150DEO^・・
... Jetanolamine crosslinking agent L-5309 ... Organosilicon foam stabilizer manufactured by Nippon Unicar Co., Ltd. L-1020 ... 33χ of triethylenediamine catalyst
Diethylene glycol solution NEM...N-ethylmorpholine catalyst T20
...80/20 TDI and crude MDI 80:2
Example 1: 2350 parts of polyol, 150 parts of polyol R, DEO
A5.0 parts, crosslinking agent A 10.0 parts, L-5309vI
! 5.0 parts of foaming agent, 14.0 parts of water, L-1020 catalyst 2.
0 parts and 2.5 parts of N2M catalyst were mixed to prepare a resin liquid. This resin solution was mixed with 193.0 parts of T20 polyisocyanate and immediately heated to 60°C! J! Adjusted inner dimension 350
Pour into a 350 x 100 mould, close the lid, and foam. After heating and curing in a hot air oven at 100°C for 10 minutes, the foam was taken out from the mold.The physical properties of the obtained foam were as shown in Table 1. In this example, the equivalent ratio of isocyanate groups to active hydrogen ( NCO/)
I) is 1.00.

Examples 2-6 Crosslinking agent B in the amount shown in Table 1 in Example 1.

C or D, respectively, and TM-20 polyisocyanate has an equivalent ratio of isocyanate groups to active hydrogen (NG
The treatment was carried out in exactly the same manner as in Example 1, except that the ratio (O/H) was always 1.00.

The physical properties of the obtained foam were as shown in Table 1.

Comparative Example 1 Completely the same as Example 1 except that 25 parts of crosslinking agent C was used instead of crosslinking agent A in Example 1, and 189.0 parts of TM-20 polyisocyanate (NGO/H・1.00) was used. Treated in the same way. As shown in Table 1, the results showed that the hardness was low and the moisture and heat aging resistance was poor.

Comparative Example 2 The process was carried out in exactly the same manner as in Comparative Example 1, except that 65.0 parts of crosslinking agent C was used in Comparative Example 1.

The results are shown in Table 1. Comparative Example 3 The mechanical strength was low. In Example 1, crosslinking agent E was replaced with crosslinking agent A at 10.
0 parts of TM-20 polyisocyanate was used, and 191 parts of TM-20 polyisocyanate was used.
．． The entire process was carried out in the same manner as in Example 1, except that 0 part was used.

As shown in Table 1, the mechanical strength of the foam was low.

Comparative Example 4 In Example 1, crosslinking agent F was replaced with crosslinking agent A at 10.
0 parts of TM-20 polyisocyanate was used.
The process was carried out in exactly the same manner as in Example 1 except that 5 parts were used. As shown in Table 1, the hardness of the foam was low.

Claims (1)

[Claims] A non-amine type tetrafunctional compound having an active hydrogen terminal in a flexible, highly elastic polyurethane foam obtained by reacting a mixture of a polyol, a crosslinking agent, a catalyst, a foam stabilizer, a blowing agent, and other auxiliaries with a polyisocyanate. A flexible, highly elastic polyurethane foam obtained by adding 1 to 10 parts by weight of a crosslinking agent in which 2 to 10 moles of ethylene oxide is added to 1 mole of polyol.