JPS62148517A - Highly elastic foam - Google Patents

Abstract

PURPOSE:The titled foam, obtained by adding a specific diol as a crosslinking agent to a reaction mixture in reacting a polyol with catalyst, foaming agent, polyisocyanate, etc., to give a polyurethane foam and capable of retaining a high hardness at the same density without deteriorating elongation. CONSTITUTION:A foam obtained by reacting a mixture containing a polyol having preferably 20-150mgKOH/g hydroxyl value, a catalyst, foaming agent, foam stabilizer, another assistant and a diol prepared by addition polymerization of 2-10mol ethylene oxide (E.O) with 1mol bisphenol A, preferably a mixture with 2-6mol average amount of added E.O under pressure with a polyisocyanate as a crosslinking agent. The amount of the above-mentioned diol to be used is normally 1-10pts.wt. based on the polyol and can be used together with another crosslinking agent, e.g. ethylene glycol, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to flexible polyurethane foams, and particularly to high modulus polyurethane foams with improved hardness and mechanical strength.

(Prior art) Flexible polyurethane foam has moderate elasticity and excellent shock absorption performance, so it is widely used in bedding, car seats, furniture cushions, etc. Flexible polyurethane foam is usually made of slab foam or Manufactured by hot mold foaming. G) Even in the case of misalignment, it takes a huge amount of energy to heat the furnace, and compared to foam made from rubber latex, it is less flexible and has lower elasticity, so the comfort you feel when sitting on rubber latex foam is lower. The drawback was that it was not recognized.

High modulus polyurethane foams were developed to improve this drawback. This foam uses a polymer polyol obtained by polymerizing ethylene monomers such as acrylnide and styrene in a highly active polyol as a part of the polyol, and reacts it with polyinsyanate, then heats it to room temperature to 80℃ after foaming. It is manufactured by leaving it to stand and performing a so-called cold cure. This highly elastic polyurethane foam has a very good feel when sitting on it, so it is widely used in passenger car cushions.

(Problems to be Solved by the Invention) Since high-elastic polyurethane foam is frequently used in passenger car cushions, it is required to reduce the density of the foam, improve waist strength, and improve mechanical strength.

If the density of the foam is reduced, the stiffness and therefore the hardness will be reduced, and the mechanical strength will also be reduced. If the density is lowered while maintaining the hardness and mechanical strength, the elongation will decrease. Another problem is that if the hardness and mechanical strength are increased, the elongation decreases.

(Means for solving the problem) As a result of various studies on high elastic polyurethane foam that maintains higher hardness at the same density and does not reduce elongation even when hardness and mechanical strength increase, we found the following. reached the invention of.

That is, in the present invention, when producing a highly elastic foam of flexible polyurethane by reacting a mixture consisting of a polyol, a crosslinking agent, a foam stabilizer, a blowing agent, and other auxiliaries with a polyisocyanate, 2 ethylene oxides are added to 1 mole of bisphenol A.
This is a highly elastic foam characterized by adding up to 10 moles of diol obtained by addition polymerization.

The diols of the invention are used as crosslinking agents. The manufacturing method is to use 2 to 2 to 1 mole of bisphenol A in the presence of a catalyst.
10 moles of ethylene oxide are subjected to pressure addition polymerization.

A particularly suitable average addition amount of ethylene oxide is 2 to 6.
It is a mole. The product is a mixture of diols with different amounts of ethylene oxide addition.

ζ ”ji + 11
As an example, when 4 moles of ethylene oxide are reacted,
4 molar adduct 36% by weight, 3 molar adduct 31% by weight, 2
10% by weight of molar adduct, 23% by weight of adduct of 5 moles or more
A diol mixture consisting of

Addition of such diol mixtures can improve the hardness, tensile strength, tear strength, and elongation of high modulus polyurethane foams. The amount used is polyol 100
It is appropriate to use 1 to 10 parts by weight. Addition amount is 1
If the amount is less than 10 parts by weight, no effect will be observed, and if it exceeds 10 parts by weight, the compression set of the highly elastic foam will increase, resulting in problems such as decreased practicality.

This diol can be used as other crosslinking agents such as ethylene glycol,
Diethylene glycol, 1,3- and 1,4-butanediol, pentaerythritol, triethanolamine,
It can also be used in combination with compounds having active hydrogen such as jetanolamine, ethylenediamine, diphenylmethanediamine, and tolylene diamine, and compounds obtained by adding ethylene oxide to these compounds and having a hydroxyl value of 200 m and 9 KOH/g or more.

The polyols used in the present invention include water, ethylene glycol, propylene glycol, diethylene glycol, triethylene glycol, cyfropylene glycol, trimethylene glycol, 1,3- and 1,4-butanediol, 1,5-bentanediol, 1,2-hexylene glycol, 1,1o-decanediol, 1,2-cyclohexanediol, 2-butene-1,4-diol, 6
-Cyclohexane-1,1-dimetatool, 4-methyl-6-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-aryloxy-1
, 5-bentanediol, 2-allyloxymethyl-2-
Methyl-1,3-bentanediol ((4,4-pentyloxy)-methyl]-1,6-propanediol, 3-
(0-propenylphenoxy) -1,2-propanediol, 2,2'-diisopropylidenebis(p-phenyleneoxy)jethanol, glycerin, 1,2.
6-hexanetriol, 1,1,1-trimethylolethane, 1.1.1-)limethylolpropane, 6-
(2-hydroxyethoxy) -1,2-propanediol, 5-(2-hydroxypropyl) -1,2-propanediol, pentaerythritol, sorbitol, sucrose, lactose, α-methylglucoside, α-hydroxyalkyl Glucosides, novolac resins, polyhydric hydroxy compounds such as phosphoric acid, benzene phosphoric acid, polyphosphoric acid (for example tripolyphosphoric acid and tetrapolyphosphoric acid), phenol-aniline-formaldehyde ternary condensation products, aniline-formaldehyde condensation products ethylenediamine, diethylenetriamine, triethylenetetramine, methylene orthochloroaniline, 4,4'-diphenylmethanediamine, 2.4-1 lylenediamine, 2,6-
Polyether polyols obtained by adding one or more of ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide, etc. to polyamines such as tolylene diamine, and alkanolamines such as triethanolamine and jetanolamine. or polytetramethylene ether glycol. Also, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, trimethylene glycol, 1,5- 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 nrubinoto, and malonic acid, maleic acid, succinic acid, adipic acid, tartaric acid, pimelic acid, sebacic acid,
Polyester polyols obtained from one or more compounds having at least two carboxyl groups such as oxalic acid, phthalic acid, terephthalic acid, trimellitic acid, and hemimellitic acid, or cyclic esters such as polycaprolactone. Ring-opened polymers are also used. In addition, special public service No. 39-2
4737. Tokuko Sho 41-3473, Tokuko Sho 43-221
08. Special Publication No. 44-8230, Special Publication No. 47-47597
．． Special Publication No. 47-47999, No. 48-34991
, JP-A-51-50398, JP-A-51-70286,
JP-A-52-11249, JP-A-53-4092. Ethylene in polyether polyols and/or polyester polyols described in JP-A-53-13700, JP-A-54-64264, JP-A-53-78297, JP-A-54-135599, JP-A-55-5988, etc. A so-called polymer polyol composition obtained by graft polymerizing an unsaturated compound 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-tolylene diinocyanate, 2,6-1-lylene diinocyanate, 2.
The isomer ratio of 4-tolylene diisocyanate and 2.6-1 lylene diisocyanate is 80/20 (TDI-80)
, +55155 (TD Aero 5), crude tolylene diisocyanate, diphenylmethane diisocyanate, polyphenylmethylene polyisocyanate (crude M
(known as DI, regardless of the manufacturing method), various known modified diphenylmethane diisocyanates modified with carbodiimide groups, dianisidine diisocyanate, toluidine diisocyanate, xylylene diinocyanate, bis(2-incyanatoethyl) fumarate, Bis(2-incyanatoethyl)malate, bis(
2-incyanatoethyl) carbonate, bis(2-incyanatoethyl) carbonate, 1,6-hexamethylene diisocyanate, 1,4-tetramethylene diisocyanate, 1゜10-decamethylene diisocyanate, cumene-2,4- Diisocyanate, 4-methoxy-
1,3-furinylene diisocyanate, 4-bromo-1
, 3-phenylene diisocyanate, 4-ethoxy-1
, 3-phenylene diisocyanate, 2,4'-diisocyanatodiphenyl etherpe 5,6-dimethyl-1
, 3-phenylene diisocyanate, 2,4-dimethyl-1,6-phenylene diisocyanate, 4゜4'-diisocyanatodiphenyl ether, bis5゜6-(2-
incyanatoethyl)bicyclo[2,2,i]hept-
2-ene, benzidine 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-4,4'-diisocyanatodiphenyl, 6,3'-dimethyl-4,4
1-diisocyanatodiphenyl, 1,4-anthracene diisocyanate, 2,5-fluorene diisocyanate, 1,8-naphthalene diisocyanate, 2,6-diisocyanatobenzfuran, 2.4.6-1-lentolisocyanate or , carbodiimide modified products, billet modified products, dimers of these organic polyisocyanates,
dimers, NCO group-terminated prepolymers made from these organic polyisocyanate compounds and the above-mentioned active hydrogen-containing compounds, which 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-occudecylmorpholine, monoethanolamine, jetanolamine, triethanolamine, N-methyljetanolamine, N,N -dimethylethanolamine, diethylenetriamine, N,N.

Hl, 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 amino groups of primary and secondary amines, azacyclic compounds such as N,N-dialkylpiperazines, various N,N',N"-trialkylaminoalkylhexahydrotriazines, especially Kosho 52
β-Amine carbonyl catalyst of -43517, Japanese Patent Publication No. 1983
Organometallic urethanation catalysts (tin acetate, tin octylate, tin oleate, tin laurate, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin dichloride, lead octoate, lead naphthenate, nickel naphthenate, cobalt naphthenate, etc.). These catalysts may be used alone or in combination, and the amount used is o, oooi based on 100 parts by weight of the compound having active hydrogen (in the present invention, parts indicate parts by weight).
~100 copies.

The blowing agent in the present invention is a mixture of one or more of water, trichloromonofluoromethane, dichlorodifluoromethane, methylene chloride, trichlorotrifluoroethane, cyfuromotetrafluoroethane, 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-36
01, L-5305, L-5307, L-5309, L
-5710, L-5720, L-5740M1L-62
02, etc., and 5H-1 manufactured by Toray Silicone Co., Ltd.
90,5H-192,5H-194,5H-200,5
RX-253,5RX-2740%5F-2961,5
F-2962, 5RX-28OA, 5RX-294A, etc., F-114, F-1 manufactured by Shin-Etsu Silicone Co., Ltd.
21, F-122, F-220, F-230, F-25
8, F-260B, F-317, F-341, F-6
01, F-606, X-20-200, X-20-20
1, etc., and TFA-420 manufactured by Toshiba Silicone Co., Ltd.
0, TFA-4202, etc.

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

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

To carry out the present invention, a polyol, a crosslinking agent, a catalyst, a foam stabilizer, a foaming agent, and other auxiliary agents are mixed to form a resin liquid. A resin liquid and a polyisocyanate are injected into a mold at a predetermined ratio in a foaming manner and are foamed. Room temperature ~ 80° after foaming
A highly elastic polyurethane foam can be obtained by leaving it in an atmosphere of C for 5 to 30 minutes to cure it and then removing it from the mold.

(Functions and Effects) The high elasticity polyurethane foam obtained according to the present invention can maintain higher hardness at the same density, so it is strong and has increased tensile strength, elongation, and tear strength. . Further, even if the density is lowered, the same hardness, tensile strength, elongation, and tear strength as in the case of using a conventionally known crosslinking agent can be maintained. Moreover, the high modulus foam according to the invention does not suffer from a decrease in elongation even when the density is decreased.

(Example) Examples will be described below.

The following raw materials were used in the examples.

Polyol E...Polyether triol polyol with a hydroxyl value of 54 m and 9KOR/19 obtained by addition polymerizing propylene oxide and ethylene oxide to pentaerythritol POP...Chrycerin? Polymer polyol with a hydroxyl value of 28 m&KOH/g (7) obtained by polymerizing acrylonitrile using a polyether triol with a hydroxyl value of 33 mgKOH/g obtained by addition polymerization of propylene oxide and ethylene oxide as a solvent.

Crosslinking agent B... Hydroxyl value 28 obtained by reacting 4 moles of ethylene oxide with 1 mole of bisphenol A
Crosslinker of the invention with 0 mg KOH/&.

L-5509: Organic silicone non-foaming agent manufactured by Nippon Unicar Co., Ltd.

L-1020... Triethylenediamine catalyst 6
3-tidiethylene glycol solution.

NEM...N-ethylmorpholine catalyst A-1...
... Bis(dimethylaminoethyl)ether catalyst.

F-11... Trichloromonofluoromethane blowing agent.

MDI-TM2D...'1' DI-80 and crude MD
80:20 weight ratio mixture with I.

In the examples, parts indicate parts by weight, and hardness was measured using a 25q6 indentation compression load (LD).

Examples 1 to 4 6 parts of polyol E, 35 parts of polyol POP, 3.0 parts of crosslinking agent B, 10 parts of L-5309 organosilicon non-foam stabilizer
parts, L-1020 catalyst 0.55 parts, HEM catalyst 0.4 parts, A-1 catalyst 0.05 parts, water 33 parts, F-11 blowing agent 5
．． Mix 0 parts to make a resin solution. MDI this resin liquid
- Rapidly mix with 412 parts of TM20 polyisocyanate and immediately pour into a mold with internal dimensions of 350 x 350 x 100 + am, close the lid and allow to foam. After heating the mold at 60°C for 6 minutes, the molded high modulus foam is removed.

When pouring into the mold, pour slightly more than the calculated amount,
The density of the high modulus foam is adjusted by adjusting the injection amount.

The physical properties of the obtained highly elastic foam are shown in Table 1.

Table 1 [Examples 5 to 8 In Examples 1 to 4, 6.0 parts of crosslinking agent B was used, and MD
All treatments were carried out in the same manner as in Examples 1 to 4, except that 42.6 parts of I-TM20 polyisocyanate was used.

The physical properties of the obtained highly elastic foam are shown in Table 2.

Comparative Examples 1 to 4 In Examples 1 to 4, 2.0 parts of triethanolamine and 0 parts of jetanolamine were used as crosslinking agents instead of crosslinking agent B.
．． The entire process was carried out in the same manner as in Examples 1 to 4, except that 44.9 parts of MDI-TM20 polyisocyanate was used. The physical properties of the obtained foam are shown in Table 3.

Table 6 The above results are summarized in Figures 1-4. It is clear from Figures 1 to 4 that the high modulus polyurethane foam using the crosslinking agent of the present invention has higher hardness (25% indentation compressive load), tensile strength, and Both elongation and tear strength increase. Furthermore, even if the density is lowered, the same hardness, tensile strength, elongation, and tear strength can be maintained as when other crosslinking agents are used. Furthermore, as is clear from FIG. 3, even when the density of the high modulus foam according to the present invention is reduced, the elongation does not decrease as seen in high modulus foams using other crosslinking agents.

[Brief explanation of drawings]

FIG. 1 shows the relationship between the 25-inch compression indentation load and the density. Figure 2
indicates the relationship between tensile strength and density. Figure 3 shows the relationship between elongation and density. Figure 4 shows the relationship between tear strength and density.

Claims (1)

[Claims] When producing a highly elastic flexible polyurethane foam by reacting a mixture of a polyol, a crosslinking agent, a catalyst, a foam stabilizer, a blowing agent, and other auxiliary agents with a polyisocyanate, 2 to 10% of ethylene oxide is added to 1 mole of bisphenol A.
A highly elastic foam characterized by adding diol obtained by molar addition polymerization.