JPS58204019A - Production of polyurethane foam - Google Patents

Abstract

PURPOSE:To obtain a polyurethane foam having high hardness, high elasticity and excellent flame retardancy and moldability, by mixing specified three kinds of polyol components and reacting the mixture with a polyisocyanate in the presence of a blowing agent and a catalyst. CONSTITUTION:About 1-100pts.wt. halogenated polyether-polyol of the formula (wherein x is 0-7, y is 2-3, A is a brominated polyol rsidue, R is H or a 1-5C alkyk) is mixed with 100pts.wt. polyether-polyol having a functionality of 2-8, a weight ratio of added propylene oxide to added ethylene oxide of 75-95/25- 5, and an OH value of about 15-100mgKOH/g, and about 1-15pts.wt. aliphatic alkanolamine. The obtained polyol component is reacted with a polyisocyanate in the presence of a blowing agent and a catalyst to obtain the purpose polyurethane foam.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing polyurethane foam that has high hardness, high elasticity, and excellent flame retardancy and moldability.

Conventionally, soft or semi-rigid polyurethane foams have been used as cushioning materials for furniture and vehicles such as automobiles. In particular, cushioning materials for automobiles are made by mold foaming)
In general, hot-cure molded products are the mainstream, but in recent years cold-cure molding technology has been developed as an energy-saving mold foaming technology and is gradually gaining popularity. Generally, highly reactive polyether polyolefins are used as raw materials for cold cure systems.
Furthermore, there are modified polyols such as polymers/polyols, which are obtained by radical polymerizing monomers having double bonds in polyols and grafting a part of them with polyols, and polyols called PHD polyols. A polyurea dispersion polyol obtained by coordinating addition polymerization of a polyisocyanate and a polyamine in μ is used. By using these polyol-Ns, it is possible to obtain a polyurethane foam that cures quickly and has high elasticity. However, in cold cure systems, products with increased functional groups such as rounding, modified tolylene diisocyanate and crude diphenylmethane diisocyanate (C-MDI), modified tolylene diisocyanate (C-MDI), and modified Sipheny 7V methane diisocyanate are used to accelerate curing. Usually, 1 is used.
, it is necessary to modify the d-lysocyanate side. On the other hand, in the case of hot cure molds,
Tolylene diisocyanate (polyisocyanate)
(TD Any 0) can be used, and there is no need to modify the polyisocyanate side, but the curing temperature can be increased to 20
0 to 300℃, and after demolding, it takes time to lower the temperature to 40 to 50℃, and the demolding time is also 10℃.
It has the disadvantage of being long, over a minute.

In view of the above-mentioned circumstances, the inventors of the present invention have conducted extensive studies on a method for producing combustible polyurethane foam that is flame retardant and has excellent moldability. -μ, (2) number of functional groups is 2 to 8. A polyether polyol in which the weight ratio of propylene oxide and ethylene oxide is in the range of 75 to 95,725 to 5, and the hydroxyl value is approximately 15 to 100 WKOH/9. (3) Aliphatic alkanolamine is used as the polyol component. In particular, it was found that the above-mentioned problems were solved at once, and a polyurethane foam with 4% higher hardness and high elasticity could be obtained, and based on this knowledge, the present invention was completed.

That is, the present invention relates to (1) the general formula [wherein,
represents hydrogen or an alkyl μ group having 1 to 5 carbon atoms].

(2) The number of functional groups is 2 to B, and the weight ratio of propylene oxide and ethylene oxide is 75 to 95,725 to 5.
and has a hydroxyl value of approximately 15 to 100. Misaki KO
This is a method for producing a polyurethane foam characterized by using a polyether polyol of H/9 and (3) an aliphatic alkanolamine as polyol components, and reacting this with a polyisocyanate in the presence of a blowing agent and a catalyst.

Examples of (1) halogenated polyether polyol used in the present invention include polyether polyols represented by the following formula (e.g., Japanese Patent Publication No. 56-24654,
(as described in Japanese Patent Application Laid-open No. 70312/1983).

[In the formula, X is the number of O to 7, y is the number of 2 to 3, A is the brominated saturated or unsaturated lion residue with the number of functional groups y, R is hydrogen, and 9 is the number of carbon atoms. represents a μkyl group of 1 to 5] Halogenated polyether polyol-y represented by the above formula
is, for example, the following general formula [where X, 7. A has the same meaning as above] A polyglycidyl ether of Ebikulo and Dorin oligomer was prepared in a diluted acidic medium (
Example: nitric acid.

Hydrolyzed with perchloric acid, etc.) The carbon number is 1 or more.
5 monohydric aliphatic alcohols (e.g. methano-μ, diII/
-μ, Propane-lnior-/I', 3rd M third voice μ
Obtained by alcohol rinsing using Aycorμ.

The polyglycide of the Ebiclo/&/Drin oligomer of the above formula can be initiated by a brominated saturated or unsaturated aliphatic dihydroxy compound having 2 to 6 carbon atoms in a manner known per se. It is produced by dehydrochlorination of a hydrogenated polyether polyol μ having terminal chlorohydrin groups obtained by oligomerization of epichlorohydrin.

For example, glycerol motupromhydrin, 3,4-dibromo-butane-1,2-dio-μ, 2,3-dibromobutane-1,4-dio-y, 2゜3-dibromobutane-2
-En 1,4-di-μ, 3,4-dibrombudo 2-
1,2-diols, 2,2-bis-bromomethyl-propane 1,3-dio-y> and 1,2.5.6-tetrapromhexane 3,4-dio- saturated brominated di-μs, tri-μs such as pro-chlorinated pentaerythritol, etc., obtained by oligomerization of shrimp Vxμ hydrins, obtained by dehydrochlorination of nine-halogenated polyether polyols, and halogens. polyether pvrl Rio〃 is a polyether polyether / L' (approximately 1 part by weight per 23,100 parts by weight), which will be described later.
It is preferable to use 100 parts by weight. More preferably, it is about 10 to 70 parts by weight.

(2) Polyether polyols used in the present invention include, for example, ethylene glyco-μ, glopylene glycol μ, ethylene glyco-y, glycerin, trimethylopropane, triethanoamine, bentaerythritol, α -Methyl coside, tolylenediamine,
4, 4'diphenylene-methanediamine, xylide-y
, active hydrogen-containing compounds such as sorbitol, especially propylene oxide and ethylene oxide in a weight ratio of 7.
5-95/25-5, preferably 80-90/20-1
A hydroxyl value of about 15 to 1 that is addition-polymerized in an amount that makes it 0.
00 town KOH/f polyether polyol-μ is mentioned. The order of the addition of propylene oxide and ethylene oxide is not particularly limited.
It may be of the "chip" type, or one in which ethylene oxide polymerized Glock is dispersed in propylene oxide steel, or one in which it is randomly copolymerized.

Examples of (3) aliphatic γμ amines used in the present invention include jetanolamine, diisozolopanolamine, triethanolamine, and triisopropanolamine.
μ amine, 2-amino-2-mef! -1.3-de4panedio-μ, 2-aminodi2-ethylμm1.3-propanedio-voice, tris(hydroxymethyllv)aminomethane. Products added with alkylene oxide such as propylene oxide, and any other known aliphatic arycanolamines can also be used, but among these, jetanolamine and triethanolamine are particularly preferred from the viewpoint of workability and versatility. .

The aliphatic alkanolamine is preferably used in an amount of about 1 to 15 parts by weight, more preferably about 3 to 12 parts by weight, per 100 parts by weight of the above-mentioned (2:J polyny*,n-liol).

The polyisocyanate component used in the present invention includes:
For example, tolylene diisocyanate, diphenylmethane diisocyanate), 1.5 naphthylene diisocyanate, Irimethylene polyphenylene polyisocyanate) (
C-MDI), tolylene diisocyanate having the composition, and so-called prepolymers obtained by reacting these with polio-μ in an excess amount of polyisocyanate can also be used. Moreover, mixtures of these can also be used. Among these, a particularly preferred polyisocyanate component is hatolylene diisocyanate.

Amount of polyisocyanate used in the present invention (NG
Although the O index is not particularly limited, it is usually about 0.5 to 2.0 equivalents, preferably about 0.8 to 1.5 equivalents, based on 1 equivalent of active hydrogen in the polyol-μ component.

In the case of a company using water as a blowing agent, which will be described later, the above amount is used per equivalent of the sum of the active hydrogen of this water and the polio-μ component.

In the present invention, any blowing agent may be used, such as water, chlorinated fluorinated hydrocarbons such as trichlorofluoromethane and dichlorofluoromethane.

When water is used as a blowing agent, the amount of water is (2) Boliate Polyol*1oO! x to part i and approximately 0°1 to 5M
It is used to a certain extent. When using a blowing agent from Hiharagai, the amount is about 0.1 to 60 parts by weight per 100 parts by weight of the polyether polyol in (2). Preferably about 0
．． It is about 1 to 30 parts by weight. The amount of blowing agent is appropriately selected depending on the required foam density, construction method, etc.

Catalysts used in the present invention include, for example, methi, Mmofi76phosphorus, ethylmorpholine, triethylamine,
Examples include tertiary amines such as dimethylethanolamine, dimethylchlorohexylamine, ethylenediamine, propanediamine, tetramethylhexamethylenediamine, pentamethyldiethylenetriamine, and triethylenediamine. Further examples include organometallic compounds such as Nutanus octoate, dibutyl/L'tin silaurylate, and the like. These catalysts may be used alone or in combination, and the use of the catalyst is not particularly limited in the present invention. Generally, it is about 0.001 to 1 per part of polyether polyol-1v100 in (2).
In the present invention, a foam stabilizer may be used during foaming.

In this case, as the foam stabilizer used, there is no need to use a special silicone oil that has a foam-breaking effect, and silicone foam stabilizers that are generally used for urethane foams can be used. Generally, it is used in an amount of about 0.05 to 5 parts by weight per 100 parts by weight of polyether ydrio* (2).

In addition to the catalyst and foam stabilizer, for example, stabilizers, fillers, flame retardants, pigments, etc. may be added as necessary.

The reaction is carried out by means known per se, such as the one-cimit method, the prepolymer method, or the flowing method.

According to the present invention, polio-N components (1), (2)
By appropriately changing the type and blending ratio of (3) or the type and amount of polyisocyanate, a polyurethane foam having soft to semi-rigid properties can be easily obtained.

According to the method of the present invention, tolylene diisocyanate alone is used without using modified isocyanates or mixtures of isocyanates, and the curing temperature is 50 to 6.
High hardness with demolding time of 7 minutes or less under conditions as low as 0°C.
It is possible to obtain a polyurethane foam with high elasticity and excellent flame retardant properties. Rounded crushing prevents shrinkage caused by closed cells during demolding, which is a drawback of cold cure mode foams. How to obtain a good mold form without the need for #-1? Furthermore, the foam is extremely homogeneous, and a clean foam with open cells can be obtained.

Furthermore, the polyurethane foam obtained by the method of the present invention has excellent compressive strength and rebound modulus, and is also excellent in low shrinkage. By changing the density, various physical properties, etc. of the urethane foam obtained by the method of the present invention, various sweep foams can be produced for furniture, vehicles, etc., heat insulation materials, shock absorbers, cushioning materials, etc. It can be used in a wide range of products, such as products and various molded foam products.

The present invention will be explained in more detail with reference to Examples below. Examples Sea urchin It has characteristics. Engineering xol B-251 is 0HH0,330MfKOH/g
, viscosity, (25°C) 6sooO, p3, Br content, 32
%, C1 content, 7%, on the other hand, xol M-1
25 has properties of 0HNo, 235flllJKOH/9, viscosity, approximately 2500 cps (at 25°C), and Br content of 33
Excellent, halogenated polyether polyol with C1 content of 711
μ.

Example/ Actco/l'M1i' in the poly beaker of 2Il
-05 (diglycerin base, POfi85fft*,
KOJ115wt%, OH value 32) 1oo9. Jetano μ amine 5g, Ko-XOI B-25130g, silicone F121 (silicone foam stabilizer manufactured by Shin-Etsu Chemical) 0°6
g, pure water 3. (1, Dove: ff, 0.5g of 33LV (Nippon Nyuka Taxidermy), Stacked (Stannas Octoate manufactured by Yoshitomi Pharmaceutical) o, osy on a scale or in a bowl, stir to make it homogeneous, and then add 65g of tolylene diisocyanate) Pour in TDI-80) and stir evenly to make 25C11X 25C! ! X
Inject into the 20CII box.

The temperature of each liquid was adjusted to 20℃, and the reactivity was 14 seconds for cream time, 54 seconds for gel time, and 65 seconds for rice time.
In seconds, I could see Subaru. The resulting nine foam has a fine seven-dimensional structure and a density of 46.6 kg7'a3. D Engineering N 65% Compressive strength 0, 19 kg/cm2゜Hysteresis loss 41%, Tensile strength 0.831c1cm2,
Elongation 9096. Tear strength 0.46kg/cm2.50
Excellent compression set (50%, 70°C, 22 hours)4. 19
6.Y repellency modulus was 58%, self-extinguishing property was found in STMD-1692@flammability test, burning time was 27 seconds, burning distance was M41au*.

Example λ Mold injection was carried out using the same formulation as in Example 1. −
f: The first lead is made of aluminum 300x150x501 (thickness)
The stock solution was poured into the mold while maintaining the mold temperature at 45°C. After injection, the lid was placed on the mold, set at 55°C, held for 6 minutes in a press, and demolded.The surface skin condition was good, with uniform cells, no swelling, and no crushing after demolding. A good mold form can be obtained. The density of this mold form is 71 kg/m 3 and DI! ff65% compressive strength 0.25kg/am”, hysteresis loss 36
Excellent, tensile strength 1°18 klcta”, elongation 67gl
6. Tear strength 0.61kg7-2, rebound modulus 59%,
The 50% compression set was 5.3 excellent.

Examples 3 to j Polyurethane foams were produced in the same manner as in Example 1 with varying amounts of jetanolamine as shown in Table 1, and their physical properties were investigated.

Example 6~! Example 1 in the same manner as in Example 1! ! lX0L as shown in
Polyurethane foams were produced with nine different blends, varying the amount of B-251, and their physical properties were investigated.

Table 1 Act-x-#M'F'-05100too 10
0 100 100 100 Nidiethanolamine 358558゛lX0LB-25130303
0154560゜Silicone r-121, II)
10 10 Qj5 (160,6:.

Pure water 25 concave aO
(9) □□□ □Dub ff 33LV 02
04 04 O5O504・Stanori
(u9 0.19 (1160050
D5 o, xol cream time seconds 1.1
12 13 10 14 16 gel time e
l 60 50 49 67 53 54゜Rice time seconds 78 62 60 85 71 54
・DIN6Fs compression strength %cxl' O21023Q,
15 013 040 041 'Hysteresis loss*
39 42 35 44 56 50
'Tensile strength 1tkg/c♂LO511)O'Q83 Q5
! 5' Li2122 growth! 11 8
5 77 73 90 64 56' pull 9
Strong mcv'cv? -056047039032ogl,
osr50 excellent compression permanent distortion excellent '7258 Sen
Four companies 74 ・”JS-, 38＠ '＄ -mm
---, -34-, 3 sounds-1,47, -rule-knee, %
6-' 3i, 1 Example~/3゜Example/ Polyurethane foam was prepared in the same manner as in Table 2 (by changing the amount of triethanolamine and changing the type of polyol as shown in Table 2). Manufactured and investigated physical properties.

1 nl bottom left: Table 2 5”-“°ゝ ”°°”°°. .・Polio~Z 3) ) Ref-1/-fi/1 My' 25
'5.0 &OLZo 12.0 11X
OL B-251303030303011 Dafco 3
3I4 (1400,400,400,40oso;
Star ) Rito 0.25 02
5 0.125 teP dirhexane diamine
α16
0.10 □TD I 80 57 61
6'j--Bar 1 good-::-Maja-ηmiii;'----
Suspended i-side---105 □05105゜Cream tie sec 10 10 9 13 12i
)y'yvl im #lJ 55 63 47 55
53j Rice Time -6173597570゜DI
N65% reverse iα1g α19 α30 (L26
(122i, -fuel-λ!u-;”y-lee-A7
J-11 [μm 3i-jl) Trimethylolpropane/Ventaeri'? ) - Le base, po amount 90 wt
*, KO amount 10 vt%, OH value 34 2) Soμ Pito μ base p Q amount 90 wt%, EO
O120wt96,08 value 34 3) Glycerin base, PO amount 90 wt%, EO amount 1
0wt*, OH number 32 Comparative Examples/~2 In Examples/Table 3, polyurethane foams were produced with formulations that did not use halogenated polyether polyol-μ and the physical properties were compared. The obtained 9-form had a non-uniform shape, a low D■M65% compressive strength, and a low-grade releasability.

Comparative example 3~! As shown in Table 3, according to Examples, polyurethane foams were manufactured using nine different combinations using other reactive or additive flame retardants instead of halogenated polyether polyol-μ). The obtained 7 ohm was unsuccessful because the cell shape was non-uniform and the DIN65* compressive strength was low. There were also some items that could not be made into a form.

(,'7^l'Buddha'mouth, Table 3 actco/l/MP'-05'100"
100 100 100 polyol z' i
o.

, jetanolamine 8 8 8
8 Fire Shaft 2) 30 Torin 2 H Gorokodari Ref Recess Fukoko)
20'S/! J
:! -1F-121' Q, 6 0.6 0
．． 6 0.6 0.6 pure water 2
5 λ0 Mouse Mouse Mouse Dafco 33I4 α
30 Q, 20 1160 Change 040 Nutanorito 0.19 Momome 0.15 Change 0.15N Methylmorpholine α09 0.30
−nee ■−↓, −−1e1−2 −=ji−,−,53−
,-,-,,-6z-,-6,6NCO1ndex
, t5- 1s---iL-, -%,----, 9.
8-Cream Time ele 10 8
9 12 gel time @1) 52
77 60 Fu 541) Dimethi IL'M, M-
Bis(2-hydroxyethyl hydroxyethyl) phosphoroamidate (Ihara Chemical Industry, 0Hfi400)
Example/g TD as polyisocyanate with the same formulation as in Example
A polyurethane foam was obtained by mixing I-80 and C-MDI in a weight ratio of 80,720 and using 81 parts of a round product. Reactivity is cream time 11 seconds, gel time 3
It was 9 seconds. The density of this foam is 50,4 kg
/m DIN6596 EEIM strength 0.41-
”, hysteresis loss 50%, tensile strength 0.95kg
/cm2. Elongation: 53 Excellent, tear strength: 0.55-/12. AST with rebound modulus of 53% and 50% compression set of 6.2%
MD1692 combustion test is self-extinguishing and the burning distance is 32
It was m.

Example 73~/B Example carried out in the same manner as Example λ! A mold form was created with a composition of , /2. The obtained foam can be demolded in 7 minutes or less as in Example 2, has a good surface skin condition, has a fine cell structure, does not bulge, and does not shrink even if left without crushing after demolding. Good mold form.

Example/7 Replacement of Ixol B-251 in the same manner as Example/)
For this purpose, Kogyo XOI M-125 was used. The formulation is Actco
7%/MF'-05 10 (1, jetanolamine 8
f, lX0I M-125309, pure water 2.59
゜Siri: I-:/F'-1210,69, Dub: f33
LVO, 659, stacked sail 05g, TDI-806
39 (NCO1ndex 1.05), and its reactivity was 10 seconds for cream time, 60 seconds for gel time, and 90 seconds for rise time. The resulting nine foam has a fine cell structure, a density of 44.6 kg/m, and a DIN65q6
Compressive strength 0.16km2. Hysteresis loss 39th, tensile strength 1 + 03kg/cm", elongation 9596
．． Tear strength (L 52 kg/cm", rebound modulus 54
%, in the A3TMD-169211 flammability test, the combustion distance f
It was self-extinguishing at i35naa.

Comparative Examples B to D In the same manner as in Example λ, Comparative Examples/, 2, 3. ! A mold form was created using the following formulation. The obtained form is 7
Demolding for less than 10 minutes caused blistering, and it was necessary to hold the mold for 10 minutes or more and shrink if it was not crushed after demolding. The cell structure was also non-uniform and the compressive strength was very low.

By comparing the above Examples and Comparative Examples, it is clear that the Examples provide polyurethane foams with high hardness, high elasticity, flammability, and excellent moldability.

”：□〜

Claims (2)

[Claims] (1) General formula [wherein, or represents an alkyl μ group having a carbon number of 1 to 5]. (2)! The number of functional groups is 2 to 8. The amount of propylene oxide and ethylene oxide added is 75 to 95,725 in weight ratio
5, and the hydroxyl value is approximately 15 to 100'F
KOEI/f Obo9 x-furl IJ k-IV
> Yobi (31flFj aliphatic alkano-amine to polyol/L
A method for producing a polyurethane foam, which comprises reacting this with a polyisocyanate in the presence of a blowing agent and a catalyst.