JPS61120819A - High-hardness flexible polyurethane foam - Google Patents

Abstract

PURPOSE:The titled foam having well-balanced strength/elongation properties and improved in a hardness without increasing an apparent density, prepared by foaming a specified mixed polyol component and a polyisocyanate component in the presence of a blowing agent, a catalyst and a foam stabilizer. CONSTITUTION:The purpose flexible polyurethane foam is obtained by reacting an at least bifunctional OH-containing polyol component with an at least bifunctional polyisocyanate component in the presence of a blowing agent, a catalyst and a foam stabilizer. Said polyol component includes a mixed polyol comprising a trifunctional polyol for flexible foam and 2,2-bis(4-hydroxyphenyl) propane/propylene oxide adduct, an aromatic amine-based polyoxyalkylene polyol and/or a polymer polyol. Particularly suitable is an aromatic polyisocyanate.

Description

DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) This invention relates to flexible polyurethane foams used in automobiles, furniture, bedding, or daily necessities.

(Prior art) Conventionally, flexible polyurethane foam has a density of 1
Products in the range of 0 to 50 are produced, of which 14 to 25
Suno form is the mainstream.

For foams in this range of apparent density, there is generally a proportional relationship between apparent density and hardness, and the higher the apparent density, the higher the hardness. The foam ranges from 5.5 to 3.5 kg.

Recently, there has been a strong demand for weight reduction in various application fields including the automobile field, and research is being conducted from various angles on technology that can stably produce foams with increased hardness without decreasing apparent density. It is becoming.

Measures to do so include ■combining the use of polyols with four or more functional functions, ■creating high isocyanate intex, ■increasing the amount of water blended,
■Methods such as the combined use of polymer polyols are being considered.

However, method (■) has the disadvantage that the strength and elongation properties and compression set properties decrease, and methods (■) and (2) generate significant heat during the reaction, which tends to cause scorch inside the foam, and in some cases, there is a risk of ignition. There was a problem with this.

Furthermore, method (2) has the disadvantage that the obtained foam has poor heat resistance and is prone to scorch, so none of the methods has reached the point where it can be used as a decisive factor.

On the other hand, as a polyol for polyurethane, a propylene oxide adduct of 2,2-bis(/I-hydroxyphenyl)propane (hereinafter abbreviated as bisphenol A-PO adduct) is used alone or at least as a difunctional aromatic amine base. The technology used in combination with polyoxyalkylene polyol (hereinafter abbreviated as aromatic amine-based polyol) is disclosed in Japanese Patent Application Laid-open No. 59-1989.
This technique, which is known in No. 47223, is aimed at improving the heat resistance of rigid polyurethane resins or rigid methane foams.

(Problems to be Solved by the Invention) The present invention overcomes the drawbacks of the prior art as described above, and has a rigid molecular structure and high viscosity that are normally unimaginable, as well as trifunctionality for soft foams. By making it possible to incorporate bisphenol A-PO adducts, which have poor compatibility with polyols, it has well-balanced strength and elongation properties.
Moreover, the object is to obtain a soft urethane foam with increased hardness without increasing the apparent density of the foam.

(Structure of the invention) One component of the mixed polyol used in the present application is 2.2-
It is a propylene oxide adduct of bis(4,hydroxyphenyl)propane.

This can be obtained by reacting 1 mole of 2,2bis(4-hydroxyphenyl)propane (hereinafter referred to as bisphenol A) with 2 or more moles of propylene oxide (hereinafter referred to as PO).

This bisphenol A-PO adduct was disclosed in JP-A-59-47
The one described in Japanese Patent No. 223 is suitable, and commercially available examples include BISOL-2P manufactured by Toho Chiba Chemical.

Further, the aromatic amine-based polyol, which is another component of the mixed polyol used in this application, has at least a bifunctional hydroxyl value (hereinafter abbreviated as OH value) of 200 to 700.
Aromatic monoamines such as aniline or 2,4- and 2,6-l-lylene diamines (TDA) and so-called crude TDA, 4,4
'-diaminodiphenylmethane and one or more of aromatic diamines and aromatic polyamines such as polymethylene polyphenylene polyamine obtained by condensation of aniline and formalin, ortho-, meta- or para-phenylene diamine, meta- or para-xylylene diamine, etc. , propylene oxide, ethylene oxide, etc., by adding one or more alkylene oxides, and the free 1
It is at least a bifunctional polyol in which substantially no primary or secondary amine remains, and a commercially available product such as GR-30 manufactured by Narita Pharmaceutical Co., Ltd. falls under this category.

The bisphenol A-PO adduct mentioned earlier has poor compatibility with general-purpose polyols for soft foam, and even if the two are stirred and mixed, they will separate into two layers over time. The polyol has excellent compatibility with general-purpose soft foam polyols, especially trifunctional polyols,
Mixing and stirring these three materials not only creates a uniform layer, but also
It has the effect of lowering the viscosity of mixed polyol systems, so
It is an indispensable component because it also has the effect of significantly improving the mixing operation with other compounding agents.

In addition, in order to make the effect of this aromatic amine-based polyol more effective, in order to lower the viscosity of the aromatic amine-based polyol itself and improve processability, the following are added in addition to the aromatic amines at the synthesis stage: These aliphatic glycols and the like can be used as co-initiators.

For example, polyfunctional aliphatic glycols such as ethylene glycol, dipropylene glycol, propylene glycol, dipropylene glycol, glycerin, trimethylolpropane, glucose, sorbitol, sucrose, fats such as ethanolamine, jetanolamine, triethanolamine, ethylenediamine, etc. Examples thereof include group amines and aliphatic alkanolamines, and these co-initiators are preferably used in an equimolar or less amount relative to the aromatic amines.

In this application, as the trifunctional polyol for soft foam used, all known polyester polyols and polyether polyols having an O8 value of 35 to 65 can be used, but in particular polyoxypropylene ether polyols having an O8 value of 56 can be used. Preference is given to polyol or polyoxyethylene propylene ether polyol.

This invention is a technology characterized by increasing the hardness of a flexible urethane foam using a mixed polyol of a trifunctional polyol for softness, a bisphenol Δ-PO adduct, and an aromatic amine-based polyol. The ratio of each polyol used is 0.2 to 8 parts by weight of the bisphenol A-PO adduct to 77 to 99.6 parts by weight of the trifunctional polyol for the flexible four 11, preferably 0.6 parts by weight.
-2 parts by weight of the aromatic amine-supported polyol, preferably 0.2 to 8 parts by weight, preferably 0.6 to 2 parts by weight.

The bisphenol A-PO adduct and the aromatic amine-based polyol are preferably used in a ratio of 0.6 to 1.4 of the aromatic amine-based polyol to 1 part of the bisphenol A-PO adduct, and optimally, they are used in equal amounts. used in

Although the hardness of foams made from these mixed polyols is clearly improved, the 1 strength elongation properties may be slightly lowered.

When such a tendency is observed, it is preferable to add a small amount of diol (bifunctional polyol) to the above i'B mixed polyol.

The diol used in this case is 08 valence 28-28
0 (molecular weight 400-4000) preferably OH number 28
-112 (molecular weight 1000-4000) is suitable; as the molecular weight decreases, the resulting foam tends to shrink more easily. The amount of diol added is 0.00 parts by weight per 100 parts by weight of mixed polyol. The range of /I to 12 parts by weight is good, and if it is less than 0.4 parts by weight, the effect of improving strength and elongation properties is poor.

On the other hand, increasing the addition amount to 12 parts by weight or more is not preferable because it will adversely affect the compression set characteristics of the obtained foam.

Even if a polymer polyol is used in place of the amine-based polyol, which is one component of the mixed polyol, the same effects can be obtained, namely, compatibility with the bisphenol A-PO adduct and increased hardness of the foam.

All known polymer polyols can be used in this case, such as commercially available POP31/28.34/2g and 32/45.36/2 manufactured by Mitsui Nisso.
4.36728.40745 and the like. The amount of polymer polyol added is from 77% to 77% for soft trifunctional polyol
The range of 0.4 to 33 parts by weight is suitable for 99.2 parts by weight. If it is less than 0.4 parts by weight, no hardening effect will be observed, and if it is more than 33 parts by weight, the heat generation temperature inside the foam will increase. Larger and more likely to cause scorch. Even when a polymer polyol is used, the effect of improving strength and elongation properties can be observed by the combined use of a diol, so it is recommended to add it as necessary.

This specification requires the use of a mixed polyol consisting of a trifunctional polyol, a bisphenol A-PO adduct, and an amine-based polyol or a polymer polyol as a polyol component. If the amount is within 40% of the total amount of bisphenol A-PO adduct and amine-based polyol or polymer polyol, 08 valence 28 to 850
An aromatic polyol having at least a difunctional ○H group can be used in combination. As the aromatic polyol having a valence of 28 to 850 and having at least a bifunctional OH group, (a) monocyclic or Polyols with a hydroxyl value of 28 to 600 obtained by adding alkylene oxides such as propylene oxide and ethylene oxide to polycyclic aromatic compounds.Aromatic polybasic acids such as (bro)phthalic acid, isophthalic acid, terephthalic acid, and 1-helimellitic acid. Polyol with a hydroxyl value of 28 to 500 obtained by adding alkylene oxide such as propylene oxide or ethylene oxide (c) metaxylylene glycol, paraxylylene glycol (d) aromatic dicarboxylic acid such as phthalic acid, isophthalic acid, terephthalic acid, or Anhydrides or lower alcohol esters thereof, and/or aliphatic dicarboxylic acids such as adipic acid and succinic acid are used as acid components, and aliphatic polyols such as ethylene glycol, 1,4-butylene glycol, and 1-ramethylolpropane, 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol β, β, β, β-telhelamethyl-2,4,8,1
0-tetraoxaspiro (5,5)-undecane-3
, 9-jetanol, etc., or polyester polyols having a hydroxyl value of 28 to 450 whose polyol component is a polyol of 2 (a), (b), or (c).

As the polyisocyanate component used in the present application, all known at least difunctional polyisocyanes 1- can be used, but in particular aromatic polyisocyanes 1-
~ are preferred, such as 2,4- and 2゜6-1-lylene diisocyanate (TDI), orthotoluidine diisocyanate (TODI), naphthylene diisocyanate 1-
(NDI), xylylene diisocyanate 1- (X D
T) 4.4'-diphenylmethane diisocyanate (MDI) and carposiimide-modified MDT (for example, Nippon Polyurethane Co., Ltd. MTL), polymethylene polyphenylisocyanate-1, (PAPI).

Polymeric polyisocyanate-1- (for example, Sumitomo Bayer Urethane 44v) and the like can be used alone or in combination.

In the present invention, when making a urethane foam by reacting polyols with isocyanate, etc., the isocyanate 1-index is preferably 103 to 130, but
The amount can be increased or decreased as appropriate based on desired physical properties.

Furthermore, the present invention can be applied not only to soft slab forms but also to mold forms.

Furthermore, in the present application, in order to produce flexible polyurethane foam, catalysts, blowing agents, foam stabilizers, and flame retardants, pigments, fillers, etc. are used as necessary, but there are no particular restrictions on these, and known ones may be used. All available.

(Example) This will be explained in detail below based on examples.

Example 1 Trifunctional polypropylene glycol (Mitsui Nisso #3
050. OI-1 value 56) 980 g Ni-tin catalyst (8% stack 1~ made by Yoimiya) L6 g, silicone foam stabilizer (ST-1-190 made by Toray Silicone) 10 g, 1-methyl 4 (dimethylamino) as an amine catalyst A mixed solution was prepared by adding 1.2 g of ethyl piperazine. To this, BI manufactured by Toho Chiba Chemical was added as a bisphenol A-PO adduct.
10 g of SOL-2P (OH value 320), G R-30 (O
Tolylene diisocyanate (Mitsui Nisso T D
530 g of I-80) was added and immediately stirred for 7 seconds using a homomixer, followed by free foaming. At this time, a thermometer was inserted into the center of the foam to measure the maximum exothermic temperature. After that, the temperature side was removed, the foam was heated for 10 minutes in a constant temperature bath at 100°C, and after cooling for 24 hours, J I
The trowel hardness, impact resilience, and compressive residual strain of S K6/+01 were determined by the method of JIS K6301.
The apparent density was measured by the 4T method. The results are shown in Table 1.

Comparative Example 1 1000 g of polypropylene glycol was taken and BIS
A foam was obtained in exactly the same manner as in Example 1 without adding OL-2P and GR-30, and the physical properties were measured.

The results are also listed in Table 1.

Examples 2 to 5 Forms having the formulations shown in Table 2 were prepared in exactly the same manner as in Example 1, and the results of measuring the physical properties are also listed in Table 1.

Examples 6 to 9 Actokol #3000 (OH value 56) manufactured by Substitute Yakuhin was used as the trifunctional polypropylene glycol, Freon 1 (manufactured by Mitsui Chlorochemical) was used as the blowing agent, and N-methylmorpholine (N A foam was prepared from the formulations shown in Table 3 in exactly the same manner as in Example 1 except that MM) and 1-methylpentadiamine (abbreviated as TMPDA) were used, and the physical properties were measured. are shown in Table 4.

Comparative Example 2 BISOL-2P and GR-
Create a form without adding 30 and measure its physical properties,
It is also listed in Table 4.

Example 10 62 parts by weight of trifunctional polyol HF3013 (Daiichi Kogyo tlI! Yakuhin, 08 value 56), 33 parts by weight of polymer polyol 36/24 (manufactured by Mitsui Nisso, OH value 42), bisphenol A, - B I 5QL- as PO adduct
2P (manufactured by Toho Chiba Chemical, OH value 320) 1 part by weight,
1 part by weight of aromatic amine-based polyol GR-30 (manufactured by Yayoi Yakuhin Kogyo Co., Ltd., 08 value 4°O), 3 parts by weight of bifunctional polyol (Diol 2000.08 value 56 manufactured by Asahi Denka Co., Ltd.), silicone foam stabilizer (Japanese) L5740M manufactured by Unicar) 1 part by weight, tin catalyst (Stack 1~ manufactured by Yoimiya Pharmaceutical Co., Ltd.) 0.02 part by weight,
Flame retardant TH], 01. (manufactured by Olin Corporation) were mixed at a ratio of 7 parts by weight to prepare Solution A.

On the other hand, 4.5 parts by weight of deionized water, 0.14 parts by weight of triethylenediamine as an amine catalyst, and trifunctional polyol P-333 (manufactured by Dai-Kogyo Seiyaku, 011 value 56) 15
Part by weight was added to prepare Solution C.

To 216 g of liquid A obtained in this way, 39.3 g of liquid C, B
Tolylene diisocyanate (Mitsui Nisso TD) as a liquid
1-80), stirred and mixed for 7 seconds with a homomixer, and placed in a 32 x 32 x 7 cm pen 1~hole.
The foam was injected into a mold equipped with a foam. After foaming was completed, the mold was heated in an oven at 150° C. for 15 minutes, left to cool, and then removed from the mold. The physical properties of the obtained mold form were measured in the same manner as in Example 1, and the results are shown in Table 5.

Comparative Example 3 Example: Bisphenol A-PO adduct in the case of 0, aromatic amine-based polyol, and bifunctional polyol were not blended, and trifunctional polyol HF 3013 was mixed with 65% of trifunctional polyol HF 3013.
parts by weight, 35 parts by weight of polymer polyol 36/24,
A mold form was created in the same manner except that TDI-80 was changed to 85 g, and the physical properties were measured.
Also listed in the table.

Table 5 (Effects of the invention) Trifunctional polyol and bisphenol A for soft foam
By using the -PO adduct and the aromatic amine-based polyol together, (1) it is possible to uniformly make the highly viscous (suphenol Δ-PO adduct), which has poor compatibility with the trifunctional polyol for soft foam, uniformly compatible with the polyol. The viscosity can be increased to a range where it is easy to use for one-shot one-form applications.

(2) There is no problem in compatibility with known compounding agents such as diols other than trifunctional polyols and flame retardants, and it can be applied to the production of not only slab foam but also mold foam.

(3) The obtained foam has a hardness of approximately 1k [X/3] without reducing tensile strength, elongation, tear strength, and compressive residual strain properties.
The technology of the present invention can be applied to a wide range of applications such as cushioning materials for automobiles and furniture, insulation materials, and daily miscellaneous goods, as it exhibits excellent effects such as being able to double-sided by 2 cnl or more.

Claims (1)

[Claims] a polyol component having at least a difunctional hydroxyl group;
In a flexible polyurethane foam obtained by reacting at least a bifunctional polyisocyanate component in the presence of a blowing agent, a catalyst, and a foam stabilizer, a 2,2- Screw(
A highly hard and flexible polyurethane foam characterized by using a mixed polyol consisting of a propylene oxide adduct of 4-hydroxyphenyl)propane, an aromatic amine-based polyoxyalkylene polyol, and/or a polymer polyol.