JPS59219344A - Production of non-rigid polyurethane foam - Google Patents

Abstract

PURPOSE:To obtain a polyurethane foam having improved elongation and/or hardness and suitable for use as cushioning material, etc., by reacting a polyether polyol with a polyisocyanate in the presence of a prim. arom. monoamine. CONSTITUTION:A polyol (A) mainly composed of a polyether polyol, e.g. propylene oxide adduct of glycerol, a polyisocyanate (B), e.g. tolylene diisocyanate or diphenylmethanediisocyanate, not more than 4pts.wt. (per 100pts.wt. component A) arom. monoamine (C), e.g. phenylamine or toluidine, and additives (D) such as a catalyst, e.g. triethylamine, a blowing agent, e.g. methylene chloride, a foam stabilizer, e.g. a silicone compd., etc. are mixed together. The mixture is expanded to obtain the desired non-rigid polyurethane foam.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing flexible polyurethane foams having improved mechanical properties, and more particularly to a method for producing flexible polyurethane foams having improved elongation and/or hardness. be. Conventional methods for producing flexible polyurethane foam include the slab foam method, in which polyether polyol and polyisocyanate are mixed together with blowing agents, catalysts, foam stabilizers, and other auxiliary agents, and discharged onto a conveyor for free foaming; The hot-cure foam method involves pouring a mixture of ether polyol-1 and polyisocyanate into a mold, closing the mold, and foaming and curing in a high-temperature (100°C or higher) heating oven. There is a cold cure foam method in which a mixture of polyols such as ether polyols or polymer polyols is injected into a mold and foamed and cured at a relatively low temperature (100'C or less). The method for producing flexible polyurethane foam of the present invention relates to a method for producing foam obtained by the slab foam method and the hot cure foam method. Processed into cushioning materials, interior materials, toys, miscellaneous goods, etc. 〇 Obtaining a high hardness foam with a constant specific gravity means that the requirement for a constant hardness can be met with a low specific gravity foam. Therefore, it has the advantage of reducing the amount of raw materials used. Conventionally, for this purpose, the reaction was carried out by increasing the equivalent ratio of the incyanate group to the active hydrogen of the polyol, or the polyfunctional polyether polyol-/I/ obtained from a tetrafunctional or higher functional compound was used as a starting material. A method is known in which the entire reaction is carried out using a polyether polyol (V) containing polyester, but the foam produced by such a method has a high hardness but a marked decrease in elongation. Such foams are unsuitable, for example, as cushions for automobiles. Adding various crosslinking agents was considered as a method to further increase the hardness, but the foam shrank and a good foam could not be obtained.In view of these circumstances, the present inventors developed a flexible polyurethane foam with high hardness and high elongation. As a result of intensive studies, we found that when producing flexible polyurethane foam by reacting polyols containing polyether polyol as the main ingredient with polyisocyanate, 4 parts by weight or less of aromatic primary foam should be added to 100 parts by weight of polyether polyol. It has been discovered that by adding a class monoamine, the elongation of the produced flexible polyurethane foam can be increased without reducing the hardness.

Generally, as the number of parts of the aromatic primary monoamine added increases, the elongation of the foam increases, but it is 4 parts by weight or less, more preferably 0.5 to 3. It was found that when 0 parts by weight of aromatic primary monoamine was added, the elongation of the foam was improved and the reactivity was well balanced.In addition, the conventional method of obtaining a foam with a constant specific gravity and high hardness, namely polyol. In the method of increasing the equivalent ratio of the isocyanate group of the polyisocyanate to the active hydrogen of the type, or in the method of jointly using a polyfunctional polyether polyol obtained from a tetrafunctional or higher functional compound as a starting material, an aromatic primary monoamine is added. For the first time, we have discovered that it is possible to produce a flexible polyurethane foam with high hardness and improved elongation. The polyether polyol used in the present invention is prepared by addition polymerizing a compound having three active hydrogen atoms or a mixture of this and a compound having two active hydrogen atoms with an alkylene oxide as a starting material, or by addition polymerizing a compound having three active hydrogen atoms with an alkylene oxide. It is obtained by mixing an alkylene oxide addition-polymerized compound with an active hydrogen atom and an alkylene oxide addition-polymerized compound with two active hydrogen atoms. Examples of compounds having three active hydrogen atoms include ethylene glycol and glopylene glycol; examples of compounds having three active hydrogen atoms include glycerin and trimethylolpropane; Ether polyols are made by addition-polymerizing alkylene oxide to a single or a mixture of compounds selected so that the starting material has 4 or more active hydrogen atoms, or by adding-polymerizing alkylene oxide to two or more compounds alone. It is obtained by mixing, and pentaerythritol, sorbitol, sugar, etc. are used as compounds having four or more active hydrogen atoms. As the alkylene oxide, ethylene oxide and propylene oxide are preferable. Polyether polyols produced by zero-boost addition polymerization reaction have an OH value in the range of 40 to 60 and are used in the present invention. The polyfunctional polyether polyol consisting of the above-mentioned compounds having an OH value in the range of 28 to 6o is used in the present invention.

The polyether polyol used in the slab foam method is preferably a polymer of propylene oxide alone or a block or random copolymer of ethylene oxide glopylene oxide containing a small amount (2% by weight or less) of ethylene oxide.

On the other hand, the polyether polyol used in the hot cure method is preferably an ethylene oxide-propylene oxide block or random copolymer containing 2 to 25% by weight of ethylene oxide. A polyfunctional polyether polyol consisting of a compound having 4 or more functional groups is used as a starting material to obtain a flexible polyurethane foam gold having high hardness and improved elongation.
It is desirable to contain 1 to 50 parts by weight, preferably 5 to 30 parts by weight of the 0 parts by weight. If it is less than 0.1 parts by weight, there is no hardness effect, and if it is more than 50 parts by weight, the moldability of the produced foam will be poor.

The polyisocyanates used in the present invention are tolylene diisocyanate (hereinafter referred to as TDI), diphenyl remethane diisocyanate, and a combination of aniline and formaldehyde.
Examples of the polymethylene polyphenyl polyisocyanate obtained by converting the compound into / are preferred, and a preferred polyisocyanate is TDI.

The catalysts used in the present invention are tertiary amines such as triethylamine, triethylenediamine, tetramethylethylenediamine, and dimethylethanolamine, and organic metals such as stannath octoate, dibutyltin dilaurate, and lead octylate. Any commonly used catalyst can be used.

The blowing agent used in the present invention is water or a volatile solvent, and examples of volatile solvents include monofluoro-trichloromethane and methylene chloride.

In addition, the foam stabilizer useful in the present invention may be selected appropriately depending on the use of the polyurethane foam; for example, Shin-Etsu Silicone F-220, F-230, and
60, F-305, F-307 and bundle V silicone 5H-
190,5H-192,5H-193°5H-194,
Silicone compounds such as 5H-195, 5H-2904, 5RX-294A are used. As auxiliary agents, use the necessary amounts of discoloration inhibitors, flame retardants, coloring agents, etc., depending on the purpose of the polyurethane foam. Just add it.

In order to produce a flexible polyurethane foam with high hardness and improved elongation, it is necessary to calculate the aromatic primary monoamine as monofunctional. It is necessary to carry out the reaction in a range where the equivalent ratio of the active hydrogen groups of the J O /l/ type and the isocyanate groups of the polyisocyanate is in the range of 1:1.02 to 1.20, and if it is less than 1:1.02, the increase in hardness will be small. Also 1:1
．． If it is more than 20, the internal heat generation of the produced foam will cause significant discoloration.

The aromatic primary monoamine in the present invention contains one or more selected from phenylamine, toluidine, and aningine. There is a method of adding the agent and other auxiliary agents at the same time when uniformly mixing them in a short time, or a method of dissolving them in advance in the polyether polyol, but there is no particular limitation on the method of addition.

The present invention will be explained below with reference to Examples.

Examples 1 to 4) Glycerin with propylene oxide added with a molecular weight of about 3000. 10 kq of trifunctional polyneedle polyol (polyol A) with an OH value of 56 mg k OH/g, 400 Da of water as a foaming agent, 100 P of Toshi Silicone 5R-192 as a foam stabilizer, ) lyethylenediamine),
Oy,! : A mixed catalyst of Stanus Octoate 30Ii+ and Para)/Reizin 200y or 400y were added and thoroughly stirred with a screw type stirrer (approximately 2.00 Or, pom). This polyol composition contains 2.4 TDI
and 2.6 TD! A polyisocyanate compound having an isomer ratio of 80:20 (hereinafter referred to as T-80) has an equivalent ratio of isocyanate groups to active hydrogen of 1.00.1.02.
．． 1.05.1.20, and stirred for about 10 seconds with a screw type stirrer (about 2.00 Or, p, In), so that the upper part of each of the length, width, and height is 1 to 71 is open. Then, the stirring solution was poured into a wooden box with paper pasted on the inside and foamed.

After being left for one day, the physical properties of the foam were examined. The results are shown in Table 1.

Example 5 Polio-/l/A]-0kLI used in Example 3
Polio-/l/ A 7 A; instead of ! / and sorbitol with propylene oxide added, molecular weight approximately 1.1
．． The same procedure as in Example 3 was carried out except that 3 kq of hexafunctional polyether polyol/l/(Polyonode-B) with 000° OH value mgkOH/f/ was used. The results are shown in Table 1 Example 6 Example 3 except that phenylamine f200f was used instead of 200 g of paratoluidine used in Example 3.
I did the same thing. The results are shown in Table 1.

Example 7 The same procedure as in Example 3 was carried out except that 2200 y of para-anisidine was used instead of 200 y of para-anisidine used in Example 3. The results are shown in Table 1.

Comparative Example 1 The same procedure as in Example 3 was carried out except that 200 ff of para-toluidine used in Example 3 was not added and the equivalent ratio was changed from 1.05 to 1.00. The results are shown in Table 1.

Comparative Example 2 The same procedure as in Example 1 was carried out except that the equivalent ratio 'i of Example 1 was changed from 1.00 to 1.25.

The results are shown in Table 1.

Comparative Example 3 Para-toluidine 200f used in Example 3 was replaced with 4
Everything was carried out in the same manner as in Example 3 except that 50y was used.

The results are shown in Table 1.

Comparative Example 4 Polyol A7k (j and polyol/
4.5 kg of polyol A instead of 3 kg of V B
The procedure was the same as in Example except that 5.5 kg of polio/I/B was used.

The results are shown in Table 1.

Examples 8 to 11 Mixed alkylene oxide with a weight ratio of propylene oxide and ethylene oxide of 90:10 was added to glycerin, and the molecular weight was about 3000. OH value 56.0 mykOa/g
trifunctional polyether polyol-/I/(polyol C)
100 copies, Wednesday 45 copies, East v v IJ-1-N5RX-
1.0 part of 294A, 0.1 part of triethylenediamine,
Add 0.1 part of Stanus octoate and 2 or 4 parts of para-carrot, and mix with a screw type stirrer (approximately 200
The mixture was thoroughly stirred using the r, p, m). This polyol composition has an equivalent ratio of incyanate groups to active hydrogen of 1.00.1.
Add T-80 so that it becomes 02.1.05.1.15,
About 10 minutes with a screw type stirrer (about 200 Or, p, m)
Stir for seconds. Length, width and height are 40cm, 40an,
Pour the above stirring liquid into a 7 cm aluminum mold and cover it with a lid. This was heated in an open air at 200° C. for about 15 minutes, then demolded, and the physical properties of the molded foam were examined. The results are shown in Table 2.

Example 12 Instead of 100 parts of polyol C used in Example 10, 70 parts of polyol C and sorbitol were added to prohyde?・Molecular weight approximately 11,00000 with added mixed alkylene oxide with a weight ratio of gin oxide and ethylene oxide of 90:1O
The same procedure as in Example 10 was carried out except that 30 parts of hexafunctional polyether polyol/I/(polyol D) having an H value of 30 rJIkOH/f was used. The results are shown in Table 2.

Example 13 The same procedure as in Example 10 was carried out except that 2 parts of para-toluidine was used instead of 2 parts of para-anisidine used in Example 10.

The results are shown in Table 2.

Example 14 The same procedure as in Example 10 was repeated except that 2 parts of phenylamine was used instead of 2 parts of para-anisidine used in Example 1O.

The results are shown in Table 2.

Comparative example 5 Para-anisidine 2ooy' used in Example 7.

The same procedure as in Example 7 was carried out except that no addition was made. The results are shown in Table 2.

Comparative Example 6 All procedures were carried out in the same manner as in Comparative Example 5 except that the equivalent ratio of Comparative Example 5 was changed from 1.00 to 1.25.Results are shown in Table 2.Comparative Example 7 200g of para-aniroginseng used in Example 10 Table 2 shows the results obtained in the same manner as in Example 10 except that 450 g was used instead of .

Comparative Example 8 Example 1 except that 45 parts of polyol/L/C and 55 parts of polio-7+zD were used instead of 70 parts of polyol/L/C and 70 parts of polyol C used in Example 12.
It was done in the same way as 2.

The results are shown in Table 2.

Procedural amendment (method) 1. Indication of the case 1982 Patent Application No. 94414 Seizouhouhou 2, Title of the invention Method for producing soft polyurethane foam 3, Person making the amendment Relationship to the case Patent applicant Amagasaki Kukuchi Address Kuguchi, Amagasaki City, Hyogo Prefecture 3-chome 13-26-4,
Date of amendment order: August 10, 1982 5. Subject of amendment: Specification

Claims (1)

[Scope of Claims] (1) Polyop-p whose main ingredient is polyether polyol
A method for producing flexible polyurethane foam gold by reacting polyisocyanate with a polyurethane foam, characterized in that 4 parts by weight or less of an aromatic primary monoamine is added to 100 parts by weight of polyether polyol/L'. Method of manufacturing polyurethane foam. (2. A flexible polyurethane foam characterized in that the aromatic primary monoamine according to claim (1) is one or a mixture of two or more selected from phenylamine, toluidine, and aningine. (3) In the method described in claims (1) and (2), the equivalent ratio of active hydrogen groups of the polyols to isocyanate groups of the polyisocyanate is 1:1.
．． A method for producing flexible polyurethane foam, characterized in that the reaction is carried out in the range of 0.02 to 1.20. (4) In the method described in claims (1), (2), and (3), the starting material is 4 or more functional polyether polyol/L' in 100 parts by weight of the total polyether polyol/L'. A method for producing a flexible polyurethane foam, comprising 1 to 50 parts by weight of a polyfunctional polyether polyol obtained from a compound.