JPH06336514A - Production of flexible foamed synthetic resin - Google Patents

Abstract

PURPOSE:To obtain the subject resin having low hardness, reduced in compression set, and excellent in curability, etc., by reacting and foaming a mixture of an organic polyisocyanate with specific polyhydroxy compounds in the presence of water and a specific additive which serve as a catalyst, a foam stabilizer, and a foaming agent. CONSTITUTION:A mixture of an organic polyisocyanate with polyhydroxy compounds containing 0.1-30wt.% polyoxyalkylene polyol which is obtained by polymerizing an alkylene oxide by ring-opening polymerization using a heterocyclic polyamine [e.g. N-(2-aminoethyl)piperazine] and has a mol.wt. of 150-2,500 per OH group is reacted and foamed in the presence of water and a given amount of an additive which serve as a catalyst, a foam stabilizer, and a foaming agent. The additive comprises at least one member selected from castor oils (derivatives) and compounds represented by formulae I to IV (wherein R and R<1> each is a 1-30C hydrocarbon group; R<2> and R<3> each is a 2-4C hydrocarbon group; R<4>, R<6>, and R<7> each is a 5-25C hydrocarbon group; R<5> is a 1-15C hydrocarbon group; (k) is 1-60; (m) is 1-25; and (n) is 1-10).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a soft foam synthetic resin using substantially only water as a foaming agent.

[0002]

2. Description of the Related Art Conventionally, trichlorofluoromethane (commonly known as R-11) or dichlorodifluoromethane (commonly known as R-) has been used in the production of foamed synthetic resin such as soft or rigid polyurethane foam used for heat insulating materials, automobile seats, furniture, cushions and the like. 12) has been used as a foaming agent.

However, due to the recent ozone problem, R
There is an urgent need to reduce the amounts of -11 and R-12 used, and as a substitute for them, a method of foaming with carbon dioxide generated in the reaction between water and isocyanate is being studied.

However, in this manufacturing method, there are problems in the moldability and foam physical properties of the foamed synthetic resin obtained,
In particular, there are many problems in the production of low-density foamed synthetic resin that uses a large amount of foaming agent.

[0005]

Particularly, in the molding of a flexible polyurethane foam, the surface skin portion of the molded polyurethane foam has a poor cure property, and the polyurethane foam is liable to peel and break when the polyurethane foam is released from the mold. The peeled skin adheres to the mold, making it difficult to clean the mold, and the appearance is very poor. Further, there are drawbacks in the physical properties of the foam, such as an increase in hardness of the obtained polyurethane foam and deterioration of compression set.

In order to solve these problems, there is a method of using a specific additive, but the method is not perfect. For example, addition of propylene carbonate reduces the hardness of polyurethane foam, but lowers the compression set and the curability. large.

The present invention eliminates the above-mentioned drawbacks in the conventional method for producing a foamed synthetic resin by water-foaming, and provides a method for producing a soft foamed synthetic resin which is excellent in foam physical properties, moldability, and surface curability and has low hardness. The purpose is to

[0008]

The present invention relates to a method for producing a soft foam synthetic resin by foaming a polyhydroxy compound, an organic polyisocyanate in the presence of a catalyst, a foam stabilizer, water as a foaming agent and an additive. 0.1 to 30% by weight of the polyhydroxy compound is a polyoxyalkylene polyol having a molecular weight of 150 to 2500 per OH group obtained by ring-opening polymerization of an alkylene oxide using a heterocyclic polyamine as an initiator, and A method for producing a soft foam synthetic resin, characterized in that 0.1 to 15% by weight of at least one additive selected from the following (A) to (E) is used as an additive based on the polyhydroxy compound. .

(A) Castor oils and / or derivatives thereof. ^{(B) RCOO- (R 2 -O} ) k -COR 1, where k = 1~60, R, a hydrocarbon group of R _¹ = C ¹ ~C _30, hydrocarbon R _² = C ² ~C ₄ The groups, provided that k R ^{2 s} are the same or different, respectively. _{(C) H 2 C = C} (CH 3) -COO- (R 3 -O) m
—CH ₃ , where m = 1 to 25, R ³ ═C _{2 to} C ₄ hydrocarbon group,
However, m R ^{3 s} may be the same or different. (D) R ⁴ —COO—R ⁵ , where R ⁴ = C ₅ -C ₂₅ hydrocarbon group, R ⁵ = C ₁ -C
₁₅ hydrocarbon radicals. ^{(E) R 6 COO- (CH} 2) n -OCOR 7, wherein n = 1 to 10, a hydrocarbon group of _{^{R 6, R 7 = C 5}} ~C 25.

The heterocyclic polyamine used as an initiator in the present invention includes the following. (1) A polyamine represented by the following general formula (1) having two active hydrogen atoms in a heterocycle;

[0011]

[Chemical 1]

(In the formula, R ⁸ and R ⁹ represent a divalent hydrocarbon group and form a 5-membered ring or a 6-membered ring together with the nitrogen atom.)

Specifically, for example, piperazines [piperazine and its C-lower alkyl-substituted compounds (2-methyl-piperazine, 2-ethyl-piperazine, 2-butyl-piperazine, 2-hexyl-piperazine, 2,5- Dimethyl-piperazine, 2,6-dimethyl-piperazine, 2,3
-Dimethyl-piperazine, 2,2-dimethyl-piperazine, 2,3,5,6-tetramethyl-piperazine, 2,
2,5,5-Tetramethyl-piperazine, etc.)]; imidazolidines (imidazolidine and its C-lower alkyl substituted products: the same expression will be used hereinafter); pyrazolidines and the like.

(2) Aminoalkyl-substituted heterocyclic amine;
Aminoalkyl-substituted heterocyclic polyamines such as piperazines, imidazolidines, and pyrazolidines represented by the above general formula (1) [aminoethyl-substituted compounds, aminopropyl-substituted compounds (N-substituted compounds, N, N'- Di-substituted and C
-Including substitutions)]. Specifically, for example, N- (2-
Aminoethyl) piperazine, N, N′-di (2-aminoethyl) piperazine and the like can be mentioned.

It is necessary that these heterocyclic polyamines have two or more active hydrogen atoms, and those having 2 to 6 and preferably 2 to 4 active hydrogen atoms are suitable. Among the above heterocyclic polyamines, piperazines and aminoalkyl-substituted piperazines are particularly preferable. Among them, N- (2-aminoethyl) piperazine is preferable from the viewpoints of reactivity, physical properties of the produced polyurethane, and moldability.

Two or more of the above heterocyclic polyamines may be used in combination. Moreover, you may use together with another amine compound. As such an amine compound, for example, a compound having two or more active hydrogen atoms, monoethanolamine,
Alkanolamines such as diethanolamine, triethanolamine; alkylenediamines, polyalkylenepolyamines, phenylenediamines, tolylenediamines, xylylenediamines, polyphenylpolyamines, cyclohexylenediamines, etc., aliphatic, aromatic or alicyclic polyamines; etc. Is mentioned.

The heterocyclic polyamine-initiated polyoxyalkylene polyol can be obtained by ring-opening polymerization of alkylene oxide by a conventional method using a heterocyclic polyamine as an initiator.

A small amount of other monoepoxides such as halogen-containing alkylene oxides such as epichlorohydrin, tetrahydrofuran, styrene oxide, glycidyl ether, etc. may be added together with the alkylene oxide, but preferably substantially only the alkylene oxide is added. Is used.

The alkylene oxide has 2 to 4 carbon atoms.
The alkylene oxide of is suitable, and propylene oxide alone or a combination of propylene oxide and ethylene oxide is particularly preferable. When propylene oxide and ethylene oxide are used in combination (usually in a weight ratio of 30:70 to 95:
5, especially 70:30 to 95: 5), a mixture of the two may be added, they may be added separately in sequence, or these may be combined. The hydroxyl value of the polyoxyalkylene polyol is adjusted by the amount of alkylene oxide added.

When ethylene oxide is added last, it is a cap of ethylene oxide. Also, the proportion of primary hydroxyl groups can be adjusted by further adding a small amount of propylene oxide after the ethylene oxide cap.

The addition of the alkylene oxide is carried out without catalyst or in the presence of a catalyst such as an alkali catalyst, an amine catalyst and an acidic catalyst (particularly in the latter stage of the addition of the alkylene oxide) under normal pressure or pressure. The heterocyclic polyamine may be used as it is or in an inert liquid such as xylene or DMF, an active hydrogen atom-containing liquid such as water, a polyhydric alcohol such as ethylene glycol or glycerin, or a polyalkylene oxide adduct of a polyamine prepared in advance. The alkylene oxide can be ring-opening polymerized in the presence of a suitable medium.

The molecular weight per OH group of the heterocyclic polyamine-initiated polyoxyalkylene polyol can be varied over a wide range depending on the physical properties of the desired foamed resin. When manufacturing flexible polyurethane foam, O
The molecular weight per H group is 150 to 2500, preferably 300 to 2000, more preferably 500 to 1700.
Is.

The heterocyclic polyamine-initiated polyoxyalkylene polyol is a polyhydroxy compound of 0.1
.About.30% by weight, preferably 0.1% of the polyhydroxy compound.
It is preferable to use 5 to 15% by weight.

As the polyhydroxy compound other than the heterocyclic polyamine-initiated polyoxyalkylene polyol used in the present invention, at least one polyoxyalkylene polyol having an average hydroxyl value of about 10 to 90 and /
Alternatively, a polyol whose main component is a polyoxyalkylene polyol containing polymer fine particles is preferable.

The polyoxyalkylene polyol and / or the polymer fine particle-containing polyoxyalkylene polyol may be a mixture of two or more kinds, and a small amount (not more than about 20% by weight based on the total polyol) of non-polyoxyalkylene. It may contain a polyol, for example, a polyester-based polyol or a polydiene-based (especially butadiene homopolymer or copolymer) polyol having two or more hydroxyl groups.

The polyhydroxy compound preferably consists essentially of polyoxyalkylene polyol or polyoxyalkylene polyol containing polymer fine particles. However, a polyol having a low molecular weight (usually about 600 or less) called a cross-linking agent or a chain extender is not included in the polyol as used herein.

The present invention is particularly suitable for a method for producing a flexible polyurethane foam among flexible foamed resins. The flexible polyurethane foam is roughly classified into a hot cure foam and a cold cure foam according to the curing method, but any of them can be applied.

The average hydroxyl value of the polyol for hot cure foam in the present invention is usually in the range of about 40 to 90, particularly about 50 to 80. Therefore, it is preferable that the average hydroxyl value of the polyol is within this normally used range. Suitably the average number of hydroxyl groups in the polyol is about 2-8, especially about 2-4, most preferably about 2.
It is preferably 5 to 3.5.

The average hydroxyl value of the polyol for cold cure foam in the present invention is usually about 10 to 7.
0, especially in the range of about 15-65. Therefore, it is preferable that the average hydroxyl value of the polyol is within this normally used range. The average number of hydroxyl groups in the polyol is about 2
A value of 8 is suitable, particularly about 2 to 4, most preferably about 2.5 to 4.5.

The polyoxyalkylene polyol can be produced by the usual method as described above. The initiator will be described later.
It may be a so-called primary polyoxyalkylene polyol having a primary hydroxyl group obtained by capping ethylene oxide at the terminal, and the terminal having an oxyethylene group inside the oxyalkylene chain may be capped or capped with ethylene oxide. It may be a polyoxyalkylene polyol which is not. In this case, it is preferable that the oxyethylene group content in the polyoxyalkylene polyol is 30% by weight or less on average, including the ends and the inside of the oxyalkylene chain.

As the initiator, polyhydric alcohols, polyhydric phenols, monoamines or polyamines other than the above-mentioned heterocyclic polyamines, and others can be used, but polyhydric alcohols and polyhydric phenols are suitable, and particularly polyhydric alcohols. Is preferred. Also, two or more initiators can be used in combination. Specific examples of the initiator are shown below, but the initiator is not limited thereto. Particularly preferred initiators are trihydric polyhydric alcohols,
Alternatively, it is a mixture with a divalent or tetravalent or higher initiator containing it as a main component.

Divalent initiators: ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, bisphenol A. Trivalent initiator: glycerin, trimethylolpropane, hexanetriol. Tetravalent or higher-valent initiator: pentaerythritol, diglycerin, ditrimethylolpropane, dextrose, sorbitol, sucrose,
Novolac.

The polymer fine particle-containing polyoxyalkylene polyol containing the polymer fine particles is prepared by polymerizing an ethylenically unsaturated monomer in the polyol, mixing the separately prepared polymer fine particles with the polyol, or an ethylenically unsaturated group. It is produced by a method of polymerizing a macromonomer having OH and an ethylenically unsaturated monomer in a polyol. This polymer fine particle-containing polyoxyalkylene polyol is also called a polymer polyol.

Examples of the ethylenically unsaturated monomer include styrene and acrylonitrile. For example, a polymer polyol obtained by graft-polymerizing these monomers in a polyol in the presence of a free radical polymerization catalyst can be used as a part or the whole amount of the polyhydroxy compound. The amount of the polymer fine particles is 50% by weight or less, especially 30% by weight based on the total polyoxyalkylene polyol.
The following are preferred.

The other main raw material for producing the soft foamed resin is a polyisocyanate compound. As the polyisocyanate compound, various compounds having two or more isocyanate groups can be used, but aromatic polyisocyanates are particularly suitable. As the aromatic polyisocyanate, a mononuclear or polynuclear compound having an isocyanate group bonded to an aromatic nucleus or a modified product thereof is suitable.

Specific examples include tolylene diisocyanate, diphenylmethane diisocyanate, polymethylene polyphenyl isocyanate, and their prepolymer type, carbodiimide type, urea type and other modified products.

Two or more of these polyisocyanate compounds can be used in combination. The amount of the polyisocyanate compound to be used is preferably about 85 to 120, particularly about 90 to 110, which is expressed as 100 times the number of isocyanate groups with respect to the number of active hydrogens in the total active hydrogen-containing compound (usually called isocyanate index).

The polyhydroxy compound is mainly a polyol such as the above polyoxyalkylene polyol, but it also contains a small amount of water as a foaming agent, and depending on the case, a small amount of the chain extender or the crosslinking agent may be used. You can These are usually compounds having a molecular weight of about 600 or less and having two or more active hydrogens, and particularly include polyhydric alcohols having a molecular weight of 400 or less, low molecular weight polyether polyols, alkanolamines and polyamines.

The other one of the essential components of the foamable mixture is a catalyst. As a catalyst for producing a flexible polyurethane foam, a tertiary amine catalyst and an organic metal compound, especially an organic tin compound are usually used, and they are usually used in combination. Various tertiary amine-based catalysts can be used as the tertiary amine-based catalyst.

For example, triethylenediamine, N-ethylmorpholine, N, N-dimethylaminoethylmorpholine, triethylamine, N, N, N ', N'-tetramethylhexamethylenediamine, bis (2-dimethylaminoethyl) ether, N, N ′, N′-trimethylaminoethylethanolamine, and the like.

Two or more of these can be used in combination. A preferred tertiary amine-based catalyst is triethylenediamine,
Especially preferred is the mixture of triethylenediamine and dipropylene glycol in the weight ratio 1: 2, known under the trade name "abco-33LV".

The amount of the polyhydroxy compound 1 used can be varied depending on the desired reaction conditions, etc.
About 0.01 to 2.0 parts by weight, preferably 0.02 to 1.5 parts by weight, relative to 00 parts by weight, is suitable.
It is suitable to use 0.1-1.0 part by weight as "co-33LV".

The organometallic compound catalyst is most preferably an organotin compound catalyst, for example, stannas octoate, stannas laurate, dibutyltin dilaurate, dibutyltin dimaleate, dibutyltin diacetate, dioctyltin diacetate. is there. Particularly, stannas octoate and dibutyltin dilaurate are preferable.

The amount of the organotin compound catalyst used is usually 0.01 to 1.0 part by weight based on 100 parts by weight of the polyol. However, the amount of this catalyst used must be delicately changed depending on the type and reactivity of the polyol and other conditions, and various optimum ranges are relatively narrow.

The additives used in the present invention are (A) to
It is at least one selected from (E). (A) Castor oils and / or derivatives thereof. ^{(B) RCOO- (R 2 -O} ) k -COR 1, where k = 1~60, R, a hydrocarbon group of R _¹ = C ¹ ~C _30, hydrocarbon R _² = C ² ~C ₄ The groups, provided that k R ^{2 s} are the same or different, respectively. _{(C) H 2 C = C} (CH 3) -COO- (R 3 -O) m
—CH ₃ , where m = 1 to 25, R ³ ═C _{2 to} C ₄ hydrocarbon group,
However, m R ^{3 s} may be the same or different. (D) R ⁴ —COO—R ⁵ , where R ⁴ = C ₅ -C ₂₅ hydrocarbon group, R ⁵ = C ₁ -C
₁₅ hydrocarbon radicals. ^{(E) R 6 COO- (CH} 2) n -OCOR 7, wherein n = 1 to 10, a hydrocarbon group of _{^{R 6, R 7 = C 5}} ~C 25.

The compounds (A) to (E) will be described. (A) Castor oils and / or derivatives thereof. The castor oils and / or their derivatives (A) may be refined castor oil, semi-refined castor oil, unrefined castor oil, or a derivative of castor oil such as hydrogenated castor oil. Specifically, URIC H- made by Ito Oil
However, the number is not limited to this.

(B) RCOO- (R ² —O) _k —COR ¹ , where k = ^{1 to} 60, R, R ¹ = C _{1 to} C ₃₀ hydrocarbon group, R ² = C _{2 to} C ₄ Of the hydrocarbon groups, provided that k R ^{2 s} are the same or different. As k, 5 to 50 is particularly preferable, and 10 to 40 is most preferable.
Is. R and R ¹ are alkyl groups or alkenyl groups having 1 to 30 carbon atoms and may be the same or different. R
² is an ethylene group, a propylene group, a butylene group or the like.

As (R ² —O) _k , a polyoxyethylene chain, a polyoxypropylene chain or a polyoxyethylene / polyoxypropylene copolymer chain is particularly preferable. The copolymer chain may be either random or block copolymer chain. These polymer chains can also be obtained by ring-opening polymerization of ethylene oxide and / or propylene oxide with water, propylene glycol, ethylene glycol, 1,4-butanediol and the like. Specifically as (B), Unisafe NKL-9520 made by NOF CORPORATION
However, the present invention is not limited to these.

(C) H ₂ C = C (CH ₃ ) -COO-
(R ³ —O) _m —CH ₃ , where m = 1 to 25, R ³ ═C _{2 to} C ₄ hydrocarbon group,
However, m R ^{3 s} may be the same or different. Especially as m, 1-20 are preferable and 1-10 are the most preferable. R ³ is an ethylene group, a propylene group, a butylene group or the like.

As (R ³ —O) _k , a polyoxyethylene chain, a polyoxypropylene chain or a polyoxyethylene / polyoxypropylene copolymer chain is particularly preferable. The copolymer chain may be either random or block copolymer chain. It is particularly preferably a polyoxyethylene chain. Specific examples of (C) include Bremmer PME-400 manufactured by NOF CORPORATION, but are not limited thereto.

(D) R ⁴ --COO--R ⁵ , where R ⁴ = C ₅ -C ₂₅ hydrocarbon group, R ⁵ = C ₁ -C
₁₅ hydrocarbon radicals. R ⁴ is a residue of a carboxylic acid having 5 to 25 carbon atoms, particularly a residue of a carboxylic acid such as oleic acid, stearic acid, palmitic acid, lauric acid and erucic acid. R ⁵ is an alkyl group, especially methyl, ethyl,
Examples include butyl and octyl groups. Specific examples thereof include Unistar MB-816 manufactured by NOF CORPORATION, but are not limited thereto.

(E) R ⁶ COO— (CH ₂ ) _n —OCOR ⁷ , where n = 1 to 10 and R ⁶ and R ⁷ ═C _{5 to} C ₂₅ hydrocarbon groups. R ^6, R ⁷ is the residue of a carboxylic acid of 5 to 25 carbon atoms, in particular oleic acid, stearic acid, palmitic acid, lauric acid, residues of carboxylic acids such as erucic acid. R ⁶ and R ⁷ may be the same or different. n is especially 3
~ 6 are preferred.

The amount of the above additives used is 0.1 to 15% by weight based on the polyhydroxy compound. It is preferably 0.5 to 10% by weight, especially 3 based on the polyhydroxy compound.
-10 wt% is preferable.

Another component added to the foamable mixture is a foaming agent. As the foaming agent, only water is particularly preferable, but a halogenated hydrocarbon-based foaming agent, a low boiling point gas such as air, or another foaming agent may be used together in a small amount.

Examples of the halogenated hydrocarbon-based blowing agent include trichlorofluoromethane, dichlorodifluoromethane, dichloromethane, monochlorodifluoromethane, 1,1-dichloro-2,2,2-trifluoroethane, 1,1-dichloro. -1-Fluoroethane and the like. The amount of the foaming agent used may vary depending on the density of the desired foam, but is usually about 1 to 100 parts by weight of the polyol.
10 parts by weight, especially about 2-8 parts by weight.

Still another normally essential component is a siloxane-based foam stabilizer such as polydialkylsiloxane and polydialkylsiloxane-polyoxyalkylene block copolymer. Other optional components include, for example, colorants, antioxidants, ultraviolet absorbers, light stabilizers, flame retardants, and other additives that can be used in the production of foamed synthetic resins.

The soft foam synthetic resin having high skin strength obtained by the present invention is particularly suitable as a cushion sheet material for automobiles. However, the present invention is not limited to the automobile seat material, and can be applied as a cushion seat material for other uses, or to the field where the soft foam synthetic resin has been used in the past.

[0058]

EXAMPLES The present invention will be specifically described below with reference to Examples and Comparative Examples. Parts indicate parts by weight. (Polyol) Polyol A; Hydroxyl value obtained by addition polymerization reaction of propylene oxide with glycerin 70.1 mgKOH /
g of polyoxypropylene polyol. Polyol B: Hydroxyl value obtained by addition polymerization reaction of propylene oxide with glycerin: 34.0 mgKOH /
g of polyoxypropylene polyol. Polyol C: A polymer polyol having a hydroxyl value of 28.0 mg KOH / g, which is obtained by subjecting glycerin to an addition polymerization reaction of propylene oxide and further graft-polymerizing acrylonitrile.

Additive A: URIC H-30 (made by Ito Oil Co., Ltd.). Additive _{B; CH 3 COO- [CH 2} -CH (CH 3) -
O] _k -COCH ₃ , molecular weight 1070. Additive C: Bremmer PME-400 (manufactured by NOF CORPORATION). Additive D: Unistar MB-816 (made by NOF Corporation). Additive E: propylene carbonate (manufactured by Atlantic Richfield).

Heterocyclic polyamine-initiated polyalkylene polyol F; a polyol having a molecular weight of 3000 and an ethylene oxide content of 10% by weight, which is obtained by addition-polymerizing propylene oxide and ethylene oxide to N- (2-aminoethyl) piperazine. Heterocyclic polyamine-initiated polyalkylene polyol G; a polyol having a molecular weight of 5000 and an ethylene oxide content of 15% by weight, which is obtained by an addition polymerization reaction of N- (2-aminoethyl) piperazine with propylene oxide and ethylene oxide.

Example 1 90 parts of polyol A, 5 parts of additive A, 5 parts of heterocyclic polyamine-initiated polyalkylene polyol F, 5.5 parts of water, amine catalyst [Dabc
o-33LV (Sankyo Air Products) 0.32 parts, D
abco-XDM (Sankyo Air Products) 0.05
Part and NC-IM (made by Sankyo Air Products) 0.05
Part mixture], a foam stabilizer SZ-1142 (manufactured by Nippon Unicar) 1.5 parts and stanas octoate 0.12 parts in a mixture of TDI-80 (2,4-TDI / 2,6-TDI).
= 80/20 mixture) was mixed under the conditions of a liquid temperature of 25 ° C. and an isocyanate index of 95.

Next, 350 mm × 350 mm × 100 mm
Foaming was performed at a mold temperature of 40 ° C. using the aluminum mold. After curing in a 170 ° C. oven for 10 minutes, the temperature was kept at 150 ° C. and the mold was removed. Table 1 shows the evaluation results of the physical properties of the soft polyurethane hot mold foam after demolding.

(Examples 2 to 4 and Comparative Example 1) The additives shown in Table 1 were used instead of the additive A, and the polyol A and the heterocyclic polyamine-initiated polyalkylene polyol F and the additives were used in the proportions shown in Table 1. A flexible polyurethane hot mold foam was produced in the same manner as in Example 1 except that was used. The evaluation results are shown in Table 1.

Comparative Example 2 A flexible polyurethane hot mold foam was produced in the same manner as in Example 1 except that the additive and the heterocyclic polyamine-initiated polyalkylene polyol F were not used. The evaluation results are shown in Table 1.

(Example 5) 60 parts of polyol B, 30 parts of polyol C, 5 parts of additive A, 5 parts of heterocyclic polyamine-initiated polyalkylene polyol G, 3.0 parts of water,
Amine catalyst [Dabco-33LV 0.65 parts and N
aax-A-1 (made by Union Carbide) 0.05 part mixture], a foam stabilizer SF-2962 (made by Toray Dow Corning Silicone) 1.00 parts and triethanolamine 2.0 parts in a mixture TM -20 [TDI-80 / mixture of crude MDI = 80/20] was mixed under the conditions of a liquid temperature of 25 ° C. and an isocyanate index of 105, and foaming was performed at a mold temperature of 60 ° C. using the same mold as in Example 1. .

Next, curing was carried out in an oven at 80 ° C. for 6 minutes to produce a flexible polyurethane cold cure foam. Table 1 shows the evaluation results of physical properties.

Examples 6 to 9 and Comparative Example 3 Same as Example 5 except that the additives shown in Table 2 and the heterocyclic polyamine-initiated polyalkylene polyol G were used and the raw materials were used in the proportions shown in Table 2. A flexible polyurethane cold cure foam was manufactured by the method described in 1. The evaluation results are shown in Table 2.

Comparative Example 4 A flexible polyurethane cold cure foam was produced in the same manner as in Example 5 except that no additive was used. The evaluation results are shown in Table 2.

[0069]

[Table 1]

[0070]

[Table 2]

[0071]

EFFECT OF THE INVENTION It is possible to prevent foaming in water and deterioration of compression set and cure property due to additives, and to obtain a foam having a low density and a low hardness.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁵ Identification code Internal reference number FI technical display area C08L 75:04

Claims (2)

[Claims] 1. A method for producing a soft foam synthetic resin by foaming a polyhydroxy compound and an organic polyisocyanate in the presence of a catalyst, a foam stabilizer, water as a foaming agent and an additive. 30% by weight has a molecular weight of 150 to 150% per OH group obtained by ring-opening polymerization of an alkylene oxide using a heterocyclic polyamine as an initiator.
2500 polyoxyalkylene polyol and at least one additive selected from the following (A) to (E) as an additive is added to the polyhydroxy compound in an amount of 0.
A method for producing a soft foam synthetic resin, which comprises using 1 to 15% by weight. (A) Castor oils and / or derivatives thereof. ^{(B) RCOO- (R 2 -O} ) k -COR 1, where k = 1~60, R, a hydrocarbon group of R _¹ = C ¹ ~C _30, hydrocarbon R _² = C ² ~C ₄ However, k R ^{2 s} may be the same or different. _{(C) H 2 C = C} (CH 3) -COO- (R 3 -O) m
-CH _3, wherein m = 1 to 25, a hydrocarbon group of R ³ = C ₂ ~C _4, however, m-number is R ³ may be each the same or different. (D) R ⁴ —COO—R ⁵ , where R ⁴ = C ₅ -C ₂₅ hydrocarbon group and R ⁵ = C ₁ -C ₁₅ hydrocarbon group. ^{(E) R 6 COO- (CH} 2) n -OCOR 7, wherein n = 1 to 10, a hydrocarbon group of _{^{R 6, R 7 = C 5}} ~C 25. 2. The method for producing a flexible foamed resin according to claim 1, wherein the heterocyclic polyamine is N- (2-aminoethyl) piperazine.