JPH07258374A - Production of flexible urethane foam - Google Patents

Abstract

PURPOSE:To produce the foam which can exhibit high performance even in a low filling ratio by using a polyol containing a dispersed diurea compound obtained by reacting an aromatic monoamine with a diisocyanate in the polyol. CONSTITUTION:An organic-filler-filled polyurethane foam is obtained by using a polyol component (A') at least partially consisting of a polyol (A) containing 0.1-20wt.% dispersed diurea compound obtained by reacting an aromatic monoamine (C) with a diisocyanate compound (B) in polyol A, a polyisocyanate, a blowing agent and additives. The polyol component used in the above production may further contain a low-molecular, polyether, castor oil or the like polyol. The diurea compound obtained by using 4,4'-diphenylmethane diisocyanate as component B and aniline as component C is desirable. Component A' is obtained by heating an A/C mixture under agitation and adding component B to the reaction mixture under agitation. According to this process, a flexible urethane foam of good properties can be obtained.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to a method for producing a flexible urethane foam using an organic filler-containing polyol. More specifically, it relates to a method for producing a flexible urethane foam using a polyol in which a diurea compound is dispersed.

[0002]

2. Description of the Related Art It is known to fill polyurethane such as polyurethane foam with a powdered filler. For example, Japanese Patent Publication No. 1-51492 and Japanese Patent Publication No. 3-368.
No. 8 and US Pat. No. 4,108,791. A method for producing polyurea as a filler is also known.

[0003]

However, when a powdered filler is filled in polyurethane such as polyurethane foam by the conventional technique, the tensile strength, elongation and the like generally decrease. It is considered that this is because the adhesion between the urethane resin and the filler is not good. Therefore, it has been attempted to maintain the physical properties of the filler by surface-treating it with a fatty acid, a silane coupling agent, titanate, etc., but this is not sufficient.

In the case of producing polyurea as a filler, for example, a method of mixing polyurea produced in a suitable solvent with polyurethane produced separately in a solvent in an arbitrary blend is generally known. However, this method is not preferable as an industrial method for producing polyurethane because the production process is complicated. Moreover, although a method for producing polyurea in a polyol is already known,
In most of these, 20% by weight or more of polyurethane is made of polyurea, and it is desired to obtain good physical properties with a small amount of filler. This is also true for the method of separately producing polyurethane and polyurea.

An object of the present invention is to provide a flexible urethane foam which has good physical properties even with a relatively small amount of filler and is reinforced without significantly impairing other properties.

[0006]

Means for Solving the Problems The inventors of the present invention have conducted extensive studies to solve such conventional problems, and as a result, have found a diurea compound-dispersed polyol obtained by reacting a diisocyanate compound with an aromatic monoamine in the polyol. By using it, good physical properties can be obtained with a relatively small amount of filler, and a flexible urethane foam that can be reinforced without significantly impairing other properties has been provided.
That is, the polyol component (A) and the polyisocyanate (B
1) In the method for producing a flexible urethane foam using a foaming agent and an additive, as the polyol component (A),
Part or all of the aromatic monoamine (C) and diisocyanate compound (B2) in the polyol (A1)
Is a diurea compound-dispersed polyol (A2) containing 0.1 to 20% by weight of a diurea compound obtained by the above reaction.

Polyol component (A) used in the present invention
Examples of the polyol (A3) other than (A2) include low molecular weight polyols, polyether-based polyols, polyester-based polyols, castor oil-based polyols, and polycarbonate polyols. These can be used alone or as a mixture of two or more kinds.

As the low molecular weight polyol, divalent ones such as ethylene glycol, diethylene glycol, propylene glycol, 1,4-butanediol,
1,6-hexanediol, neopentyl glycol,
Examples of trivalent or higher valent compounds such as hydrogenated bisphenol A (three to eight valent compounds) include glycerin, trimethylolpropane, hexanetriol, pentaerythritol, sorbitol and sucrose. The low molecular weight polyol has an equivalent weight of 31 to 400, the other polyol has an equivalent weight of 400 to 10,000, and 2 to 16 per molecule.
It contains one hydroxyl group.

The polyether polyol preferably has an equivalent weight of 300 to 5000 and has 2 to 4 hydroxyl groups in one molecule, and examples thereof include ethylene glycol, diethylene glycol, propylene glycol,
Glycols such as dipropylene glycol, glycerin, trimethylolethane, trimethylolpropane,
Examples thereof include hydroxyl group-containing polyether polyols obtained by additionally polymerizing polyols such as pentaerythritol and the like with alkylene oxides such as ethylene oxide and propylene oxide.

The polyester polyol preferably has an equivalent weight of 300 to 5000 and has 2 to 4 hydroxyl groups in one molecule, and examples thereof include ethylene glycol, diethylene glycol, triethylene glycol, 1,2-propylene glycol and One or two of compounds having at least two hydroxyl groups such as 1,3-butanediol, 1,4-butanediol, tetramethylene glycol, hexamethylene glycol, glycerin, trimethylolpropane, pentaerythritol and sorbitol. It can be produced by a known method using one or more species and a polycarboxylic acid compound. Also included are polyester polyols such as those obtained by ring-opening polymerization of caprolactone.

As a castor oil-based polyol, an equivalent weight of 30
Examples thereof include ester exchange polyols of castor oil and castor oil or castor oil fatty acid with the aforementioned low molecular weight polyols, polyether polyols and polyester polyols, or esterified polyols.

Polycarbonate polyols having an equivalent weight of 300 to 5000 are exemplified by alcohol condensation reaction of glycols and dialkyl carbonate such as dimethyl and diethyl, phenol condensation reaction of glycols and diphenyl carbonate, or glycols and ethylene carbonate. Examples thereof include those obtained by ethylene glycol condensation reaction and the like. Examples of the glycols include aliphatic diols such as 1,6-hexanediol, diethylene glycol, propylene glycol, 1,4-butanediol, 3-methyl-1,5 pentanediol and neopentyl glycol, or
Examples thereof include alicyclic diols such as 1,4-cyclohexanediol and 1,4-cyclohexanedimethanol. A particularly preferred polyol (A3) is a polyether polyol containing 3 hydroxyl groups in one molecule and having an equivalent weight of 1000 to 6000.

As the polyol (A1) used in the diurea compound-dispersed polyol (A2) in the polyol component (A) of the present invention, for example, a polyester having 2-3 hydroxyl groups per molecule and having an equivalent weight of 500-3000. Polyols and polyether polyols can be used. Particularly preferred is a polyether polyol,
This is the reaction of propylene oxide and ethylene oxide with a divalent or trivalent initiator in sequence to 1000-2000.
Obtained by making an equivalent amount of primary hydroxyl terminated polyether. Such compounds are described, for example, in US Pat. No. 4,394,491.

The aromatic monoamine (C) used in the present invention has no substituent other than an amino group or is meta-substituted, such as aniline, metachloroaniline, metabromoaniline, metatoluidine, and These mixtures are mentioned. The aromatic monoamine is preferably 0.05 to 5.0 parts by weight with respect to 100 parts by weight of the polyol.

Diisocyanate compound (B2) used in the diurea compound-dispersed polyol (A2) of the present invention
Examples thereof include diphenyltan diisocyanate, diphenyltan diisocyanate hydride, isophorone diisocyanate, and mixtures thereof.
A particularly preferred diurea compound is the reaction product of aniline and 4,4'-diphenylmethane diisocyanate.

The compounding ratio of the aromatic monoamine (C) and the diisocyanate compound (B2) is 0.1 to 1.0 mol of the diisocyanate compound, preferably 0.4 to 0.6 mol, and more preferably 1 mol of the aromatic monoamine. Is preferably 0.5 mol. Diisocyanate compound 1 molecule of NCO
Two amino groups of two aromatic monoamines react with two groups, respectively, and the resulting diurea compound aggregates to have an aspect ratio of an average length of less than 10 μm and an average diameter of at least 4 and a melting point of more than 200 ° C. It becomes an organic filler having.

The diurea compound-dispersed polyol (A2) of the present invention contains about 60 parts of a mixture containing 0.05 to 5.0 parts by weight of the aromatic monoamine (C) per 100 parts by weight of the polyol (A1). By stirring at 30 ° C. for 30 minutes, adding the diisocyanate compound at a ratio of 0.1 to 1.0 mol with respect to 1 mol of the aromatic monoamine, and stirring for 1 hour or more, and reacting the aromatic monoamine and the diisocyanate compound in the polyol. can get.

The diurea compound in the diurea compound-dispersed polyol of the present invention is preferably contained in an amount of 0.1 to 20 parts by weight. If it is less than 0.1% by weight, the effect as a reinforcing material is not exhibited, and if it exceeds 20 parts by weight, the viscosity of the diurea compound-dispersed polyol increases and it becomes difficult to work, which is not preferable.

The polyisocyanate (B
In 1), one molecule has at least two NCO groups on average, and the NCO group may be bonded to an aromatic or aliphatic carbon atom. Preferred aromatic isocyanates are, for example, 2,4- or 2,6-toluene diisocyanate, diphenylmethane diisocyanate (hereinafter abbreviated as MDI), p-phenylene diisocyanate, polymethylene polyphenyl polyisocyanate (hereinafter abbreviated as polymeric MDI). ), And mixtures thereof. Further, derivatives of MDI and the MDI prepolymer or its quasi-prepolymer are also effective. Particularly preferred aliphatic isocyanates include, for example, hydrogenated derivatives of the aromatic isocyanates, hexamethylene diisocyanate, isophorone diisocyanate and cyclohexane diisocyanate. A particularly preferred polyisocyanate is polymeric MDI. Further, the polyisocyanate (B1) having an NCO content of 0.5 to 30% by weight.
The prepolymers and quasi-prepolymers are also effective.

The diisocyanate compound has a ratio of NCO groups of 0.7 to 5, preferably 0.8 to 1.5, and more preferably 0.95 to 1.2 with respect to 1 equivalent of active hydrogen groups in the diurea compound-dispersed polyol. A larger amount of the diisocyanate compound (B2) can be used, but is reacted, but which involves the formation of an isocyanurate-containing polyurethane.

The flexible urethane foam of the present invention is characterized in that it is produced using a diurea compound-dispersed polyol and a polyisocyanate as basic reaction components, but other polyols and additives can be used if necessary.
Examples of the additives include a foaming agent, a foam stabilizer, a catalyst, a surfactant, a viscosity reducing agent, a pigment or a dye, a flame retardant, an antioxidant, an ultraviolet absorber, a filler, and other auxiliary agents.

Water is preferable as the foaming agent, but if necessary, it does not seriously affect the global environment,
Alternatively, other known materials having less problems can be used. This known blowing agent includes methylene chloride, monochlorodifluoromethane, dichlorodifluoromethane, dichloromonofluoromethane, and so-called azo blowing agents,
Water, hydrocarbons, halogenated methane or mixtures thereof are preferred, although finely divided solids or other substances which evolve gas under the conditions of the foaming reaction are included. Water is advantageously used in an amount of 0.5 to 10, preferably 1 to 5 parts per 100 parts by weight of polyol. Hydrocarbons and halogenated alkanes are advantageously used in amounts of 5 to 75 parts per 100 parts by weight of polyol.

As the foam stabilizer, there may be mentioned known ones generally used in the production of polyurethane foam. Examples thereof include polydimethylsiloxane-polyalkylene oxide block polymer and vinylsilane-polyalkylene polyol polymer.

As the catalyst, known organometallic catalysts and tertiary amine compounds used in the production of polyurethane foam are used. As the organic metal catalyst, for example, dibutyltin dilaurate is preferable. Other catalysts include, for example, tertiary amines, diazahirocycloalkenes and salts thereof, and organometallic compounds described in U.S. Pat. No. 4,495,081, which may be used as a mixture. It is possible. The catalyst is polyol 1
0.001 to 0.5 parts of the organometallic catalyst is used with respect to 00 parts by weight. Tertiary amine is 0.1 per 100 parts by weight of polyol.
Advantageously, it is used in the range from 3 parts.

[0025]

According to the present invention, it is possible to provide a flexible urethane foam with a relatively small amount of organic filler without significantly impairing other properties. In addition, since the filler is manufactured in polyol, it is a manufacturing method that is industrially well-used and has excellent performance, so it is effective for furniture, beds, cushion materials for automobile seats, automobile parts and other applications. Is.

[0026]

EXAMPLES The present invention will be described in more detail with reference to Examples and Comparative Examples, but the present invention is not limited thereto. In Examples and Comparative Examples, "part" means "part by weight" and "%" means "% by weight".

Example 1 Preparation of Diurea Compound-Dispersed Polyol In a four-necked flask equipped with a thermometer, a stirrer, and a nitrogen seal tube, 2.2 parts of aniline was added with a trifunctional polyol (Asahi Denka Kogyo, EL-823, molecular weight). 5000) 995 parts, and the mixture was stirred and mixed at 60 ° C. for 30 minutes. Next, 2.8 parts of MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MT) was added and reacted at 60 ° C. for 1 hour to give a diurea compound of 0.
White diurea compound-dispersed polyol containing 5% (A
2) was obtained. Production of Polyurethane Foam Molded Product 100 parts of the above-mentioned polyol (A2), 3.5 parts of water as a foaming agent, 1.0 part of triethylenediamine (containing 66.7% of dipropylene glycol) as a catalyst and Bis-
(2-dimethylaminoethyl) ether (containing 30% dipropylene glycol) and 1.0 part of SZ-1306 (manufactured by Nippon Unicar) as a foam stabilizer are mixed in advance, and MDI-based polyisocyanate (manufactured by Nippon Polyurethane Industry, Coronate 110)
6) and 25 were heated to 25 ° C., and the mixture having the NCO index of 100 was stirred with a homomixer for 10 seconds.
At the same time as pouring into the open mold to allow free foaming, 5
It was poured into a mold of 300 × 300 × 100 mm preheated to 5 ° C., and after 5 minutes, it was demolded and cured at 25 ° C. for 16 hours to obtain a polyurethane foam molded product. The physical properties of the obtained polyurethane foam molded product are shown in Table 1.

Example 2 To a four-necked flask equipped with a thermometer, a stirrer and a nitrogen sealed tube, 4.3 parts of aniline and 990 parts of trifunctional polyol (EL-823, Asahi Denka Kogyo, molecular weight 5000) were added. And mixed at 60 ° C. for 30 minutes. Next, add 5.7 parts of MDI (manufactured by Nippon Polyurethane Industry Co., Ltd., Millionate MT) to give 6
When reacted at 0 ° C. for 1 hour, a white diurea compound-dispersed polyol (A2) containing 1.0% of the diurea compound was obtained. A polyurethane foam molding similar to that of Example 1 was obtained using the above polyol (A2). The physical properties of the obtained polyurethane foam molded product are shown in Table 1.

Example 3 A white diurea compound-dispersed polyol (A2) containing 1.0% of the diurea compound obtained in Example 2 and a trifunctional polyol (manufactured by Sanyo Kasei Kogyo, GP-1000, molecular weight 1000) 10 A polyurethane foam molded article similar to that of Example 1 was obtained using the polyol added with parts. The physical properties of the obtained polyurethane foam molded product are shown in Table 1.

Comparative Example 1 Production of Polyurethane Foam Molded Product 100 parts of the trifunctional polyol having a molecular weight of 5000 used in Example 1, 3.5 parts of water as a blowing agent, and triethylenediamine (66.7% of dipropylene glycol as a catalyst).
1.0 parts) and Bis- (2-dimethylaminoethyl) eth
er (containing 30% dipropylene glycol) and 1.0 part of SZ-1306 (manufactured by Nippon Unicar) as a foam stabilizer were added in advance, and MDI polyisocyanate (manufactured by Nippon Polyurethane Industry Co., Ltd., Coronate 1106) was added at 25 ° C. Warm, N
A mixture having a CO index of 100 was stirred with a homomixer for 10 seconds, then poured into an open mold to allow free foaming, and at the same time, preheated to 55 ° C. 300 × 30
It was poured into a 0 × 100 mm mold, and after 5 minutes, it was demolded and cured at 25 ° C. for 16 hours to obtain a polyurethane foam molded product. The physical properties of the obtained polyurethane foam molded product are shown in Table 1.

Comparative Example 2 The same polyurethane as in Example 1 was prepared by using the trifunctional polyol having a molecular weight of 5000 used in Example 1 and 0.5% silica (Nipseal manufactured by Nippon Silica Industry Co., Ltd.) as an inorganic filler. A foam molding was obtained. The physical properties of the obtained polyurethane foam molded product are shown in Table 1.

Comparative Example 3 A polyurethane foam molding similar to that of Example 1 was obtained by using the trifunctional polyol having a molecular weight of 5000 used in Example 1 and containing 1% of silica as an inorganic filler. The physical properties of the obtained polyurethane foam molded product are shown in Table 1.

[Physical Property Test] The test was carried out based on the methods of JIS K 6382 and JIS K 6402.

[0034]

[Table 1]

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Claims (1)

[Claims] 1. A method for producing a flexible urethane foam using a polyol component (A), a polyisocyanate (B1), a foaming agent and an additive, wherein a part or all of the polyol component (A) is a polyol (A1). ) Is a diurea compound-dispersed polyol (A2) containing 0.1 to 20% by weight of a diurea compound obtained by reacting an aromatic monoamine (C) with a diisocyanate compound (B2) in the production of a flexible urethane foam. Method.