JP6757764B2 - Polyurethane foam manufacturing composition and flexible polyurethane foam - Google Patents

Description

The present invention relates to a composition for producing polyurethane foam and a flexible polyurethane foam.

Since flexible polyurethane foam is soft and has resilience due to the communication of air bubbles in the foam, it is molded into a predetermined shape by molding or the like and used as a cushioning material for automobile seats or the like. Be done.
Mold molding, which is one of the molding methods for polyurethane foam, involves injecting a raw material for polyurethane foam into a mold and then performing a urethanization reaction of the raw material in the mold to foam and cure the cured product from the mold. The method. In order to produce a foam that is as accurate as the mold, that is, a foam with good moldability by soft molding, the flow of the raw material for polyurethane foam is to quickly spread the raw material for polyurethane foam to every corner of the mold. It is necessary to maintain the property within a certain range, and it is required that the raw material that has spread to the mold can be quickly cured and demolded, that is, the curability is good. Then, as a method for producing a polyurethane foam capable of achieving both moldability and curability, a method for producing a polyurethane foam using a specific catalyst has been presented (see Patent Document 1 and Patent Document 2).

Japanese Unexamined Patent Publication No. 2005-29658 JP-A-2007-91975

However, although the flexible polyurethane foam produced by the methods of Patent Documents 1 and 2 is excellent in moldability and curability, in order to use it as a cushioning material, after demolding in order to prevent shrinkage after cooling, etc. Further, there is a problem that a step (hereinafter referred to as a crushing step) of breaking the film (cell) of the bubbles generated during foam molding and communicating the bubbles in the foam is required.

An object of the present invention is to provide a flexible polyurethane foam which is excellent in moldability and curability and does not require a crushing step even when used as a cushioning material.

The present inventors have arrived at the present invention as a result of diligent studies to solve the above problems.
That is, in the present invention, an alkylene oxide adduct (A) of a compound having two or more active hydrogens, a diol (B) represented by the following chemical formula (1), a catalyst component (C), a foaming agent (D), It is a flexible polyurethane foam obtained by curing a polyurethane foam production composition (G) containing a foam regulating agent (E) and a polyisocyanate component (F) and satisfying the following (1) to (3).

[In equation (1), n is a number of 3.0 to 4.0 and m is an integer of 4 to 8. ]
(1) The content of the oxyethylene unit contained in the alkylene oxide adduct (A) is 13 to 20% by weight based on the total weight of the oxyalkylene unit.
(2) The content of the diol (B) is 0.7 to 2.5% by weight based on the weight of (A).
(3) The total content of the diol (B) represented by the chemical formula (1) and the catalyst component (C) is 1.0 to 3.0% by weight based on the weight of (A).

The flexible polyurethane foam of the present invention has excellent moldability and curability, and does not require a crushing step even when used as a cushioning material. Therefore, it can be produced efficiently.

The composition (G) for producing a polyurethane foam of the present invention includes an alkylene oxide adduct (A) of a compound having two or more active hydrogens, a diol (B) represented by the following chemical formula (1), and a catalyst component (C). ), Foaming agent (D), foam stabilizer (E) and polyisocyanate component (F).

[In equation (1), n is a number of 3.0 to 4.0 and m is an integer of 4 to 8. ]
(1) The content of the oxyethylene unit contained in the alkylene oxide adduct (A) is 13 to 20% by weight based on the total weight of the oxyalkylene unit.
(2) The content of the diol (B) is 0.7 to 2.5% by weight based on the weight of (A).
(3) The total content of the diol (B) represented by the chemical formula (1) and the catalyst component (C) is 1.0 to 3.0% by weight based on the weight of (A).

First, the alkylene oxide adduct (A) of a compound having two or more active hydrogens will be described.
The content of the oxyethylene unit contained in the alkylene oxide (hereinafter abbreviated as AO) adduct (A) of the compound having two or more active hydrogens is 13 to 20% by weight based on the weight of the above (A). In the following, the AO adduct of an active hydrogen-containing compound having two or more active hydrogens may be simply abbreviated as an AO adduct.

The active hydrogen-containing compound having two or more active hydrogens is a compound containing at least two (preferably 2 to 8) active hydrogens.
Examples of the compound containing active hydrogen are hydrogen atoms contained in a carboxyl group, a hydroxyl group, an amino group, and a thiol group, and examples thereof include polyhydric alcohols, polyhydric phenols, amines, polycarboxylic acids, and phosphoric acids.

Examples of the polyhydric alcohol include a dihydric alcohol having 2 to 20 carbon atoms, a trihydric alcohol having 3 to 20 carbon atoms, and a 4 to 8 valent polyhydric alcohol having 5 to 20 carbon atoms.
Divalent alcohols having 2 to 20 carbon atoms include linear or branched aliphatic diols and alicyclic diols. The linear or branched aliphatic diol includes alkylene glycol and the like, and specifically, ethylene glycol, 1,2- or 1,3-propylene glycol, 1,3- or 1,4-butanediol, 1 , 6-Hexanediol, neopentyl glycol and the like. Examples of the alicyclic diol include cycloalkylene glycol and the like, and specific examples thereof include cyclohexanediol and cyclohexanedimethanol.
The trihydric alcohol having 3 to 20 carbon atoms includes an aliphatic triol and the like. Aliphatic triols include alkanetriols and the like, and specific examples thereof include glycerin, trimethylolpropane, trimethylolethane and hexanetriols.
The 4- to 8-valent polyhydric alcohol having 5 to 20 carbon atoms includes an aliphatic polyol and a saccharide. Examples of the aliphatic polyol include an alkane polyol and the like, and specific examples thereof include pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin and dipentaerythritol. In addition, the aliphatic polyol includes an intramolecular dehydrated product of alkane triol and an alkane polyol, and an intermolecular dehydrated product of an alkane triol and / or an alkane polyol. Specific examples of the saccharide include sucrose, glucose, mannose, fructose, methylglucoside and the like, and derivatives thereof are also included.

The multivalent (preferably 2 to 8) phenol includes monocyclic polyphenol, bisphenol, a condensate of phenol and formaldehyde (novalac), polyphenol, and a combination of two or more of these. Examples of the monocyclic polyvalent phenol include pyrogallol, hydroquinone, fluoroglucin and the like. Examples of bisphenol include bisphenol A, bisphenol F and bisphenol sulfone. Examples of polyphenols include those described in US Pat. No. 3,265,641.

Examples of the amine include ammonia, linear or branched aliphatic amines, aromatic amines, alicyclic amines and heterocyclic amines, and those having 2 to 8 active hydrogens are preferable.
Examples of the linear or branched aliphatic amine include alkanolamines having 2 to 20 carbon atoms (monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, aminoethylethanolamine, etc.) and alkylamines having 1 to 20 carbon atoms (n-). Butylamine and octylamine, etc.), alkylenediamine with 2 to 6 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, etc.) and polyalkylenepolyamine with 4 to 20 carbon atoms (alkylene groups having 2 to 6 carbon atoms, etc.) Specific examples thereof include diethylenetriamine and triethylenetetramine).
Examples of the aromatic amine include aromatic amines having 6 to 20 carbon atoms (aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline, diphenyletherdiamine, etc.).
Examples of the alicyclic amine include an alicyclic amine having 4 to 20 carbon atoms (isophoronediamine, cyclohexylene diamine, dicyclohexylmethanediamine, etc.).
Examples of the heterocyclic amine include heterocyclic amines having 4 to 20 carbon atoms (piperazine, aminoethylpiperazine, those described in Japanese Patent Publication No. 55-21044, etc.) and the like.

Examples of the polycarboxylic acid include an aliphatic polycarboxylic acid having 4 to 18 carbon atoms (succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid, etc.) and an aromatic polycarboxylic acid having 8 to 18 carbon atoms (phthalic acid, (Terephthalic acid, isophthalic acid, trimellitic acid, etc.) and the like can be mentioned.
Two or more of these active hydrogen-containing compounds may be used in combination. Among these, polyhydric alcohols are preferable from the viewpoint of curability and mechanical properties of polyurethane foam.

As the AO to be added to the active hydrogen-containing compound, it is preferable to use ethylene oxide (hereinafter abbreviated as EO) in combination with 1,2-AO having 3 or more carbon atoms. Examples of 1,2-AO having 3 or more carbon atoms include 1,2-propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide, styrene oxide, and the like, and among them, from the viewpoint of reactivity and the like. PO is preferred.
As the AO, it is preferable to use only EO and 1,2-AO having 3 or more carbon atoms, but other AOs may be contained in the AO in the range of 10% by weight or less (more preferably 5% by weight or less). .. As the EO and other AOs that can be used in combination with 1,2-AO having 3 or more carbon atoms, those having 4 to 8 carbon atoms are preferable, and 1,3-, 1,4-, 2,3-butylene oxide and the like can be mentioned. However, two or more of these may be used.

The addition form of two or more types of AO may be either block addition or random addition, but block addition is preferable.

The reaction for adding AO to the active hydrogen-containing compound can be carried out by a known method, and the catalyst used when adding AO to the active hydrogen-containing compound includes an alkaline catalyst (KOH, CsOH, etc.) and JP-A-2000. A catalyst described in JP-A-344881 [Tris (pentafluorophenyl) borane, etc.] and a catalyst described in JP-A-11-120300 (magnesium perchlorate, etc.) can be used.

Next, the diol (B) represented by the following chemical formula (1) of the present invention will be described.

[In equation (1), n is a number from 3.0 to 4.0 and m is an integer from 4 to 8]]
The diol (B) represented by the chemical formula (1), which is an essential component of the composition for producing polyurethane foam (G) of the present invention, contains methylamine and a linear or branched diol having 4 to 8 carbon atoms. It is a diol obtained by polycondensation. The average degree of polymerization of methylamine and a linear or branched diol having 4 to 8 carbon atoms is 3.0 to 4.0.
As a method for producing the diol (B), in the presence of a catalyst having a copper-nickel-platinum composition, a diol consisting of an integer having 4 to 8 carbon atoms and having hydroxyl groups at both ends is mixed with a predetermined amount of methylamine and an appropriate amount. It can be obtained by a method in which hydrogen gas is continuously blown and the water generated by the condensation reaction is continuously removed from the reaction system and reacted while stirring at a temperature of 150 to 200 ° C. under atmospheric pressure (for example). See JP-A-2005-29658).
As the diol (B), a commercially available one may be used, and "Kaorizer P200" manufactured by Kao Corporation or the like can be obtained from the market.
If the average degree of polymerization is less than 3.0, the swelling speed during molding of the polyurethane foam is high and the moldability deteriorates, and if it exceeds 4.0, the hardness of the polyurethane foam decreases.

In the present invention, the composition (G) for producing a polyurethane foam includes an alkylene oxide adduct (A) of a compound having two or more active hydrogens as a polyol component and a diol (B) represented by the chemical formula (1). May contain other polyols, active hydrogen-containing compounds, polyester polyol (a1), polyhydric alcohol (a2) having no polyoxyalkylene unit, and a vinyl monomer polymerized among these polyols. Examples thereof include the obtained polymer polyol (a3), amine (a4), and a mixture thereof.

The polyester polyol is a compound having two or more ester bonds and two or more hydroxyl groups, and examples of the polyester polyol (a1) include the following (1) to (5).
(1) Ester of polyhydric alcohol and polycarboxylic acid or ester-forming derivative thereof Examples of the polyhydric alcohol include the same polyhydric alcohols as those exemplified as the active hydrogen-containing compound used in (A) above. ..
Polycarboxylic acids or ester-forming derivatives thereof are acid anhydrides, lower alkyl (alkyl groups having 1 to 4 carbon atoms) esters and the like, and are adipic acid, sebacic acid, maleic anhydride, phthalic anhydride and dimethyl terephthalate. And so on.
(2) Condensation reaction product of carboxylic acid anhydride and AO The carboxylic acid anhydride is an anhydride of a polycarboxylic acid, and the polycarboxylic acid is an aliphatic polycarboxylic acid, preferably a fat having 4 to 18 carbon atoms. Group polycarboxylic acids (eg succinic acid, adipic acid, sebacic acid, glutaric acid, azelaic acid), aromatic polycarboxylic acids, preferably aromatic polycarboxylic acids with 8-18 carbon atoms (eg terephthalic acid, isophthalic acid, Orthophthalic acid, trimellitic acid, pyromellitic acid), alicyclic polycarboxylic acid, preferably alicyclic polycarboxylic acid having 8 to 15 carbon atoms (for example, cyclohexane 1,4-dicarboxylic acid) and two or more of them. Examples thereof include a mixture of.
Examples of the AO include those similar to the AO exemplified as the active compound used in the above (A).
(3) Examples of the AO (EO, PO, etc.) adduct AO described in (1) and (2) above include those similar to the AO exemplified as the active hydrogen-containing compound used in (A) above.
(4) Polylactone polyol Examples thereof include those obtained by ring-opening polymerization of a lactone (ε-caprolactone or the like) using a polyhydric alcohol as an initiator.
(5) Examples thereof include a reaction product of a polycarbonate polyol polyhydric alcohol and an alkylene carbonate.
Examples of the polyhydric alcohol include the same polyhydric alcohols used in (A).

Examples of the polyhydric alcohol (a2) having no polyoxyalkylene unit include the same polyhydric alcohols as exemplified as the active hydrogen-containing compound used in the above (A). Two or more of these may be used in combination.

The polymer polyol (a3) obtained by polymerizing a vinyl monomer among the polyols is a mixture of the polyol composed of at least one of (A) and (a1) to (a2) and the polymer compound particles.
Preferred (a3) is in the presence of a radical polymerization initiator in a polyol consisting of an alkylene oxide adduct (A) of a compound having two or more active hydrogens and at least one of (a1) to (a2). Examples thereof include polymer particles obtained by polymerizing an ethylenically unsaturated monomer (p) dispersed in a polyol.
The polymer polyol obtained by polymerizing the ethylenically unsaturated monomer (p) in the polyol is preferable in terms of dispersion stability. Specific examples of the method for obtaining (a3) include the methods described in US Pat. No. 3,383,351, Japanese Patent Publication No. 39-25737, and the like.

As the radical polymerization initiator used for the polymer polyol (a3), one that generates a free group to initiate polymerization can be used, and an azo compound [2,2'-azobisisobutyronitrile, 2,2'- Azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylbutyronitrile), etc.], organic peroxides [dibenzoyl peroxide, dicumyl peroxide, benzoyl peroxide, lauroylper Oxide and persuccinic acid, etc.] and inorganic radical [persulfate, perborate, etc.] and the like. In addition, these can be used in combination of 2 or more types.

Examples of the ethylenically unsaturated monomer (p) used for the polymer polyol (a3) include unsaturated nitriles (p1), aromatic ring-containing monomers (p2), (meth) acrylic acid esters (p3), and other ethylenically unsaturated monomers. Examples thereof include a monomer (p4) and a mixture of two or more of these.
Examples of the above (p1) include acrylonitrile and methacrylonitrile.
Examples of the above (p2) include styrene, α-methylstyrene, hydroxystyrene, chlorostyrene and the like.
The (p3) is composed of C, H and O atoms, for example, (meth) acrylic acid alkyl ester (alkyl group having 1 to 24 carbon atoms) [methyl (meth) acrylate, butyl (meth) acrylate, Nonyl (meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, eikosyl (meth) acrylate and docosyl (meth) acrylate, etc.], hydroxyalkyl (2-5 carbon atoms) (meth) acrylate [hydroxyethyl (meth) acrylate ) Acrylate, etc.] and hydroxypolyoxyalkylene mono (meth) acrylate [the number of carbon atoms of the alkylene group is 2 to 4, the number average molecular weight of the polyoxyalkylene chain is 200 to 1000, etc.].
Examples of (p4) include ethylenically unsaturated carboxylic acids and derivatives thereof [(meth) acrylic acid and (meth) acrylamide, etc.], aliphatic or alicyclic hydrocarbon monomers [alkenes (ethylene, propylene, norbornene, etc.). ) And alkaziene (butadiene, etc.)], Fluorine-based vinyl monomer [Fluorine-containing (meth) acrylate (perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, etc.), etc.], Chlorine-based vinyl monomer (vinylidene chloride, etc.) ), Nitrogen-containing vinyl monomer excluding (meth) acrylamide [nitrogen-containing (meth) acrylate (diaminoethyl methacrylate, morpholinoethyl methacrylate, etc.), etc.], vinyl-modified silicone, and the like.
Among these (p), the above-mentioned (p1) and (p2) are preferable, and acrylonitrile and / or styrene are more preferable, from the viewpoint of moldability.

The weight ratios of the (p1), (p2), (p3) and (p4) in the ethylenically unsaturated monomer (p) can be changed according to the required physical properties of the polyurethane and are particularly limited. Although not, an example is as follows.
Based on the total weight of (p), the above (p1) and / or (p2) is preferably 50 to 100% by weight, more preferably 80 to 100% by weight. The weight ratio of (p1) and (p2) is not particularly limited, but 100/0 to 20/80 is preferable. The above (p3) is preferably 0 to 50% by weight, more preferably 0 to 20% by weight, based on the total weight of (p). The above (p4) is preferably 0 to 10% by weight, more preferably 0 to 5% by weight.

The content of the ethylenically unsaturated monomer (p) in the polymer polyol (a3) in the polymer is preferably 50% by weight or less from the viewpoint of moldability based on the weight of the above (a3). , More preferably 3 to 30% by weight.

Examples of the amine (a4) include those similar to the amine exemplified as the active compound used in the above (A). In addition, these can be used in combination of 2 or more types.

The composition for producing polyurethane foam (G) used in the present invention contains polydiene polyols such as polybutadiene polyols and hydrogenated products thereof as polyol components; acrylic polyols (Japanese Patent Laid-Open Nos. 58-57413 and JP-A-A). Hydroxy group-containing vinyl polymer described in JP-A-58-57414); Natural fat-based polyols such as sunflower oil; Natural fat-based polyols such as castor oil modified products (polyhydric alcohol transesterification products, hydrogenated products, etc.) Denatured product;
A terminal radically polymerizable functional group-containing active hydrogen compound (including monool) described in WO98 / 44016, a modified polyol obtained by jumping a polyether polyol with an alkylenedihalide such as methylenedihalide; a polyether polyol. OH-terminal prepolymer; etc. may be included.

The content of (A) is preferably 8 to 98% by weight based on the total weight of the polyol components from the viewpoint of curability and mechanical properties of the polyurethane foam.
In the present invention, when the composition (G) for producing a polyurethane foam contains the polymer polyol (a3) and the above (A) is contained in the above (a3), it is contained in (a3) (A). Is also included as the content of (A) above.

The content of the oxyethylene unit contained in (A) is 13 to 20% by weight, preferably 13 to 19% by weight, and more preferably 14 to 18% by weight based on the weight of (A). If the content of the oxyethylene unit contained in (A) is less than 13% by weight, the emulsifying property of the polyol and the isocyanate deteriorates, so that the urethanization reaction at the time of foam foaming becomes insufficient and the foamed foam collapses and is molded. Sex gets worse. If it exceeds 20% by weight, the closed cell ratio of the foam becomes high, and crushing is required.
The content of the oxyethylene unit contained in the (A) is determined from the weight ratio of the oxyethylene unit contained in the (A). The weight ratio of the oxyethylene unit possessed by (A) is a calculated value obtained from the ratio of the amount of AO charged at the time of (A) synthesis and the amount of EO charged therein.
Examples of the method for keeping the content of the oxyethylene unit contained in the (A) within the above range include a method for adjusting the amount of EO charged at the time of the synthesis (A) to the above-mentioned preferable range.

Next, the catalyst component (C) will be described.
The catalyst component (C) used in the present invention comprises at least one catalyst (c1) selected from the group consisting of carboxylic acid salts of tertiary amines and tertiary amines, carboxylic acid metal salts and organometallic compounds. ..

Among the above (c1), examples of the carboxylic acid salt of the tertiary amine and the tertiary amine include triethylenediamine, N-ethylmorpholin, diethylethanolamine, N, N, N', and N'-tetramethylhexamethylenediamine. 1,2-dimethylimidazole, 1-isobutyl-2-methylimidazole, 1,8-diazabicyclo- [5,4,0] -undecene-7 (carboxylic acid salt) and bis (dimethylaminoethyl) ether (carboxylic acid salt) ) Etc. can be mentioned.
Examples of the metal carboxylic acid salt include potassium acetate, potassium octylate, and stanas octoate.
Examples of the organometallic compound include stannous octylate, dibutylstantic dilaurylate, lead octylate and the like.

The contents of the diol (B) represented by the chemical formula (1) and the catalyst component (C) are 1.0 to 3.0% by weight, preferably 1.1 to 2.% based on the weight of the above (A). It is 5% by weight, more preferably 1.3 to 1.8% by weight. If the contents of (B) and (C) are less than 1.0% by weight based on the weight of (A), the curability of urethane is slow and the production efficiency is deteriorated, and 3.0% by weight is used. If it exceeds this, the foaming speed at the time of foam molding becomes too fast, so that the liquid cannot spread completely on the mold surface, or the mold crushes the foaming liquid at the time of mold clamping, and air voids and foam collapse increase.

The content of the diol (B) represented by the chemical formula (1) is 0.7 to 2.5% by weight, preferably 1.2 to 2.0% by weight, more preferably 1.2 to 2.0% by weight, based on the weight of the above (A). Is 1.4 to 1.8% by weight.
If the content of the diol (B) is less than 0.7% by weight based on the weight of the above (A), the curability of urethane is slow and the production efficiency is deteriorated, and if it exceeds 2.5% by weight, during foam molding. Since the foaming speed of the mold becomes too high, the liquid cannot spread completely on the surface of the mold, or the mold crushes the foaming liquid at the time of mold clamping, and air voids and foam collapse increase.

The foaming agent (D) used in the flexible polyurethane foam of the present invention preferably contains water, and more preferably water alone.
The content of the foaming agent (D) needs to be adjusted according to the density of the foam to be molded, and is preferably 1 to 7% by weight, more preferably 1 to 5% by weight, based on the weight of the polyol component (A). is there.
If the content of the foaming agent (D) is less than 1% by weight, the foam has a molding density of 80 kg / m3 or more, and the amount of raw materials used is large and the cost is high. If it exceeds 7% by weight, the amount of isocyanate used increases, the emulsifying property with the polyol deteriorates, the foam collapses, the heat of reaction increases, and there is a risk that the foam spontaneously ignites during curing after foam molding. There is.
When water is used as the foaming agent (D), hydrogen atom-containing halogenated hydrocarbons, low boiling point hydrocarbons, liquefied carbon dioxide gas and the like may be used in combination, if necessary.

As the foam stabilizer (E) used in the flexible polyurethane foam of the present invention, a known foam stabilizer used in the production of polyurethane foam can be used, and a silicone foam stabilizer is preferable.
Silicone foam stabilizers include polyether-modified dimethylsiloxane-based foam stabilizers ["SZ-1328", "SZ-1346" and "SF-2962" manufactured by Toray Dow Corning Co., Ltd., and Momentive Performance Materials. Examples thereof include "L-3640" manufactured by the company, and a dimethylsiloxane-based foam stabilizer ["TEGOSTAB B8738LF2" and "TEGOSTAB B8715LF2" manufactured by EVONIK] and the like.
The amount of the foam stabilizer (E) used is preferably 3% by weight or less, more preferably 2.5% by weight or less, based on the total weight of (A) above, from the viewpoint of moldability.

As the polyisocyanate component (F) used in the flexible polyurethane foam of the present invention, a divalent or higher (preferably 2 to 8 valent) organic polyisocyanate used in the polyurethane foam can be used, and an aromatic polyisocyanate or a straight chain can be used. Alternatively, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic aliphatic polyisocyanates and modified products thereof can be mentioned.

The aromatic polyisocyanates include aromatic diisocyanates having 6 to 16 carbon atoms (the same applies to the following polyisocyanates) excluding carbon in the NCO group, aromatic triisocyanates having 6 to 20 carbon atoms, and crude products of these isocyanates. , 2,4- or 2,6-tolylene diisocyanate (hereinafter abbreviated as TDI), 1,3- or 1,4-phenylenediisocyanate, 2,4'-or 4,4'-diphenylmethane. Examples thereof include diisocyanate (hereinafter abbreviated as MDI), polymethylene polyphenylene polyisocyanate (crude MDI), naphthylene-1,5-diisocyanate and triphenylmethane-4,4', 4''-triisocyanate.

Examples of the linear or branched aliphatic polyisocyanate include linear or branched aliphatic diisocyanates having 6 to 10 carbon atoms, such as 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate and lysine diisocyanate. Can be mentioned.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms, isophorone diisocyanate, 4,4'-dicyclohexylmethane diisocyanate, 1,4-cyclohexanediisocyanate, norbornane diisocyanate and the like.

Examples of the aromatic aliphatic polyisocyanate include aromatic aliphatic diisocyanates having 8 to 12 carbon atoms, such as xylylene diisocyanate and α, α, α', α'-tetramethylxylylene diisocyanate.

Examples of the modified polyisocyanate include a urethane group, a carbodiimide group, an allophanate group, a urea group, a burette group, an isocyanurate group, an oxazolidone group-containing modified product, and the like, and examples thereof include a carbodiimide-modified MDI.

The polyisocyanate component (F) is preferably an aromatic polyisocyanate from the viewpoint of moldability of the polyurethane foam, and more preferably MDI, crude MDI, or a modified product of these isocyanates.

As the polyisocyanate component (F), two or more kinds of isocyanates and modified products thereof may be used in combination.
The isocyanate group content (NCO%) of the polyisocyanate component (F) as a whole is preferably 20 to 34% from the viewpoint of moldability of the polyurethane foam.

The isocyanate index [(number of NCO groups / number of active hydrogen atoms) × 100] in the production of polyurethane foam is preferably 70 to 125, more preferably 75 to 120, and particularly preferably 80, from the viewpoint of moldability of polyurethane foam. ~ 115. It should be noted that the active hydrogen also contains two hydrogen atoms contained in water, which is a foaming agent, and water is included in the calculation of the isocyanate index.

The polyurethane foam manufacturing composition (G) used for the flexible polyurethane foam of the present invention may further contain known auxiliary components such as a colorant, a flame retardant, an antiaging agent and an antioxidant, if necessary. You may react in the presence of it. Colorants include dyes and pigments. The flame retardant includes a phosphoric acid ester, a halide phosphate, and the like. Anti-aging agents include triazole-based and benzophenone-based anti-aging agents. Examples of the antioxidant include hindered phenol-based and hindered amine-based antioxidants.
The amount of these auxiliary components used is preferably 1% by weight or less based on the weight of (A) above, from the viewpoint of curability and mechanical properties of polyurethane foam, and the flame retardant is curable and polyurethane foam. From the viewpoint of mechanical properties of the polyurethane foam, it is preferably 5% by weight or less, more preferably 2% by weight or less, and the antiaging agent is preferably 1% by weight or less from the viewpoint of curability and mechanical properties of the polyurethane foam, further preferably 0. The amount is 5.5% by weight or less, and the amount of the antioxidant is preferably 1% by weight or less, more preferably 0.01 to 0.5% by weight, from the viewpoint of curability and mechanical properties of the polyurethane foam.

The composition for producing polyurethane foam (G) is an alkylene oxide adduct (A), a diol (B) catalyst component (C), a foaming agent (D), and a foam stabilizer (E) of a compound having two or more active hydrogens. ) And the polyisocyanate component (F) are mixed by a known method such as using a mixing container equipped with a stirrer.

The flexible polyurethane foam of the present invention can be obtained by curing the above-mentioned composition for producing polyurethane foam (G) by the method described in the section of the following method for producing flexible polyurethane foam.

The flexible polyurethane foam for automobile seats of the present invention is the soft polyurethane foam for automobile seats of the present invention obtained by curing the polyurethane foam manufacturing composition (G) into a predetermined shape as it is or by performing necessary cutting. It can be a polyurethane foam. Since the flexible polyurethane foam does not require a crushing step, it is suitable for a flexible polyurethane foam for a seat, and can be suitably used for a vehicle seat or the like.

The method for producing a flexible polyurethane foam of the present invention includes an alkylene oxide adduct (A), a diol (B), a catalyst component (C), a foaming agent (D), and a foam stabilizer (a foam stabilizer) of a compound having two or more active hydrogens. A method for producing a flexible polyurethane foam, which comprises a step of reacting a polyurethane foam production composition (G) containing E) and a polyisocyanate component (F) in a mold, and satisfies the following (1) to (3). This is a method for producing a flexible polyurethane foam.

(1) The content of the oxyethylene unit contained in the alkylene oxide adduct (A) is 13 to 20% by weight based on the total weight of the oxyalkylene unit.
(2) The content of the diol (B) is 0.7 to 2.5% by weight based on the weight of (A).
(3) The total content of the diol (B) represented by the chemical formula (1) and the catalyst component (C) is 1.0 to 3.0% by weight based on the weight of (A).

The composition for producing polyurethane foam (G) is an alkylene oxide adduct (A), a diol (B), a catalyst component (C), a foaming agent (D), and a foam stabilizer (a compound having two or more active hydrogens). It is obtained by mixing E) and the polyisocyanate component (F) by a known method, and the order of mixing is not limited, but the alkylene oxide adduct (A) and diol of a compound having two or more active hydrogens ( B) A step of preparing a polyol composition containing a catalyst component (C), a foaming agent (D) and a foam stabilizer (E), and mixing the obtained polyol composition with the polyisocyanate component (F) is performed. It is preferable to obtain the composition for producing polyurethane foam (G).

With the alkylene oxide adduct (A), diol (B), catalyst component (C), foaming agent (D), foam stabilizer (E) and polyisocyanate component (F) of a compound having two or more active hydrogens. The mixing can be carried out by a known method.

Hereinafter, the present invention will be further described with reference to Examples and Comparative Examples, but the present invention is not limited thereto. Hereinafter, unless otherwise specified,% indicates a weight% and a part indicates a weight part.

<Examples 1 to 8 and Comparative Examples 1 to 9>
A predetermined amount of organic polyisocyanate B was added to the number of copies of the polyol composition shown in Tables 1 and 2 (a mixture of components obtained by removing the organic polyisocyanate from the composition for producing polyurethane foam) so as to have an NCO index of 100. After stirring at 4000 rpm for 8 seconds with a homodisper (stirring machine manufactured by Tokushu Kagaku Co., Ltd.), it is injected into a 300 mm (length) x 300 mm (width) x 100 mm (height) aluminum mold whose temperature has been adjusted to 40 ° C. and cured. Molding was performed in 3 minutes (time from injection of raw material to demolding).

Tables 1 and 2 show the moldability, curability, necessity of crushing process, and measurement results of foam physical properties of each foam.

The performance evaluation method and judgment are as follows.
<Evaluation and judgment of moldability>
The polyol component and the polyisocyanate component were mixed with a mixer, injected into a 25 cm square box, and the time until the foam reached the maximum height (rise time; seconds) was measured.
In addition, the ratio of the maximum height of the foam to the height after 5 minutes of mixing the polyol and the polyisocyanate component was calculated, and the settling rate (rate of foam drop) was calculated.
Judgment was made according to the following criteria.
⊚: Settling rate is less than 20% and rise time is 70 seconds or more 〇: Settling rate is less than 20% and rise time is 50 seconds or more and less than 70 seconds ×: Settling rate is 20% or more or rise time is less than 50 seconds

<Evaluation and judgment of curability>
Immediately after the mold was removed at a mold temperature of 40 ° C. and a cure time of 3 minutes, the amount of foam deformation after pressing at 50 N for 3 seconds was measured with a push-pull hardness tester having a diameter of 2 cm.
Judgment was made according to the following criteria.
⊚: less than 2% 〇: 2% or more and less than 5% ×: 5% or more

<Evaluation and judgment of non-crushing property>
Non-crushing shows that the shrinkage deformation of the foam is small even if the foam crushing step is omitted, and the evaluation method is that the foam is left for 24 hours without crushing after molding and demolding under the above conditions. When the shrinkage ratios of the foam in the vertical direction, the horizontal direction, and the thickness were 5% or less, the non-crushing property was set to "〇", and in other cases, it was set to "x".

<Measurement of core density, 25% -ILD hardness, elastic modulus>
The core density and elastic modulus were measured in accordance with JIS K6401.
The 25% -ILD hardness was based on JIS K6401 except that the area of the jig used for measurement was changed to 314 cm2.

The composition (G) for producing polyurethane foam in Examples and Comparative Examples shown in Tables 1 and 2 is as follows.
(A-1): PO85.3 mol was added to 1 mol of glycerin using potassium hydroxide as a catalyst (catalyst usage 0.3% by weight (reaction product weight standard)) at a reaction temperature of 95 ° C to 130 ° C. Then, after adding 21.8 mol of EO, a block-added polyoxyethylene propylene polyol obtained by removing potassium hydroxide by a conventional method. Hydroxy group value 28.0, content of terminal EO unit 16%.
(A-2): PO67.4 mol was added to 1 mol of glycerin using potassium hydroxide as a catalyst (catalyst usage 0.3% by weight (reaction product weight standard)) at a reaction temperature of 95 ° C to 130 ° C. Then, after adding 22.7 mol of EO, a block-added polyoxyethylene propylene polyol obtained by removing potassium hydroxide by a conventional method. Hydroxy group value 33.5, content of terminal EO unit 20%.
(A-3): After adding 127.0 mol of PO to 1 mol of pentaerythritol using potassium hydroxide as a catalyst (catalyst usage 0.3% by weight (based on the weight of reaction product)), potassium hydroxide was added by a conventional method. After removal, using Tris (pentafluorophenyl) borane as a catalyst (catalyst usage 50 ppm (reaction product weight standard)), PO15.2 mol was added at a reaction temperature of 50 ° C. to 75 ° C. After removing phenyl) borane, 16.6 mol of EO was added at a reaction temperature of 95 ° C. to 130 ° C. using potassium hydroxide as a catalyst (catalyst usage 0.3% by weight (based on reaction product weight)). After that, a block-added polyoxyethylene propylene polyol obtained by removing potassium hydroxide by a conventional method. The hydroxyl value is 30, and the content of terminal EO units is 8.0%.
(A-4): A mixture of 34.6 mol of PO and 111.4 mol of EO was reacted with 1 mol of glycerin using potassium hydroxide as a catalyst at a reaction temperature of 95 ° C to 130 ° C, and then hydroxylated by a conventional method. Randomly added polyoxyethylene propylene polyol obtained by removing potassium. The number of functional groups is 3.0, the hydroxyl value is 24, and the EO content is 70%.
(A-5): Addition of 2.0 mol of EO to 1 mol of sorbitol using potassium hydroxide as a catalyst (catalyst usage 0.3% by weight (based on reaction product weight)) at a reaction temperature of 95 ° C to 130 ° C. A polyoxyethylene polyol obtained by removing potassium hydroxide by a conventional method and diluting with water so as to have a water content of 15.5%. The number of functional groups is 6.0, the hydroxyl value is 1055, the EO content is 33%, and the water content is 15.5%.
(A-6): Using potassium hydroxide as a catalyst in 1 mol of pentaerythritol (the amount of the catalyst used 0.3% by weight (based on the weight of the reaction product)), PO117.0 mol was added at a reaction temperature of 95 ° C to 130 ° C. After addition, 24.5 mol of EO was added, and then potassium hydroxide was removed by a conventional method to obtain a block-added polyoxyethylene polyoxypropylene polyol (number of functional groups: 4.0, hydroxyl value: 28.0,). A polymer polyol obtained by copolymerizing styrene and acrylonitrile (weight ratio: 33/67) in a terminal EO unit content of 13.5%). The polymer content is 30%, the hydroxyl value is 21.0, and the volume average particles (R) of the polymer particles are 0.4 to 1.0 μm.
(A-7): To 1 mol of glycerin, 72.6 mol of PO was added at a reaction temperature of 95 ° C. to 130 ° C. using potassium hydroxide as a catalyst, then 15.9 mol of EO was added, and then hydroxylation was performed by a conventional method. Acrylonitrile was polymerized in a block-added polyoxyethylene polyoxypropylene polyol (4.0 functional groups, 28.0 hydroxyl value, 13.5% terminal EO unit content) obtained by removing potassium. Polymer polyol. The polymer content is 20%, the hydroxyl value is 27.0, and the volume average particles (R) of the polymer particles are 0.4 to 1.0 μm.
(B-1) of the diol component (B): A diol obtained by polycondensing methylamine and 1,6-hexanediol, and the average degree of polymerization of methylamine and 1,6-hexanediol is It was 3.0 to 4.0, and in this example, "Kaorizer P200" manufactured by Kao Corporation was used.

(C-1): "DABCO 33LV" manufactured by Evonik Industries: (33% dipropylene glycol solution of triethylenediamine).
(C-2): "DABCO NE1070" manufactured by Evonik Industries, Inc .: Aliphatic tertiary amine composition.
(C-3): "DABCO NE300" manufactured by Evonik Industries, Inc .: Aliphatic tertiary amine composition.
Foaming agent (D-1): Water (E-1): "TEGOSTAB B8715LF2" manufactured by Evonik Industries, Inc.
(E-2): "TEGOSTAB B8738LF2" (F-1) manufactured by Evonik Industries, Ltd .: "CEF-403" manufactured by Tosoh Corporation, NCO% = 28.2
Crosslinker: Triethanolamine

The flexible polyurethane foam, which is a cured product of the polyurethane foam manufacturing composition (G) of Examples 1 to 8 of the present invention, is excellent in moldability, curability, and non-crushing property (no crushing step is required).
On the other hand, Comparative Example 1 in which the diol (B) is not used has poor curability and non-crushing property.
Comparative Example 2 and Comparative Example 3 in which the total content of (B) and (C) is less than 1.0% by weight have poor curability. Comparative Example 4 in which the content of (B) is less than 0.7% by weight also has poor curability.
Comparative Example 5 in which the total content of (B) and (C) exceeds 3.0% by weight has poor moldability. Comparative Example 6 in which the content of (B) exceeds 2.5% by weight also has poor moldability. Comparative Example 7 in which the content of (B) exceeds 2.5% by weight and the total content of (B) and (C) exceeds 3.0% by weight also has poor moldability.
In Comparative Example 8 in which the content of the oxyethylene unit contained in (A) is less than 13% by weight, the settling rate is large and the moldability is poor, and the foam injected into the mold collapses to form a mold-shaped foam. It has not been obtained and the curability and non-crushing property cannot be evaluated.
Comparative Example 9 in which the content of the oxyethylene unit exceeds 20% by weight is poor in non-crushing property.

The flexible polyurethane foam of the present invention is excellent in moldability and curability, and does not require a crushing step, so that it can be efficiently produced.

Claims (3)

An alkylene oxide adduct (A) of a compound having two or more active hydrogens, a diol (B) represented by the following chemical formula (1), a catalyst component (C), a foaming agent (D), and a foam stabilizer (E). A flexible polyurethane foam obtained by curing a polyurethane foam production composition (G) containing the polyisocyanate component (F) and satisfying the following conditions (1) to (3).

[In equation (1), n is a number from 3.0 to 4.0 and m is an integer from 4 to 8]
(1) The content of the oxyethylene unit contained in the alkylene oxide adduct (A) is 13 to 20% by weight based on the total weight of the oxyalkylene unit.
(2) The content of the diol (B) is 0.7 to 2.5% by weight based on the weight of (A).
(3) The total content of the diol (B) represented by the chemical formula (1) and the catalyst component (C) is (A).
It is 1.0 to 3.0% by weight based on the weight of. The flexible polyurethane foam according to claim 1, wherein the polyisocyanate component (F) is an aromatic isocyanate. The flexible polyurethane foam according to claim 1 or 2 , which is for an automobile seat.