JP6419501B2 - Method for producing flexible polyurethane slab foam - Google Patents

Description

  The present invention relates to a method for producing a flexible polyurethane slab foam; a flexible polyurethane slab foam obtained by the production method.

  Soft polyurethane slab foam is widely used for furniture and bedding mattresses, automotive seat cushions, clothing, etc. Especially for furniture and bedding mattress applications, high hardness and high resilience polyurethane slab foam is required. ing.

  In order to improve the resilience of polyurethane foam, there is a method of increasing the number of functional groups by using two types of polyols having different numbers of functional groups (Patent Document 1). However, in such a method, a foam with high hardness is desired. However, there is a problem that the tear strength and the cut elongation are insufficient.

JP 2013-067716 A

  An object of the present invention is to provide a method for producing a flexible polyurethane slab foam having a high impact resilience and excellent tear strength and cut elongation in a high hardness region.

As a result of intensive studies to solve the above problems, the present inventors have reached the invention shown below.
That is, the present invention comprises a polyether polyol (composition) (A), a polyol component (P) containing an alkanolamine (F) having 4 to 9 carbon atoms, and an organic polyisocyanate (B). ), A flexible polyurethane foam slab foam that is reacted in the presence of a catalyst (D) and a foam stabilizer (E), wherein (A) is the average number of moles of ethylene oxide added per active hydrogen x Is 3 to 20, the primary hydroxyl group ratio y (%) of the terminal hydroxyl group is 86 to 100, x and y satisfy the relationship of the following formula (1), and the active hydrogen-containing compound (h) has 3 or more carbon atoms. A polyether polyol (A11) obtained by block addition of ethylene oxide to a 1,2-alkylene oxide-added compound and an active hydrogen-containing compound (h) having 1,2-carbon having 3 or more carbon atoms Contains one or more polyether polyols (A1) selected from the group consisting of polyether polyols (A12) in which ethylene oxide is block-added to those obtained by random addition of alkylene oxide and ethylene oxide, containing the active hydrogen The compound (h) contains a trihydric alcohol and / or a 4- to 8-valent alcohol, the number average functional group number of (A) is 2.0 to 2.6 , and the terminal hydroxyl group of (A) is primary. The hydroxyl group ratio is 85 to 95%, the content of ethylene oxide units in (A) is 10 to 20% by weight based on the weight of (A), and the total weight of (A) and (F) A method for producing a flexible polyurethane slab foam having a content of (F) based on 2 to 10% by weight; and a flexible polyurethane slab foam obtained by the above production method Over-time; it is.

  By using the production method of the present invention, a flexible polyurethane foam excellent in cutting elongation, tear strength and durability can be produced.

  In the production method of the present invention, a polyether polyol (composition) (A), a polyol component (P) containing an alkanolamine (F) having 4 to 9 carbon atoms, and an organic polyisocyanate (B) are used as a foaming agent. The reaction is carried out in the presence of (C), catalyst (D) and foam stabilizer (E).

The polyether polyol (composition) (A) used in the present invention satisfies the following (1) to (2).
(1) The primary hydroxyl group ratio of the terminal hydroxyl group of (A) is 85 to 95%.
(2) The content of ethylene oxide units is 10 to 20% by weight based on the weight of (A).

The primary hydroxyl group ratio of the terminal hydroxyl group of the polyether polyol (composition) (A) is 85 to 95%, preferably 86 to 93% from the viewpoint of improvement in tear strength and cut elongation of polyurethane foam and reactivity. More preferably, it is 87 to 92%.
A primary hydroxyl group ratio of less than 85% is not preferable because the elongation at break decreases. On the other hand, if it exceeds 95%, it becomes difficult to form polyurethane foam, which is not preferable.
The primary hydroxyl group ratio can be obtained by the following method, that is, by measuring the sample by ¹ H-NMR method after pre-treatment of the sample in advance.

The method for measuring the primary hydroxyl group ratio will be specifically described below.
<Sample preparation method>
About 30 mg of a measurement sample is weighed into an NMR sample tube having a diameter of 5 mm, and about 0.5 ml of deuterated solvent is added and dissolved. Thereafter, about 0.1 ml of trifluoroacetic anhydride is added to obtain a sample for analysis. Examples of the deuterated solvent include deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, and deuterated dimethylformamide, and a solvent that can dissolve the sample is appropriately selected.
<NMR measurement>
¹ H-NMR measurement is performed under normal conditions.

<Calculation method of primary hydroxyl group ratio>
By the pretreatment method described above, the terminal hydroxyl group of the polyether polyol reacts with the added trifluoroacetic anhydride to become a trifluoroacetic acid ester. As a result, a signal derived from a methylene group bonded with a primary hydroxyl group was observed at around 4.3 ppm, and a signal derived from a methine group bonded to a secondary hydroxyl group was observed at around 5.2 ppm (deuterated chloroform was used as a solvent). Used as). The primary hydroxyl group ratio is calculated by the following formula.
Primary hydroxyl group ratio (%) = [a / (a + 2 × b)] × 100
In the formula, a is an integral value of a signal derived from a methylene group to which a primary hydroxyl group is bonded in the vicinity of 4.3 ppm; b is an integrated value of a signal derived from a methine group to which a secondary hydroxyl group is bonded in the vicinity of 5.2 ppm. .

  The content of ethylene oxide units in (A) based on the total weight of the polyether polyol (composition) (A) is 10 to 20% by weight, and 10 to 18 from the viewpoint of improving the durability of the polyurethane foam. % By weight is preferred, more preferably 10 to 16% by weight. When the content of the ethylene oxide unit is less than 10%, it is not preferable because molding of the polyurethane foam becomes difficult. On the other hand, if it exceeds 20%, the wet heat compression residual strain of the polyurethane foam deteriorates, which is not preferable.

  The polyether polyol (composition) (A) used in the present invention contains at least one polyether polyol which is an alkylene oxide adduct of the active hydrogen-containing compound (h). The polyether polyol (composition) (A) preferably contains a polyether polyol (A1) described later from the viewpoint of improving the elongation at break.

  The active hydrogen-containing compound (h) in the present invention is a compound having two or more active hydrogens in the molecule, and includes a hydroxyl group-containing compound (h1), an amino group-containing compound (h2), a carboxyl group-containing compound (h3), It is one or more active hydrogen-containing compounds selected from the group consisting of a thiol group-containing compound (h4), a phosphate compound (h5), and a compound (h6) having two or more active hydrogen-containing functional groups in the molecule.

Examples of the hydroxyl group-containing compound (h1) include water, divalent to octavalent polyhydric alcohols, and polyhydric phenols. Specifically, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, diethylene glycol, neopentyl glycol, 1,4-bis (hydroxymethyl) cyclohexane and 1,4-bis (hydroxyethyl) Dihydric alcohols such as benzene; trihydric alcohols such as glycerin and trimethylolpropane; 4- to 8-hydric alcohols such as pentaerythritol, sorbitol and sucrose; polyhydric phenols such as pyrogallol, catechol and hydroquinone; bisphenol A, bisphenol F And bisphenols such as bisphenol S; polybutadiene polyols; castor oil-based polyols; (co) polymers of hydroxyalkyl (meth) acrylates and polyfunctional (eg, functional groups) such as polyvinyl alcohol 2 to 100) a polyol, and the like.
(Meth) acrylate means methacrylate and / or acrylate, and the same applies hereinafter.

  Examples of the amino group-containing compound (h2) include amines and amino alcohols. Specifically, ammonia; monoamines such as C1-20 alkylamines (such as butylamine) and anilines; aliphatic polyamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; heterocyclic polyamines such as piperazine and N-aminoethylpiperazine; Alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; aromatic polyamines such as phenylenediamine, tolylenediamine and diphenylmethanediamine; alkanolamines such as monoethanolamine, diethanolamine and triethanolamine; dicarboxylic acids and excess polyamines Polyamide polyamine obtained by condensation; polyether polyamine; hydrazine (such as hydrazine and monoalkyl hydrazine), dihydrazide (coma) Acid dihydrazide and terephthalic acid dihydrazide, etc.), guanidine (butyl guanidine and 1-cyanoguanidine, etc.) and the like; and mixtures of two or more thereof.

  Examples of the carboxyl group-containing compound (h3) include aliphatic polycarboxylic acids such as succinic acid and adipic acid; aromatic polycarboxylic acids such as phthalic acid and trimellitic acid; polycarboxylic acids such as (co) polymers of acrylic acid Examples thereof include polymers (functional group number 2 to 100).

As a thiol group containing compound (h4), a polythiol compound is contained and 2-8 valent polyvalent thiol is mentioned. Specific examples include ethanedithiol and 1,6-hexanedithiol.
Examples of the phosphoric acid compound (h5) include phosphoric acid, phosphorous acid, and phosphonic acid.

  Examples of the compound (h6) having two or more active hydrogen-containing functional groups in the molecule include alkanolamines such as monoethanolamine and diethylamine; amino acids such as aspartic acid; hydroxycarboxylic acids such as citric acid, and the like. .

  Among these active hydrogen-containing compounds (h), from the viewpoint of tear strength and breaking elongation of the resulting polyurethane foam, the hydroxyl group-containing compound (h1), the amino group-containing compound (h2), and two or more kinds of activities in the molecule A compound (h5) having a hydrogen-containing functional group is preferable, and water, a polyhydric alcohol, and an alkanolamine are more preferable.

  Examples of the alkylene oxide (hereinafter abbreviated as AO) to be added to the active hydrogen-containing compound (h) include ethylene oxide (hereinafter abbreviated as EO), 1,2-AO {1,2-propylene oxide (3, C3 or more). Hereinafter, abbreviated as PO), 1,2 butylene oxide and styrene oxide} and the like. Of these, PO, EO, and 1,2-butylene oxide are preferable from the viewpoints of properties and reactivity. When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

Polyether polyol (A1), which is an AO adduct of active hydrogen-containing compound (h), has 1,2-AO having 3 or more carbon atoms added to (h) from the viewpoint of the tear strength and cut elongation of urethane foam. Polyether polyol (A11) in which EO is block-added to the resultant and polyether polyol (A12) in which EO is block-added to 1,2-AO having 3 or more carbon atoms and EO randomly added 1 or more types of polyether polyols selected from the group consisting of: (A1) The average added mole number x of EO per active hydrogen x is 3 to 20, and the primary hydroxyl group ratio y (%) of the terminal hydroxyl group is It is a polyether polyol which is 40-100 and x and y satisfy | fill the relationship of following Numerical formula (1).
y ≧ 42.0x ^0.47 (1-x / 41) (1)

  When the relationship between x and y satisfies Expression (1), both the hydrophobicity and the reactivity are good, and a urethane foam having high mechanical properties and excellent durability is obtained. In general, as the amount of EO added increases, the ratio of primary hydroxyl groups of the terminal hydroxyl groups of the polyether polyol increases. However, as the amount of EO added increases, the hydrophilicity of the polyether polyol increases, and the moisture resistance of the resulting urethane foam deteriorates. Accordingly, a polyether polyol having a relatively small EO added mole number but a large primary hydroxyl group ratio is preferred in terms of both the reactivity and hydrophobicity of the polyether polyol. Equation (1) represents the preferred region.

When (A1) is a polyether polyol (A11) or (A12), 1,2-AO having 3 or more carbon atoms and EO are used as AO. In this case, as 1,2-AO, PO and 1,2-butylene oxide are preferable from the viewpoint of properties and reactivity, and PO is more preferable.
The content of 1,2-AO is preferably 10 to 100% by weight, more preferably 50 to 100% by weight from the viewpoint of properties and reactivity, based on the total weight of AO.
The content of EO is preferably 10 to 20% by weight, more preferably 10 to 16% by weight from the viewpoint of properties and reactivity, based on the total weight of AO.
AO is preferably composed of only 1,2-AO and EO. However, even if AO is used in combination with other AO within a range of 10% by weight or less (more preferably 5% by weight or less) in AO. Good. Other AOs are preferably those having 4 to 8 carbon atoms, such as 1,3-, 1,4- and 2,3-butylene oxide and styrene oxide, and two or more of them may be used.

  In the present invention, the average addition mole number x of EO per active hydrogen of the polyether polyol (A1) which is an AO adduct of the active hydrogen-containing compound (h) is 3 to 20 from the viewpoint of durability of the urethane foam. Preferably, it is 3-18, More preferably, it is 3-10, Most preferably, it is 3-9. When x is in the range of 3 to 20, the wet heat compression residual strain of the polyurethane foam is good.

  The ratio of primary hydroxyl groups of the terminal hydroxyl groups of (A1) (that is, the ratio of primary hydroxyl groups in the hydroxyl groups located at the terminals) y is 40 to 100% from the viewpoint of improving the tear strength and cutting elongation of the polyurethane foam. , Preferably 70 to 95%, more preferably 85 to 93%. When the primary hydroxyl group ratio of the terminal hydroxyl group is 40 to 100%, the tear strength and the cut elongation of the urethane foam are good.

The primary hydroxyl group ratio can be determined by the same method as described above, that is, by measuring the sample by a ¹ H-NMR method after pre-treatment of the sample in advance.

The number average functional group number of (A1) is preferably 2.0 to 8.0, more preferably 2.2 to 7.0, and particularly preferably from the viewpoint of improvement of durability and improvement of tear strength and cutting elongation. Is 2.4 to 6.0.
In the present invention, the number of functional groups of the polyether polyol (A) [including (A1)] is considered to be the same as the number of functional groups of the active hydrogen-containing compound (h) as a starting material.

The hydroxyl value (mgKOH / g) of (A1) is preferably 20 to 290, more preferably 22 to 170, particularly preferably 25 to 120 from the viewpoint of the viscosity of the polyol and the cut elongation of the polyurethane foam. It is.
The hydroxyl value is determined according to JIS K1557-1.

  Examples of the method for obtaining the polyether polyol (A1) which is an AO adduct used in the present invention include a method of adding AO to the active hydrogen-containing compound (h) in the presence of a specific catalyst (α). (Α) is used at the time of addition of 1,2-AO and EO having 3 or more carbon atoms, but is not necessarily used in all stages of addition of 1,2-AO and EO having 3 or more carbon atoms, and is usually used later. After addition of a part of 1,2-AO and EO having 3 or more carbon atoms in the presence of another catalyst (β) and using (α) only in the latter stage of the addition reaction, 2-AO and EO may be added.

Examples of (α) include those described in JP-A No. 2000-344881, specifically, a boron or aluminum compound to which a fluorine atom, a (substituted) phenyl group and / or a tertiary alkyl group are bonded. , Triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, triphenylaluminum, diphenyl-t-butylaluminum, tri (t-butyl) aluminum, tris (pentafluorophenyl) borane, bis (pentafluoro) Phenyl) -t-butylborane, tris (pentafluorophenyl) aluminum, bis (pentafluorophenyl) -t-butylaluminum and the like.
Among these, preferred are triphenylborane, triphenylaluminum, tris (pentafluorophenyl) borane and tris (pentafluorophenyl) aluminum, and more preferred are tris (pentafluorophenyl) borane and tris (pentafluoro). Phenyl) aluminum.
The addition conditions of AO may be the same as the method described in the above publication, and for example, preferably 0.0001 to 10% by weight, more preferably 0.001 to 1% by weight with respect to the ring-opening polymer to be formed. The above catalyst is used, and the reaction is preferably performed at 0 to 250 ° C, more preferably 20 to 180 ° C.

In the polyether polyols (A11) and (A12), EO is added to a 1,2-AO adduct having 3 or more carbon atoms and a random adduct of 1,2-AO and EO having 3 or more carbon atoms to further add 1 A polyol having a high ratio of secondary hydroxyl groups is obtained. A 1,2-AO adduct having 3 or more carbon atoms and a random adduct of 1,2-AO and EO having 3 or more carbon atoms in the catalyst (α), that is, a primary hydroxyl group of a terminal hydroxyl group before EO addition. Since the hydroxyl group ratio is as extremely large as 40% or more, preferably 60% or more, and more preferably 70% or more, the primary hydroxyl group ratio of the terminal hydroxyl group can be increased with a small amount of EO, and x and y are expressed by the above formula (1 ) Can be obtained. In addition, the catalyst used for the EO addition may use the boron or aluminum compound as it is or may use another catalyst (β) that is usually used instead.
Other catalysts (β) include basic catalysts such as sodium hydroxide, potassium hydroxide, cesium hydroxide, potassium carbonate, and triethylenediamine; acid catalysts such as boron trifluoride, tin chloride, triethylaluminum, and heteropolyacid. Zinc hexacyanocobaltate; phosphazene compounds and the like. Of these, basic catalysts are preferred.
Although the usage-amount of a catalyst is not specifically limited, Preferably it is 0.0001 to 10 weight% based on the weight of the polyol to produce | generate, More preferably, it is 0.001 to 1 weight%.

In the present invention, the polyether polyol (composition) (A) may contain a polyether polyol (A2) other than the polyether polyol (A1).
Examples of (A2) include AO adducts of the active hydrogen-containing compound (h) that do not fall under (A1).
The hydroxyl value (mgKOH / g) of (A2) is preferably in the same range as (A2).

  In the present invention, the content of the polyether polyol (A1) is based on the total weight of the polyether polyol (composition) (A), from the viewpoint of improvement in the tear strength and cut elongation of the urethane foam and the reactivity. It is preferably 10 to 100% by weight, more preferably 20 to 90% by weight, and particularly preferably 30 to 80% by weight.

  The number average functional group number of the polyether polyol (composition) (A) is 2.0 to 3.4, preferably 2.1 to 3.3, from the viewpoint of the tear strength and the cut elongation of the polyurethane foam. Preferably it is 2.2-3.2, Most preferably, it is 2.2-2.7.

  The hydroxyl value of the polyether polyol (composition) (A) is 20 to 290 (mgKOH / g), and preferably 22 to 170 (mgKOH / g) from the viewpoint of the viscosity of the polyol and the cut elongation of the polyurethane foam. More preferably, it is 25-120 (mgKOH / g).

  In the present invention, the content of the polyether polyol (composition) (A) in the polyol component (P) is the total weight of (P) from the viewpoint of improving the tear strength and cutting elongation of the urethane foam and the reactivity. Is preferably 20 to 98% by weight, more preferably 30 to 80% by weight.

The polyol component (P) used in the present invention contains an alkanolamine (F) having 4 to 9 carbon atoms. Examples of (F) include diethanolamine and triethanolamine. Among these, diethanolamine is preferable from the viewpoints of moldability, tactile sensation, and impact resilience.

  In the polyol component (P), the content of (F) based on the total weight of the polyether polyol (composition) (A) and the alkanolamine (F) having 4 to 9 carbon atoms is 2 to 10% by weight, Preferably it is 3 to 8% by weight. When the content of (F) is less than 2% by weight, the formability of the foam deteriorates, and when it exceeds 10% by weight, the reaction becomes too fast and the handling property deteriorates.

  In the present invention, the polyol component (P) may contain other polyol or active hydrogen component in addition to the polyether polyol (composition) (A) and, for example, the polymer polyol (P1), Examples thereof include polyester polyols, polyhydric alcohols, amines and mixtures thereof.

The polymer polyol (P1) is a polymer polyol in which polymer particles are dispersed in a polyether polyol as exemplified in the above sections (A1) and (A2).
The polymer polyol (P1) can be produced by polymerizing the vinyl monomer (g) in a polyether polyol by a known method. For example, in the polyether polyol, a vinyl monomer (g) is polymerized in the presence of a radical polymerization initiator, and the obtained polymer (g) is stably dispersed. Specific examples of the polymerization method include those described in US Pat. No. 3,383,351 and Japanese Examined Patent Publication No. 39-25737.
(G) is preferably styrene and / or acrylonitrile.
In the present invention, the polyether polyol contained in the polymer polyol (P1) is not contained in the polyether polyol (composition) (A).

  Polyester polyols include polyhydric hydroxyl group-containing compounds (including polyhydric alcohols and the aforementioned polyether polyols) and polycarboxylic acids (phthalic acid, isophthalic acid, terephthalic acid, 2,2′-bibenzyldicarboxylic acid, trimellitic acid , Hemititonic acid, trimesic acid, pyromellitic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3,6-tricarboxylic acid, diphenic acid, 2,3-anthracenedicarboxylic acid, 2,3,6-anthracentricarboxylic Ester-forming derivatives (phthalic anhydride and terephthalic acid) such as acid, pyrene dicarboxylic acid, succinic acid, fumaric acid, sebacic acid and adipic acid) or anhydrides and lower alkyl (alkyl group having 1 to 4 carbon atoms) ester Product of condensation reaction with dimethyl acid etc .; carboxylic acid of polyhydric alcohol Water and AO addition reaction products; these AO (EO, PO, etc.) addition reaction products; polylactone polyols {for example, obtained by ring-opening polymerization of lactones (e.g., ε-caprolactone) using a polyhydric alcohol as an initiator. And polycarbonate polyol (for example, a reaction product of a polyhydric alcohol and an alkylene carbonate) and the like.

  Other polyols include polydiene polyols such as polybutadiene polyol and hydrogenated products thereof; acrylic polyols, and hydroxyl group-containing vinyl polymers described in JP-A-58-57413 and JP-A-58-57414. Natural oil-based polyols such as castor oil; modified products of natural oil-based polyols;

Examples of the polyhydric alcohol include a divalent alcohol having 2 to 20 carbon atoms, a trivalent alcohol having 3 to 20 carbon atoms, and a 4 to 8 alcohol having 5 to 20 carbon atoms.
Examples of the dihydric alcohol having 2 to 20 carbon atoms include aliphatic diols (ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.) and alicyclic Diols (cyclohexanediol and cyclohexanedimethanol etc.) are mentioned.
Examples of the trihydric alcohol having 3 to 20 carbon atoms include aliphatic triols (such as glycerin and trimethylolpropane).
Examples of the 4- to 8-valent polyhydric alcohol having 5 to 20 carbon atoms include aliphatic polyols (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol and the like, and saccharides (sucrose, glucose, mannose, fructose, methyl). Glucoside and derivatives thereof).

  Examples of the amine include those similar to the aforementioned amino group-containing compound (h2) but not corresponding to (F).

  Of these other polyols or active hydrogen components, the polymer polyol (P1) is preferred.

  The method for producing a flexible polyurethane slab foam of the present invention comprises a polyol component (P) containing a polyether polyol (composition) (A) and an alkanolamine (F) having 4 to 9 carbon atoms and an organic polyisocyanate (B). , A production method of reacting in the presence of a foaming agent (C), a urethanization catalyst (D) and a foam stabilizer (E).

  As the organic polyisocyanate (B), those conventionally used for polyurethane production can be used. Examples of such isocyanates include aromatic polyisocyanates, linear or branched aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, ureas). Group, burette group, isocyanurate group, or oxazolidone group-containing modified product) and a mixture of two or more thereof.

As aromatic polyisocyanate, C6-C16 aromatic diisocyanate, C6-C20 aromatic triisocyanate, and crude products of these isocyanates (excluding carbon in the NCO group; the following isocyanates are also the same), etc. Is mentioned. Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4, 4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), and the like.
Examples of the linear or branched aliphatic polyisocyanate include linear or branched aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include alicyclic diisocyanates having 6 to 16 carbon atoms. Specific examples include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic polyisocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Specific examples of the modified polyisocyanate include urethane-modified MDI and carbodiimide-modified MDI.
Among these, TDI, crude TDI, MDI, crude MDI and modified products of these isocyanates are preferable from the viewpoint of tear strength, elongation at break and reactivity, more preferably TDI and MDI, and particularly preferably TDI.
The content of TDI in the organic polyisocyanate (B) is preferably 20 to 100% by weight, more preferably 30 to 100% by weight, particularly preferably 40 to 40% by weight based on the total weight of (B) from the viewpoint of reactivity. 100% by weight.

Examples of the foaming agent (C) include water, hydrogen atom-containing halogenated hydrocarbons, low-boiling hydrocarbons, and liquefied carbon dioxide gas, and two or more kinds may be used in combination. Water or liquefied carbon dioxide gas is preferred from the viewpoint of improving tensile strength and cutting elongation.
Specific examples of the hydrogen atom-containing halogenated hydrocarbon include dichloromethane and HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123 and HCFC-141b); HFC (hydrofluorocarbon) type (for example, HFC-245fa and HFC-365mfc) and the like.
The low boiling point hydrocarbon is a hydrocarbon having a normal boiling point of −5 to 70 ° C., and specific examples thereof include butane, pentane, and cyclopentane.
Among these, water, dichloromethane or liquefied carbon dioxide gas is preferable from the viewpoint of improving tensile strength and cutting elongation, and water or liquefied carbon dioxide gas is more preferable.
The amount of water used is preferably 1 to 8% by weight, more preferably 1.5 to 6.5% by weight, based on the weight of the polyol component (P), from the viewpoint of the calorific value and the expansion ratio.
The amount of liquefied carbon dioxide used is preferably 30% by weight or less, more preferably 25% by weight or less, based on the weight of the polyol component (P), from the viewpoint of the calorific value and the expansion ratio.
The amount of hydrogen atom-containing halogenated hydrocarbon used is preferably 50 parts by weight or less, more preferably 5 to 45 parts by weight per 100 parts by weight of the polyol component (P).
The amount of low-boiling hydrocarbon used is preferably 30% by weight or less, more preferably 25% by weight or less, based on the weight of the polyol component (P).

As the urethanization catalyst (D), an ordinary catalyst for promoting the urethanization reaction can be used, and tertiary amine {triethylenediamine, bis (N, N-dimethylamino-2-ethyl) ether and N, N, N ', N'-tetramethylhexamethylenediamine, etc.}, tertiary amine carboxylates, carboxylic acid metal salts (potassium acetate, potassium octylate, stannous octoate, etc.) and organometallic compounds (dibutyltin dilaurate, etc.) Can be mentioned.
The amount of the urethanization catalyst (D) used is preferably 0.01 to 1.5% by weight, more preferably 0.1 to 1, based on the total weight of the polyol component (P) and the organic polyisocyanate (B). .2% by weight.
As the urethanization catalyst (D), a carboxylic acid metal salt is preferably used from the viewpoints of high curing properties and high durability. In particular, it is more preferable to use stannous octoate.
Further, from the viewpoint of improving the air permeability of the slab foam, it is preferable to combine a tertiary amine in addition to the carboxylic acid metal salt. As the tertiary amine to be combined, triethylenediamine and bis (N, N-dimethylamino-2-ethyl) ether are more preferable.

As the foam stabilizer (E), those used for the production of polyurethane foam can be used, and “SZ-1959”, “SF-2904”, “SZ-1142”, “Toray Dow Corning Co., Ltd.” “SZ-1720”, “SZ-1675t”, “SF-2936F”, “SZ-3601”, “SRX-294A”, “SH-193”, “L-540” manufactured by Nippon Unicar Co., Ltd., “ L-3601 "," L-626 "manufactured by Momentive Performance Materials," B8715 LF2 "manufactured by Evonik Degussa Japan Co., Ltd., and the like.
The amount of the foam stabilizer used is preferably 0.3 to 3.0% by weight, more preferably 0.4 to 2.5% by weight, based on the total weight of the polyol component (P) and the organic polyisocyanate (B). %.

In the present invention, if necessary, a known auxiliary component such as a colorant, a flame retardant, an antiaging agent and an antioxidant may be used and reacted in the presence thereof. Colorants include dyes and pigments. Examples of the flame retardant include phosphate esters and halogenated phosphate esters. Examples of the antiaging agent include triazole type and benzophenone type antiaging 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 for the colorant, preferably 20% by weight or less, and more preferably 10% by weight or less, based on the weight of the polyol component (P). The anti-aging agent is preferably 1% by weight or less, more preferably 0.5% by weight or less, and the antioxidant is preferably 1% by weight or less, more preferably 0.01 to 0.5% by weight. It is.

In the production method of the present invention, the isocyanate index [(NCO group / active hydrogen atom-containing group) × 100] upon production of the flexible polyurethane slab foam is preferably 70 to 125, more preferably from the viewpoint of durability of the flexible polyurethane foam. Is 80 to 120, particularly preferably 90 to 115.
The active hydrogen atom-containing group includes those derived from water as a foaming agent.

Moreover, the reaction conditions of (P) and (B) may be known conditions that are usually used.
For example, a polyol component (P) containing a polyether polyol (composition) (A) and an alkanolamine (F) having 4 to 9 carbon atoms using a polyurethane low-pressure or high-pressure injection foaming machine or a stirrer. A predetermined amount of a foaming agent (C), a catalyst (D), a foam stabilizer (E) and, if necessary, an additive are mixed. Subsequently, this mixture and organic polyisocyanate (B) are rapidly mixed. The obtained mixed liquid is discharged and foamed in a box (made of metal, wood or resin) having an open top or on a belt conveyor. Let stand for a predetermined time and cure to obtain a flexible polyurethane slab foam.

  The production method of the present invention can be realized by combining a high curing property and a high durability in a reaction at room temperature, and thus is useful as a production method of a flexible polyurethane slab foam.

The core density of the foam obtained by the production method of the present invention is preferably 20 to 100 (kg / m ³ ), more preferably 22 to 80 (kg), from the viewpoint of easy weight reduction and the effects of the invention. / M ³ ), particularly preferably 25 to 60 (kg / m ³ ).
Foam hardness from the viewpoint of effect can be obtained easily in the invention, 100~350 (25% ILD, N / 314cm 2) is preferably, and more preferably 110~340 (25% ILD, N / 314cm 2), Particularly preferred is 130 to 320 (25% ILD, N / 314 cm ² ).
The impact resilience is preferably 40 to 80 (%), more preferably 50 to 75 (%), and particularly preferably 50 to 70 (%) from the viewpoint of good tactile sensation.
The cutting elongation is preferably 80 to 300 (%), more preferably 80 to 270 (%), and particularly preferably 85 to 250 (%) from the viewpoint of improving workability after molding. is there.
The core density, foam hardness, impact resilience, and cut elongation are measured by a method in accordance with JIS K6400.
Since the obtained foam has high hardness, high resilience, and excellent elongation at break, it is useful for applications such as mattresses using slab foams that require particularly high resilience.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by this. In addition, Examples 1-2, 4-7, and 10-12 are reference examples.

Examples 1-12 and Comparative Examples 1-8
Example 1
Using a stirrer, polyether polyol (composition) (A) shown in Table 1, C4-9 alkanolamine (F), polymer polyol (P1), blowing agent (C), catalyst (D) Then, a predetermined amount of the foam stabilizer (E) was hand-mixed (a method in which a stirring blade was inserted into a container and stirred), and the liquid temperature was adjusted to 25 ° C. Subsequently, this mixture and the organic polyisocyanate (B) whose liquid temperature is adjusted to 25 ° C. are hand-mixed at 5000 rpm for 6 to 20 seconds. The resulting mixed liquid is discharged into a 250 mm × 250 mm × 250 mm wood box (made of metal or resin) with the upper part open, and foamed to produce a flexible polyurethane slab foam. The whole day and night (temperature 25 ° C., humidity 50%) 24 hours) core density (kg / m ³ ), foam hardness (25% ILD, N / 314 cm ² ), impact resilience (%), tensile strength (N / cm ² ), tear strength (N / Cm), elongation at break (%), compression residual strain (%) and wet heat compression residual strain (%). In addition, the numerical value in Table 1 of compounding prescriptions other than organic polyisocyanate (B) [Isocyanate index is described] means the weight part.
The flexible polyurethane foams of Examples 2 to 12 and Comparative Examples 1 to 8 were produced in the same manner as Example 1 except that the raw materials listed in Table 1 were used.

The polyurethane foam raw materials in Examples 1 to 12 and Comparative Examples 1 to 8 are as follows.
(1) Polyether polyol (A1)
(A1-1) 56.1 mol of PO with potassium hydroxide as a catalyst was added to 1 mol of glycerin [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 ° C.] Potassium hydroxide was removed. Further, in the same manner as in Example 1 of JP-A-2000-344881, 12.0 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst: 50 ppm (based on reaction product weight), reaction temperature: 75 ° C. Then, tris (pentafluorophenyl) borane was removed by a conventional method, and 10.2 mol of EO was added using potassium hydroxide as a catalyst [amount of catalyst used: 0.3% by weight (based on reaction product weight), reaction temperature 95-105 ° C.] and obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 37.4, EO unit content 10.0% by weight, primary hydroxyl group ratio of terminal hydroxyl group 86%, number average functional group number 3.0, right side of formula (1) = 69.

  (A1-2) 74.8 mol of PO with potassium hydroxide as a catalyst was added to 1 mol of pentaerythritol [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 ° C.] To remove potassium hydroxide. Further, in the same manner as in Example 1 of Japanese Patent Laid-Open No. 2000-344881, 16.0 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst 50 ppm (based on reaction product weight), reaction temperature 75 ° C. Then, tris (pentafluorophenyl) borane was removed by a conventional method, and 13.6 mol of EO was added using potassium hydroxide as a catalyst [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature] 95-105 ° C.] and obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 37.4, EO unit content 10.0% by weight, primary hydroxyl group ratio of terminal hydroxyl group 86%, number average functional group number 4.0, right side of formula (1) = 73.

  (A1-3) 104.4 mol of PO with potassium hydroxide as a catalyst was added to 1 mol of pentaerythritol [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 ° C.] To remove potassium hydroxide. Further, in the same manner as in Example 1 of Japanese Patent Laid-Open No. 2000-344881, 16.0 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst 50 ppm (based on reaction product weight), reaction temperature 75 ° C. Then, tris (pentafluorophenyl) borane was removed by a conventional method, and 20.0 mol of EO was added using potassium hydroxide as a catalyst [amount of catalyst used: 0.3% by weight (based on reaction product weight), reaction temperature 95-105 ° C.] and obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 28.1, EO unit content 11.0% by weight, primary hydroxyl group ratio of terminal hydroxyl group 88%, number average functional group number 3.0, right side of formula (1) = 79.

  (A1-4) 72.7 mol of PO using potassium hydroxide as a catalyst was added to 1 mol of pentaerythritol [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 ° C.] To remove potassium hydroxide. Further, in the same manner as in Example 1 of Japanese Patent Laid-Open No. 2000-344881, 16.0 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst 50 ppm (based on reaction product weight), reaction temperature 75 ° C. Then, tris (pentafluorophenyl) borane was removed by a conventional method, and 16.4 mol of EO was added using potassium hydroxide as a catalyst [amount of catalyst used: 0.3% by weight (based on reaction product weight), reaction temperature 95-105 ° C.] and obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 37.4, EO unit content 12.0% by weight, terminal hydroxyl group primary hydroxyl group ratio 87%, number average functional group number 4.0, right side of formula (1) = 73.

  (A1-5) 72.6 mol of PO with potassium hydroxide as a catalyst was added to 1 mol of glycerin [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 ° C.] Potassium hydroxide was removed. Further, in the same manner as in Example 1 of JP-A-2000-344881, 12.0 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst: 50 ppm (based on reaction product weight), reaction temperature: 75 ° C. Then, tris (pentafluorophenyl) borane was removed by a conventional method, and 18.1 mol of EO was added using potassium hydroxide as a catalyst [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature] 95-105 ° C.] and obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 29.0, EO unit content 14.0% by weight, primary hydroxyl group ratio of terminal hydroxyl group 90%, number average functional group number 3.0, right side of formula (1) = 76.

  (A1-6) 73.3 mol of PO was added to 1 mol of glycerol using potassium hydroxide as a catalyst (amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 ° C.). Potassium hydroxide was removed. Further, in the same manner as in Example 1 of JP-A-2000-344881, 12.0 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst: 50 ppm (based on reaction product weight), reaction temperature: 75 ° C. Then, tris (pentafluorophenyl) borane was removed by a conventional method, and 21.8 mol of EO was added using potassium hydroxide as a catalyst. 95-105 ° C.] and obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 28.1, EO unit content 16.0% by weight, primary hydroxyl group ratio of terminal hydroxyl group 92%, number average functional group number 3.0, right side of formula (1) = 88.

  (A1-7) 48.5 mol of PO was added to 1 mol of glycerol using potassium hydroxide as a catalyst (amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 ° C.). Potassium hydroxide was removed. Further, in the same manner as in Example 1 of JP-A-2000-344881, 12.0 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst: 50 ppm (based on reaction product weight), reaction temperature: 75 ° C. Then, tris (pentafluorophenyl) borane was removed by a conventional method, and 20.5 mol of EO was added using potassium hydroxide as a catalyst [catalyst consumption 0.3 wt% (based on reaction product weight), reaction temperature 95-105 ° C.] and obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 37.4, EO unit content 20.0% by weight, primary hydroxyl group ratio of terminal hydroxyl group 92%, number average functional group number 3.0, right side of formula (1) = 86.

  (A1-8) 45.0 mol of PO was added to 1 mol of dipropylene glycol using potassium hydroxide as a catalyst [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 ° C.] Potassium hydroxide was removed by the method. Further, in the same manner as in Example 1 of JP-A-2000-344881, 12.0 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst [amount of catalyst: 50 ppm (based on reaction product weight), reaction temperature: 75 ° C. Then, tris (pentafluorophenyl) borane was removed by a conventional method, and 12.7 mol of EO was added using potassium hydroxide as a catalyst [catalyst consumption 0.3 wt% (based on reaction product weight), reaction temperature 95-105 ° C.] and obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 28.1, EO unit content 14.0% by weight, primary hydroxyl group ratio of terminal hydroxyl group 91%, number average functional group number 2.0, right side of formula (1) = 85.

(2) Polyether polyol (A2) other than (A1)
(A2-1) Potassium hydroxide is added to 1 mol of glycerin as a catalyst, and 93.6 mol of PO and 8.3 mol of EO are added [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 ° C.] And a polyoxyalkylene polyol obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 28.1, EO unit content 8% by weight, primary hydroxyl group ratio of terminal hydroxyl group 70%, number average functional group number 3.0.

  (A2-2) PO mol 121.8 and EO 18.2 mol were added to 1 mol of pentaerythritol using potassium hydroxide as a catalyst [amount of catalyst used 0.3 wt% (based on reaction product weight), reaction temperature 95 to 105 And polyoxyalkylene polyol obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 28.1, EO unit content 10% by weight, terminal hydroxyl group primary hydroxyl group ratio 74%, number average functional group number 4.0.

  (A2-3) 85.3 mol of PO and 21.8 mol of EO were added to 1 mol of glycerol using potassium hydroxide as a catalyst [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 ° C.] And a polyoxyalkylene polyol obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 28.1, EO unit content 16% by weight, terminal hydroxyl group primary hydroxyl group ratio 82%, number average functional group number 3.0.

  (A2-4) 7 mol of PO mol and 30.0 mol of EO were added to 1 mol of pentaerythritol using potassium hydroxide as a catalyst [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 to 105 And polyoxyalkylene polyol obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 37.4, EO unit content 22% by weight, primary hydroxyl group ratio of terminal hydroxyl group 85%, number average functional group number 4.0.

  (A2-5) PO mole 46.6 and EO 15.1 mole were added to 1 mole of dipropylene glycol using potassium hydroxide as a catalyst [amount of catalyst used: 0.3 wt% (based on reaction product weight), reaction temperature: 95 105 ° C.], and obtained by removing potassium hydroxide by a conventional method. Hydroxyl value 32.1, EO unit content 19% by weight, terminal hydroxyl group primary hydroxyl group ratio 86%, number average functional group number 2.0.

(2) Polymer polyol (P1)
(P1-1) Volume average particle size 0.6 μm, polymer (styrene / acrylonitrile copolymer of 70/30 weight ratio) content 44% by weight, polyol used is PO / EO block adduct of glycerin, hydroxyl group Value = 56, EO unit content 5% by weight, primary hydroxyl group ratio of terminal hydroxyl group 2%.
(P1-2) Volume average particle diameter 0.8 μm, polymer (styrene / acrylonitrile copolymer of 30/70 weight ratio) content 33.5 wt%, polyol used is PO · EO block adduct of glycerin , Hydroxyl value = 34, EO unit content 14% by weight, primary hydroxyl group ratio of terminal hydroxyl group 75%.

(3) C4-9 alkanolamine (F)
(F-1) Diethanolamine. Hydroxyl value 1600.
(4) Organic polyisocyanate (B)
(B-1) TDI trade name "Coronate T-80" (manufactured by Nippon Polyurethane Industry Co., Ltd.)
(B-2) Urethane-modified MDI NCO% = 27.5.
(5) Foaming agent (C)
(C-1) Water (6) Catalyst (D)
(D-1) “TEDA-L33” manufactured by Tosoh Corporation (triethylenediamine / dipropylene glycol = 33/67 wt% solution)
D-2: “Neostan U-28” manufactured by Nitto Kasei Co., Ltd. (stannic octylate)
(7) Foam stabilizer (E)
(E-1) “SZ-1346” manufactured by Toray Dow Corning

<Test method>
The measurement method for each item is as follows.
-The measurement method and unit of foam physical properties are shown below.
Core density: Conforms to JIS K6400, unit is kg / m ³
Hardness (25% -ILD): Conforms to JIS K6400, unit is N / 314 cm ²
Tensile strength: Conforms to JIS K6400, unit is N / cm ²
Tear strength: Conforms to JIS K6400, unit is N / cm
Cutting elongation: Conforms to JIS K6400, unit is%
Compression residual strain ratio: Conforms to JIS K6400, unit is%
Humid heat compression residual strain rate: Conforms to JIS K6400, unit is%
Rebound resilience: Conforms to JIS K6400, unit is%

  From the results of Table 1, the foams of Examples 1 to 12 have better tear strength and cut elongation than the foams of Comparative Examples 1 to 8.

  The flexible polyurethane foam obtained by the production method of the present invention can be suitably used for applications such as bedding and furniture.

Claims (4)

A polyol component (P) containing a polyether polyol (composition) (A), an alkanolamine (F) having 4 to 9 carbon atoms, and an organic polyisocyanate (B) are mixed with a blowing agent (C) and a catalyst (D). And a flexible polyurethane foam slab foam which is reacted in the presence of the foam stabilizer (E), wherein (A) is an average added mole number x of ethylene oxide per active hydrogen of 3 to 20, the terminal The primary hydroxyl group ratio y (%) of the hydroxyl group is 86 to 100, x and y satisfy the relationship of the following formula (1), and the active hydrogen-containing compound (h) has 1,3-alkylene oxide having 3 or more carbon atoms. 1,2-alkylene oxide having 3 or more carbon atoms in the polyether polyol (A11) and the active hydrogen-containing compound (h), in which ethylene oxide is block-added to And one or more polyether polyols (A1) selected from the group consisting of polyether polyols (A12) obtained by randomly adding ethylene oxide to those obtained by random addition of ethylene oxide, and the active hydrogen-containing compound ( h) contains a trivalent alcohol and / or a 4- to 8-valent alcohol, the number average functional group number of (A) is 2.0 to 2.6 , and the primary hydroxyl group ratio of the terminal hydroxyl group of (A) Is 85 to 95%, and the content of ethylene oxide units in (A) is 10 to 20% by weight based on the weight of (A), based on the total weight of (A) and (F) The manufacturing method of the flexible polyurethane slab foam whose content of (F) is 2 to 10 weight%.
y ≧ 42.0x ^0.47 (1-x / 41) (1)   The method for producing a flexible polyurethane slab foam according to claim 1, wherein the content of the polyether polyol (A1) is 10 to 100% by weight based on the weight of the polyether polyol (composition) (A).   The method for producing a flexible polyurethane slab foam according to claim 1 or 2, wherein the impact resilience of the flexible polyurethane slab foam is 40 to 80%. The flexible polyurethane slab foam according to any one of claims 1 to 3, wherein the foam hardness (25% ILD) of the flexible polyurethane slab foam is 100 to 350 N / 314 cm ² and the cut elongation is 80 to 300%. Form manufacturing method.