JP2014185335A - Polyol composition for manufacturing flexible polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition for manufacturing a low repulsion flexible polyurethane foam small in change of foam hardness even at low temperature, i.e. low in temperature dependency of foam hardness.SOLUTION: There is provided a polyol composition for manufacturing a flexible polyurethane foam (B) containing polyester triol (A) and satisfying following (1) to (6). (1) The content of (A) based on weight of the (B) is 15 to 30 wt.%. (2) The ester group concentration of (B) is 0.1 to 5.0 mmol/g. (3) A hydroxyl value of (B) is 80 to 150 mgKOH/g. (4) The content of an oxyethylene group unit of (B) is 3 to 10 wt.%. (5) The number average functional group number of (B) is 3.1 to 4.0. (6) A primary hydroxyl group ratio of (B) is 3 to 15%.

Description

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

  Flexible polyurethane foam is widely used for furniture, mattresses for bedding, seat cushions for automobiles, clothing, and the like, and in particular, pillows and mattresses for bedding are preferred to have low resilience.

  As a prior art, with respect to 100 parts of polyol, the hydroxyl value is 400 mgKOH / g or more, general formula HO- (R-O-) n-H (n represents an integer of 1 or more, and R is carbon number 2 In the amount of 0.1 to 10 parts by weight, a temperature range of −70 ° C. to −20 ° C. and 0 ° C. to 60 ° C. Each having at least one glass transition point in the temperature range of −70 ° C. to −20 ° C., the peak value of tan δ being 0.15 or more, and the peak of tan δ in the temperature range of 0 ° C. to 60 ° C. A low resilience urethane foam having a value of 0.3 or more is known (see, for example, Patent Document 1).

JP 2004-285152 A

  The polyurethane foam of the above-mentioned patent document aims at a material having “excellent low resilience at room temperature and little increase in hardness even at low temperatures”, but has a relatively high rebound resilience at about 20% at room temperature. Rebound resilience is exhibited, foam hardness at low temperature is high, and performance is not sufficient. The problem to be solved by the present invention is to provide a polyol composition for producing a low-resilience flexible polyurethane foam in which the change in foam hardness is small even at low temperatures, that is, the temperature dependence of the foam hardness is low. That is.

As a result of intensive studies to solve the above problems, the present inventor has reached the invention shown below.
That is, this invention contains polyester triol (A), The polyol composition for flexible polyurethane foam manufacture (B) formed by satisfy | filling following (1)-(6); The said polyol composition for flexible polyurethane foam manufacture And an organic polyisocyanate component (C) in the presence of a foaming agent, a catalyst (D) and a foam stabilizer.
(1) The content of (A) based on the weight of (B) is 15 to 30% by weight;
(2) The ester group concentration of (B) is 0.1 to 5.0 mmol / g;
(3) The hydroxyl value of (B) is 80 to 150 mgKOH / g;
(4) The oxyethylene group unit content of (B) is 3 to 10% by weight;
(5) The number average functional group number of (B) is 3.1 to 4.0;
(6) The primary hydroxyl group ratio of (B) is 3 to 15%.

  By using the polyol composition for producing a flexible polyurethane foam of the present invention, it is possible to produce a low-resilience polyurethane foam having low temperature dependency of foam hardness.

The polyol composition for producing a flexible polyurethane foam of the present invention contains polyester triol (A) and satisfies the following (1) to (6).
(1) The content of (A) based on the weight of (B) is 15 to 30% by weight;
(2) The ester group concentration of (B) is 0.1 to 5.0 mmol / g;
(3) The hydroxyl value of (B) is 80 to 150 mgKOH / g;
(4) The oxyethylene group unit content of (B) is 3 to 10% by weight;
(5) The number average functional group number of (B) is 3.1 to 4.0;
(6) The primary hydroxyl group ratio of (B) is 3 to 15%.

  Examples of the polyol contained in the polyol composition (B) for producing the flexible polyurethane foam of the present invention include known polyols such as the following polyhydric alcohols, polyether polyols and polyester 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).

  The polyether polyol is at least one selected from the group consisting of the polyhydric alcohol, the following polyhydric hydroxyl group-containing compound other than the polyhydric alcohol, the following amino group-containing compound, the following thiol group-containing compound, and the following phosphoric acid group-containing compound. An alkylene oxide (hereinafter abbreviated as AO) adduct of at least one kind of active hydrogen group-containing compound is exemplified. AO has 2 to 6 carbon atoms such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3-propylene oxide, and 1,2 butylene oxide. And 1,4-butylene oxide. 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.

Examples of polyhydric hydroxyl group-containing compounds other than polyhydric alcohols include polyhydric phenols. Specifically, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1,3,6,8-tetrahydroxynaphthalene, anthrol, 1,4,5,8-tetrahydroxyanthracene, 1-hydroxypyrene, etc. Polyphenol polyol; polybutadiene polyol; castor oil-based polyol; (co) polymer of hydroxyalkyl (meth) acrylate and polyfunctional (eg, having 2 to 100 functional groups) polyol such as polyvinyl alcohol, condensate of phenol and formaldehyde ( Novolak) and polyphenols described in US Pat. No. 3,265,641.
(Meth) acrylate means methacrylate and / or acrylate, and the same applies hereinafter.

  Examples of the amino group-containing compound include amines, polyamines, and amino alcohols. Specifically, ammonia; monoamines such as C1-C20 alkylamine (butylamine and the like) and aniline; aliphatic polyamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; heterocyclics such as piperazine and N-aminoethylpiperazine Polyamines; 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 Polyamines obtained by condensation with polyamines; polyether polyamines; hydrazines (such as hydrazine and monoalkylhydrazines), dihydrazides ( Etc. Haq acid dihydrazide and dihydrazide terephthalate), guanidine (butyl guanidine and 1-cyanoguanidine, etc.); dicyandiamide; and the like.

  A polythiol compound is mentioned as a thiol group containing compound. Examples of the polythiol include divalent to octavalent polyvalent thiols. Specific examples include ethanedithiol and 1,6-hexanedithiol.

  Examples of phosphoric acid compounds include phosphoric acid, phosphorous acid, and phosphonic acid.

  As the active hydrogen-containing compound, a compound having two or more active hydrogen-containing functional groups (hydroxyl group, amino group, carboxyl group, thiol group, phosphate group, etc.) in the molecule can also be used.

  The polyester polyol includes a polyhydric hydroxyl group-containing compound (including the polyhydric alcohol and the polyether polyol) and a polycarboxylic acid (aromatic polycarboxylic acid and aliphatic polycarboxylic acid) or an anhydride and a lower alkyl ( An alkyl group having 1 to 4 carbon atoms) a condensation reaction product with an ester-forming derivative such as an ester (such as phthalic anhydride and dimethyl terephthalate); an addition reaction product of the polyhydric alcohol with carboxylic acid anhydride and AO; These AO (EO, PO, etc.) addition reaction products; polylactone polyols {for example, those obtained by ring-opening polymerization of lactones (e.g., ε-caprolactone etc.) using the polyhydric alcohol as an initiator}; and polycarbonate polyols (eg, A reaction product of the polyhydric alcohol and the alkylene carbonate). It is.

Aromatic polycarboxylic acids include phthalic acid, isophthalic acid, terephthalic acid, 2,2'-bibenzyldicarboxylic acid, trimellitic acid, hemilic acid, trimesic acid, pyromellitic acid and naphthalene-1,4 dicarboxylic acid, naphthalene Examples include aromatic polycarboxylic acids having 8 to 18 carbon atoms such as -2,3,6 tricarboxylic acid, diphenic acid, 2,3-anthracene dicarboxylic acid, 2,3,6-anthracentricarboxylic acid and pyrene dicarboxylic acid.
Examples of the aliphatic polycarboxylic acid include succinic acid, fumaric acid, sebacic acid, and adipic acid.

  Examples of other polyols other than these include polydiene polyols such as polymer polyols and polybutadiene polyols and hydrogenated products thereof; acrylic polyols, JP-A 58-57413 and JP-A 58-57414, etc. Hydroxyl group-containing vinyl polymers; natural oil polyols such as castor oil; modified natural oil polyols; and the like.

  The polyol contained in the polyol composition (B) for producing the flexible polyurethane foam of the present invention contains 2 to 10 carbon atoms as the polyhydric alcohol from the viewpoint of the handling of the polyol composition and the temperature dependence of the foam hardness. A divalent to octavalent alcohol is preferred, and a divalent to tetravalent alcohol is more preferred.

The polyether polyol is preferably an AO adduct of a polyhydric alcohol and / or an amino group-containing compound, more preferably a propylene glycol PO adduct, a glycerin PO adduct, a glycerin POEO adduct, or a pentaerythritol PO. It is an adjunct.
The polyester polyol is preferably a condensation reaction product of a polyhydric hydroxyl group-containing compound and a polycarboxylic acid or ester-forming derivative, more preferably a condensation reaction product of a glycerin PO adduct and phthalic anhydride.
As other polyols, polymer polyols are preferred.

  The polyol composition (B) for producing the polyurethane foam of the present invention contains the polyester triol (A) of the above polyester polyols as an essential component. When (B) contains (A), the resilience at room temperature of the polyurethane foam formed and the temperature dependence of the foam hardness are improved. In addition, in this invention, even when the polyester polyol (A) is contained in the polymer polyol to be used, it is handled that the polyol composition (B) contains (A).

  Of the polyester triol (A), polyester triol (A1) obtained by adding AO to a half-esterified product of polyether triol and dicarboxylic anhydride is preferable from the viewpoint of impact resilience.

  As the polyether triol in the polyester triol (A1), an AO adduct having 2 to 4 carbon atoms of glycerin is preferable from the viewpoint of resilience, and a PO adduct of glycerin is more preferable. The number of moles of AO having 2 to 4 carbon atoms is preferably 20 to 40, more preferably 25 to 35.

  The dicarboxylic acid anhydride in the polyester triol (A1) is preferably an aromatic dicarboxylic acid anhydride having 8 to 18 carbon atoms, and more preferably phthalic anhydride, from the viewpoint of impact resilience.

  The hydroxyl value (mgKOH / g) of the polyester polyol (A) is preferably 50 to 150, more preferably 52 to 130, from the viewpoints of handling of the polyol composition and temperature dependency of foam hardness.

  The ester group concentration (mmol / g) of the polyester polyol (A) is preferably from 1.0 to 10.0, more preferably from 1.5 to 10.0, from the viewpoint of the handling of the polyol composition and the temperature dependence of the foam hardness. 8.0.

  The content of the polyester polyol (A) in the polyol composition (B) is usually 15 on the basis of the weight of (B) from the viewpoint of temperature dependency of foam hardness, handling of the polyol composition and moldability of the foam. From the viewpoint of handling the polyol composition, it is preferably 17 to 30% by weight.

The number of functional groups of the polyol other than (A) contained in the polyol composition (B) of the present invention is preferably 2 to 8, more preferably 2 to 4, from the viewpoint of handling of the polyol composition.
The hydroxyl value (mgKOH / g) of the polyol other than (A) is preferably from 30 to 300, more preferably from 40 to 285, from the viewpoints of handling of the polyol composition and temperature dependency of foam hardness.

  The ester group concentration (mmol / g) of the polyol composition (B) is usually from 0.1 to 5.0, preferably from 0.2 to 2.5, from the viewpoint of temperature dependency of foam hardness.

The hydroxyl value (mgKOH / g) of the polyol composition (B) is usually 80 to 150, preferably 81 to 148, more preferably 82 to 145, particularly preferably from the viewpoint of handling (viscosity) and rebound resilience during molding. Is 82-140.
In the present invention, the hydroxyl value is measured according to JISK-1557-1.

  The oxyethylene group unit content (% by weight) of the polyol composition (B) is usually 3 to 10, preferably 4 to 9, more preferably 5 to 9, particularly preferably 5 from the viewpoints of reactivity and compressive residual strain. .5-9.

  The number average functional group number of the polyol composition (B) is generally 3.1 to 4.0, preferably 3.1 to 3.8, and more preferably 3.2 to 3.7 from the viewpoint of durability.

The primary hydroxyl group ratio (%) of the hydroxyl groups possessed by the polyol composition (B) [value expressed as a percentage (%) of the number of hydroxyl groups bonded to primary carbon to the total number of hydroxyl groups] is a viewpoint of reactivity. To usually 3-15 and 4-13.
In the present invention, the primary hydroxyl group ratio is determined by ¹ H-NMR method after pre-treatment of the sample in advance. Details of the ¹ H-NMR method will be specifically described below.
Sample preparation method About 30 mg of a measurement sample is weighed into a sample tube for ¹ H-NMR 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 and the mixture is allowed to stand at 25 ° C. for about 5 minutes to make the polyol a trifluoroacetic acid ester, which is used as a sample for analysis. Here, the deuterated solvent is deuterated chloroform, deuterated toluene, deuterated dimethyl sulfoxide, deuterated dimethylformamide, or the like, and a solvent that can be dissolved in the sample is appropriately selected.
• ¹ H-NMR measurement ¹ H-NMR measurement is performed under normal conditions.
・ Calculation method of primary hydroxyl ratio Since the signal derived from the methylene group bonded with the primary hydroxyl group is observed around 4.3 ppm, the signal derived from the methine group bonded with the secondary hydroxyl group is observed around 5.2 ppm, The primary hydroxyl group ratio is calculated by the following formula [1].
Primary hydroxyl group ratio (%) = [r / (r + 2s)] × 100 [1]
However,
r: integrated value of a signal derived from a methylene group to which a primary hydroxyl group is bonded in the vicinity of 4.3 ppm s: 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 polyol composition (B) for producing a flexible polyurethane foam can be easily obtained by mixing the polyester polyol (A) and other polyols. In producing (B), any known method may be used for mixing the polyester polyol (A) and other polyols.

  The method for producing a flexible polyurethane foam of the present invention comprises a polyol composition (B) for producing a flexible polyurethane foam of the present invention and an organic polyisocyanate component (C) in the presence of a foaming agent, a catalyst (D) and a foam stabilizer. It is made to react with.

  As the organic polyisocyanate component (C), all organic polyisocyanates used in flexible polyurethane foams can be used. Aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, these Modified products (urethane groups, carbodiimide groups, allophanate groups, urea groups, burette groups, isocyanurate groups, oxazolidone group-containing modified products, etc.) and mixtures of two or more of these.

  Aromatic polyisocyanates include aromatic diisocyanates having 6 to 16 carbon atoms (excluding carbons in NCO groups; the following polyisocyanates are also the same), aromatic triisocyanates having 6 to 20 carbon atoms, and crude products of these isocyanates. Thing etc. are mentioned. Specific examples include 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and 4,4′-diphenylmethane diisocyanate ( MDI), polymethylene polyphenylene polyisocyanate (crude MDI), naphthylene-1,5-diisocyanate, and triphenylmethane-4,4 ′, 4 ″ -triisocyanate.

  Examples of the aliphatic polyisocyanate include aliphatic diisocyanates having 6 to 10 carbon atoms. Specific examples include 1,6-hexamethylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate, lysine diisocyanate, and the like.

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

Examples of the araliphatic isocyanate include araliphatic diisocyanates having 8 to 12 carbon atoms. Specific examples include xylylene diisocyanate and α, α, α ′, α′-tetramethylxylylene diisocyanate.
Specific examples of the modified polyisocyanate include carbodiimide-modified MDI.

  Of these, aromatic polyisocyanates are preferred from the viewpoint of reactivity and impact resilience, more preferably TDI, crude TDI, MDI, crude MDI and modified products of these isocyanates, particularly preferably TDI, MDI and Crude MDI.

  Examples of the foaming agent include water, liquefied carbon dioxide, and a low boiling point compound having a boiling point of −5 to 70 ° C.

  Examples of the low boiling point compound include a hydrogen atom-containing halogenated hydrocarbon and a low boiling point hydrocarbon. Specific examples of the hydrogen atom-containing halogenated hydrocarbon and low boiling point hydrocarbon include methylene chloride, HCFC (hydrochlorofluorocarbon) (HCFC-123, HCFC-141b, HCFC-142b, etc.); HFC (hydrofluorocarbon) (HFC- 152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa and HFC-365mfc), butane, pentane and cyclopentane.

  Among these, from the viewpoint of moldability, water, liquefied carbon dioxide, methylene chloride, cyclopentane, HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc and It is preferable to use a mixture of two or more of these as a foaming agent.

  The amount of water used as the foaming agent is 1.0 to 8.0 parts by weight with respect to 100 parts by weight of the polyol composition for producing flexible polyurethane foam (B) used in the production of urethane foam from the viewpoint of impact resilience. The amount is more preferably 1.5 to 4.0 parts by weight. The amount of the low boiling point compound used is preferably 30 parts by weight or less, more preferably 5 to 25 parts by weight, with respect to 100 parts by weight of the polyol component, from the viewpoint of poor molding. The liquefied carbon dioxide gas is preferably 30 parts by weight or less, more preferably 1 to 25 parts by weight.

  As the catalyst (D), any catalyst that promotes the urethanization reaction can be used. From the viewpoint of foam hardness and rebound resilience, the foaming reaction activity constant relative to the resination reaction activity constant [Kw (1)] [ It is preferable to use a catalyst having a ratio [Kw (2) / Kw (1)] of 0.15 or less, and the ratio [Kw (2) / Kw (1)] is 0.14. More preferably, the following catalysts are used.

  The ratio [Kw (2) / Kw (1)] of the foaming reaction activity constant [Kw (2)] to the resination reaction activity constant [Kw (1)] of the catalyst (D) is, for example, the technology of Tosoh Corporation. Document No. It is calculated from the resination reaction activity constant [Kw (1)] and the foaming reaction activity constant [Kw (2)] determined by the method described in B-58081.

Resinization reaction activity constant [Kw (1)] is prepared by adding an aromatic isocyanate compound monomer and a primary alcohol so that the molar ratio of isocyanate group / hydroxyl group is 1.0, and adding a certain amount of the target catalyst. The reaction rate constant when the reaction is carried out at a constant temperature in a benzene or 1,4-dioxane solvent is a value obtained by dividing by the catalyst concentration.
The foaming reaction activity constant [Kw (2)] is a value obtained under the same conditions as in the resination reaction activity constant except that the primary alcohol is replaced with water. .
The aromatic isocyanate compound monomer is selected from phenyl isocyanate or tolylene diisocyanate. The primary alcohol is selected from 2-ethylhexanol or ethylene glycol. Furthermore, reaction temperature is performed at 20-30 degreeC, and makes it constant temperature during reaction. The activity constant thus determined is, for example, Tosoh Research Report Vol. 39 (1995), edited by Keiji Iwata, “Polyurethane Resin Handbook”, Nikkan Kogyo Shimbun, published May 20, 1987, 1st edition, 118. Page.

A catalyst having a ratio [Kw (2) / Kw (1)] of the foaming reaction activity constant [Kw (2)] to the resination reaction activity constant [Kw (1)] of 0.15 or less is a tertiary amine. {Triethylenediamine, N-ethylmorpholine, N, N-dimethylaminoethanol, N- (N ′, N ′,-2-dimethylaminoethyl) morpholine, etc.} and carboxylic acid metal salts (potassium acetate, potassium octylate) , Stannous octylate, dibutylstannic dilaurate, lead octylate, etc.).
Among these, from the viewpoint of foam hardness and impact resilience, triethylenediamine, stannous octylate and dibutylstannic dilaurate are preferable.

  From the viewpoint of foam hardness and impact resilience, the catalyst (D) is used in an amount of 0.01 to 5.0 with respect to 100 parts by weight of the polyol composition (B) for producing the flexible polyurethane foam used during the production of the urethane foam. A weight part is preferable, More preferably, it is 0.05-2.0 weight part. A catalyst (D) may be used individually by 1 type, or may use 2 or more types together.

As the foam stabilizer, any of those used for the production of ordinary polyurethane foams can be used. “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 0.4 to 5.0 parts by weight, more preferably 0.4 to 3.0 parts by weight with respect to 100 parts by weight of the polyol component, from the viewpoints of moldability and impact resilience. It is.

In the method for producing the flexible polyurethane foam of the present invention, if necessary, other auxiliary agents described below may be used and reacted in the presence thereof.
Other auxiliaries include colorants (dyes and pigments), plasticizers (phthalates and adipates, etc.), organic fillers (synthetic short fibers, hollow microspheres made of thermoplastic or thermosetting resins, etc.) And known auxiliary components such as flame retardants (such as phosphate esters and halogenated phosphate esters), antioxidants (such as triazole and benzophenone), and antioxidants (such as hindered phenol and hindered amine).

  As the addition amount of these auxiliaries, the colorant is preferably 1 part by weight or less with respect to 100 parts by weight of the polyol component. The plasticizer is preferably 10 parts by weight or less, more preferably 5 parts by weight or less. The organic filler is preferably 50 parts by weight or less, more preferably 30 parts by weight or less. The flame retardant is preferably 30 parts by weight or less, and more preferably 2 to 20 parts by weight. The anti-aging agent is preferably 1 part by weight or less, more preferably 0.01 to 0.5 part by weight. The antioxidant is preferably 1 part by weight or less, more preferably 0.01 to 0.5 part by weight. The total amount of auxiliary agent used is preferably 50 parts by weight or less, more preferably 0.2 to 30 parts by weight.

  In the production method of the present invention, the isocyanate index (index) [ratio of equivalent of isocyanate group in (C) to equivalent of active hydrogen atom-containing group in (B) × 100] in the production of flexible polyurethane foam is repulsive. From a viewpoint of elasticity, 70-88 are preferable, More preferably, it is 72-87, Most preferably, it is 75-86.

  An example of a method for producing a flexible polyurethane foam according to the method of the present invention is as follows. First, a predetermined amount of a polyol component for producing a flexible polyurethane foam, a foaming agent, a catalyst, a foam stabilizer, and, if necessary, other additives are mixed. The mixture and the organic polyisocyanate component are then rapidly mixed using a polyurethane foam foamer or stirrer. The obtained mixed liquid (foaming stock solution) can be continuously foamed to obtain a flexible polyurethane foam. Alternatively, it can be poured into a sealed or open mold (made of metal or resin), subjected to a urethanization reaction, cured for a predetermined time, and then demolded to obtain a flexible polyurethane foam.

  The rebound resilience of the flexible polyurethane foam of the present invention is preferably 5 to 12%, more preferably 6 to 11%, from the viewpoints of sitting comfort and sleeping comfort.

  The ratio of the foam hardness between 0 ° C. and 25 ° C. of the flexible polyurethane foam of the present invention is preferably 1.0 to 1.7, particularly from the viewpoint of sitting comfort and sleeping comfort on days with low temperatures such as winter. 1.6 is more preferable.

  The flexible polyurethane foam of the present invention is used for furniture, bedding pillows, bedding mattresses, automobile seat cushions, clothing and the like.

  EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by this.

Examples 1 to 23, Comparative Examples 1 to 5
In accordance with the formulation shown in Table 1 and Table 2, foamed under the following foaming conditions to produce a flexible polyurethane foam, the core density of the foam after standing at a temperature of 25 ° C. and a humidity of 50% for 24 hours (kg / m ³ ) Based on the following measurement methods, hardness at 0 ° C. and 25 ° C. (25% ILD, N / 314 cm ² ), tensile strength (N / cm ² ), rebound resilience (%) and compression residual strain (%) Measured. The results are shown in Tables 1 and 2. In addition, the numerical value of raw materials other than TDI in the compounding recipes of Tables 1 and 2 means parts by weight, and TDI was used in an amount that gives the isocyanate index shown in the compounding recipes.

(Foaming conditions)
Mold size: 250mm x 250mm x 250mm
Material: Wood Mixing method: Hand mixing (foaming method in which a necessary amount of necessary reagent is charged in a predetermined container, and then a stirring blade is inserted into the container and stirred for 6 to 20 seconds at a rotational speed of 5000 rpm)
Mixing time: 6 to 20 seconds, stirring blade rotation speed: 5000 rotations / minute

The polyurethane foam raw materials in Examples 1 to 23 and Comparative Examples 1 to 5 are as follows.
(1) Polyol P-1: pentaerythritol PO adduct [hydroxyl value = 249 mgKOH / g, ester group concentration = 0 mmol / g]
P-2: Dipropylene glycol PO adduct [hydroxyl value = 112.2 mgKOH / g, ester group concentration = 0 mmol / g]
P-3: Glycerin POEO adduct [hydroxyl value = 112.2 mgKOH / g, content of oxyethylene group units = 70 wt%, ester group concentration = 0 mmol / g]
P-4: Glycerin POEO adduct [hydroxyl value = 56 mg KOH / g, oxyethylene group unit content = 7 wt%, ester group concentration = 0 mmol / g]
P-5: Glycerin PO adduct [hydroxyl value = 34 mgKOH / g, ester group concentration = 0 mmol / g]
P-6: Pentaerythritol PO adduct [hydroxyl value = 400 mgKOH / g, ester group concentration = 0 mmol / g]
P-7: Glycerin POEO adduct [hydroxyl value = 56 mgKOH / g, oxyethylene group unit content = 9% by weight, ester group concentration = 0 mmol / g]
P-8: Polyester triol in which PO is added to a carboxyl group produced by half esterification reaction of 1 mol of glycerin PO adduct (molecular weight 1700) and 6 mol of phthalic anhydride [hydroxyl value = 56 mgKOH / g, ester group concentration = 4.0 mmol / g]
P-1 to P-7 do not correspond to the polyester polyol (A) of the present invention, and P-8 corresponds to (A).

(2) Organic polyisocyanate component (D-1)
TDI: “Coronate T-80” manufactured by Nippon Polyurethane Industry Co., Ltd. (isocyanate group content = 48.3 wt%)
(3) Blowing agent Blowing agent-1: Water (4) Catalyst catalyst-1: "DABCO-33LX" manufactured by Air Products Japan Ltd. [Triethylenediamine: Ratio of foaming reaction activity constant to resination reaction activity constant { Kw (2) / Kw (1)} = 0.134]
Catalyst-2: Tin octylate [trade name: “Neostan U-28” (stannic octylate) manufactured by Nitto Kasei Co., Ltd., ratio of foaming reaction activity constant to resinization reaction activity constant {Kw (2) /Kw(1)}=0.03]
Catalyst-3: “TOYOCAT-ET” manufactured by Tosoh Corporation [ratio of foaming reaction activity constant to resination reaction activity constant {Kw (2) / Kw (1)} = 3.90]
(5) Foam stabilizer Foam stabilizer-1: “SZ-1959” manufactured by Toray Dow Corning Co., Ltd.
Foam stabilizer-2: “L-626” manufactured by Momentive Performance Materials
Foam stabilizer-3: “SF-2904” manufactured by Toray Dow Corning Co., Ltd.
Foam stabilizer-4: “SRX-294A” manufactured by Toray Dow Corning Co., Ltd.

<Test method>
The measurement method for each item is as follows.
Core density: Conforms to JIS K6400 (unit: kg / m ³ ).
Hardness (25% -ILD): Conforms to JIS K6400 (unit: N / 314 cm ² ).
Tensile strength: Conforms to JIS K6400 (unit: N / cm ² ).
Rebound resilience: Conforms to JIS K6400 (unit:%).
Compression residual strain rate: compliant with JIS K6400 (unit:%).

As is clear from Tables 1 and 2, in Examples 1 to 23 using a polyol composition containing an appropriate amount of polyester polyol (A), the impact resilience is low and the change in hardness at low temperature is small (foam hardness). Temperature dependency is low). On the other hand, in Comparative Examples 1 and 2 which do not contain the polyester polyol (A), the resilience is high and the hardness change at low temperature is large (the temperature dependence of the hardness of the foam is high). In Comparative Examples 3 and 4 in which the use amount of) is not appropriate, the foam has many closed cells, and a foam capable of measuring physical properties cannot be obtained.
It can be seen that the flexible polyurethane foam obtained by using the polyol composition of the present invention has low impact resilience and low temperature dependency of the hardness of the foam, and is particularly suitable for bedding (mattress, pillow). .

  The flexible polyurethane foam obtained by using the polyol composition of the present invention is excellent in low resilience and low-temperature properties (low foam temperature dependence), and is suitable for seat cushions, bedding, furniture and the like.

Claims (6)

Polyol composition (B) for producing a flexible polyurethane foam comprising the polyester triol (A) and satisfying the following (1) to (6):
(1) The content of (A) based on the weight of (B) is 15 to 30% by weight;
(2) The ester group concentration of (B) is 0.1 to 5.0 mmol / g;
(3) The hydroxyl value of (B) is 80 to 150 mgKOH / g;
(4) The oxyethylene group unit content of (B) is 3 to 10% by weight;
(5) The number average functional group number of (B) is 3.1 to 4.0;
(6) The primary hydroxyl group ratio of (B) is 3 to 15%.   The polyol composition for producing a flexible polyurethane foam according to claim 1, wherein the polyester polyol (A) has a hydroxyl value of 50 to 150 mgKOH / g.   The manufacturing method of the flexible urethane foam which makes the polyol composition for flexible polyurethane foam manufacture of Claim 1 or 2 and organic polyisocyanate component (C) react in presence of a foaming agent, a catalyst (D), and a foam stabilizer. .   The ratio [Kw (2) / Kw (1)] of the foaming reaction activity constant [Kw (2)] to the resination reaction activity constant [Kw (1)] of the catalyst (D) is 0.15 or less. The manufacturing method of the flexible polyurethane foam of Claim 3.   A flexible polyurethane foam having a rebound resilience of 5 to 12% obtained by the production method according to claim 3 or 4.   The flexible polyurethane foam according to claim 5, wherein the ratio of the hardness of the foam at 0 ° C. to the foam hardness at 25 ° C. is 1.0 to 1.7.