JP2013227490A - Method for producing flexible polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a flexible polyurethane foam free from scorch generation trouble.SOLUTION: There is provided a method for producing a flexible polyurethane foam by reacting a polyol component (A) with a polyisocyanate component (E) in the presence of an antioxidant (B), a catalyst (C), a foam stabilizer (D) and a foaming agent (F), wherein the aldehyde content of (A) is ≤150 ppm based on the weight of (A), the amount of (B) is 100-9,500 ppm based on the weight of (A), and the catalyst (C) comprises at least one kind of catalyst (C1) having a (foaming reaction rate constant)/(resinification reaction rate constant) ratio of 1.0×10to 9.0×10and at least one kind of catalyst (C2) having a value of the ratio of 1.0 to 10.0.

Description

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

  In recent years, the density of flexible polyurethane foam has been reduced for the purpose of cost reduction. In order to make it low density, it is necessary to use water, methylene chloride, etc. which are foaming agents (refer patent document 1 and nonpatent literature 1). However, when the amount of water used is increased, the internal temperature of the foam at the time of foam production rises and scorch occurs. Increasing the amount of methylene chloride has an adverse effect on the environment.

Japanese Patent Laid-Open No. 06-199973

Keiji Iwata, "Polyurethane Resin Handbook", Nikkan Kogyo, May 20, 1987, 1st Edition, 32 pages

  An object of the present invention is to provide a method for producing a flexible polyurethane foam which does not generate scorch.

  As a result of intensive studies to solve such problems, the present inventor solved the above problems by setting the polyol component to a specific aldehyde content and using an antioxidant and a specific catalyst. We have found out that we can do it and have reached the present invention.

That is, the method for producing a flexible polyurethane foam of the present invention comprises a polyol component (A) and a polyisocyanate component (E), an antioxidant (B), a catalyst (C), a foam stabilizer (D) and a foaming agent ( F) A process for producing a flexible polyurethane foam obtained by reacting in the presence of F), wherein the aldehyde content contained in (A) is 150 ppm or less based on the weight of (A), and the use of (B) The amount is 100 to 9500 ppm based on the weight of (A), and the value of [foaming reaction rate constant / resinization reaction rate constant] is 1.0 × 10 ^{−4 to} 9.0 × 10 ⁻ as (C). ^The gist is to use at least one catalyst (C1) that is 1 and at least one catalyst (C2) that is 1.0 to 10.0.

  According to the method for producing a flexible polyurethane foam of the present invention, a flexible polyurethane foam that does not generate scorch can be obtained.

  As the polyol component (A) used in the production method of the present invention, a compound having one or more, preferably 2 to 8 active hydrogen-containing groups can be used, and two or more compounds may be used in combination (for foaming agents). Excluding water used). Examples of (A) include polyether polyols, polyester polyols, one or more polyols selected from various other polyols, polyhydric alcohols, and alkanolamines.

  Examples of polyhydric alcohols include dihydric alcohols having 2 to 20 carbon atoms {aliphatic diols (ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc. Alkylene glycols; and alicyclic diols (cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol)}, trivalent alcohols having 3 to 20 carbon atoms {aliphatic triols (glycerin, trimethylolpropane, trimethylolethane, hexanetriol, etc.) Alkanetriol}; a polyhydric alcohol having 4 to 8 or more carbon atoms having 5 to 20 carbon atoms {aliphatic polyol (pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, etc.) Kang polyols) and those and / or intramolecular or intermolecular dehydration products of alkane triol}; and sucrose, glucose, mannose, fructose and sugar and their derivatives such as methyl glucoside) and the like.

  Examples of the alkanolamine include alkanolamines having 2 to 20 carbon atoms (for example, monoethanolamine, diethanolamine, triethanolamine, and isopropanolamine).

  Examples of the polyether polyol include a polyol having a structure in which an alkylene oxide is added to an active hydrogen-containing compound such as the polyhydric alcohol, ammonia, the alkanolamine, an amine, a polyhydric phenol, or a polycarboxylic acid, and a mixture thereof.

  As an amine, as an aliphatic amine, an alkylamine having 1 to 20 carbon atoms (for example, n-butylamine and octylamine), an alkylenediamine having 2 to 6 carbon atoms (for example, ethylenediamine, propylenediamine and hexamethylenediamine), carbon Examples include polyalkylene polyamines having 4 to 20 carbon atoms (dialkylene triamines having 6 to 6 carbon atoms in the alkylene group to hexaalkylene heptamines such as diethylenetriamine and triethylenetetramine). C6-C20 aromatic mono- or polyamines (for example, aniline, toluidine, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline and diphenyletherdiamine); C4-20 fats Cyclic amines (for example, cyclohexylamine, isophoronediamine, cyclohexylenediamine, and dicyclohexylmethanediamine); heterocyclic amines having 4 to 20 carbon atoms (for example, piperazine, aminoethylpiperazine, and those described in Japanese Patent Publication No. 55-21044) ) And the like.

  Examples of the polyhydric phenol include monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenols such as bisphenol A, bisphenol F and bisphenol sulfone; condensates of phenol and formaldehyde (novolac); Examples include the polyphenols described.

  Examples of the polycarboxylic acid include aliphatic polycarboxylic acids having 4 to 18 carbon atoms (such as succinic acid, adipic acid, sebacic acid, glutaric acid and azelaic acid), and aromatic polycarboxylic acids having 8 to 18 carbon atoms (terephthalic acid and Isophthalic acid and the like) and mixtures of two or more thereof.

  The alkylene oxide added to the active hydrogen-containing compound (which may be used in combination of two or more) is preferably one having 2 to 8 carbon atoms, such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide. (Hereinafter abbreviated as PO), 1,2-, 1,4-, 1,3- and 2,3-butylene oxide, styrene oxide, α-olefin oxide and combinations of two or more thereof (block and / or random) Addition). Preferable is PO and / or EO.

  As the polyester polyol, the above-mentioned polyhydric alcohol and / or polyether polyol (in particular, ethylene glycol, diethylene glycol, propylene glycol, 1,3- or 1,4-butanediol, 1,6-hexanediol, neopentyl glycol, etc.) Dihydric alcohols of these or mixtures thereof with trihydric or higher polyhydric alcohols such as glycerin and trimethylolpropane, and alkylene oxide low-molar (1 to 10 mol) adducts of these polyhydric alcohols), Ester-forming derivatives such as carboxylic acid or its anhydride, lower alkyl (carbon number of alkyl group: 1 to 4) ester (for example, adipic acid, sebacic acid, maleic anhydride, phthalic anhydride, dimethyl terephthalate, etc.), Or the carboxylic anhydride and Condensation reaction product with alkylene oxide; addition reaction product thereof with alkylene oxide (EO, PO, etc.); polylactone polyol, for example, lactone having 5 to 8 carbon atoms (e.g., ε-caprolactone etc.) using the polyhydric alcohol as an initiator Obtained by ring-opening polymerization of polycarbonate; polycarbonate polyol, for example, reaction product of polyhydric alcohol and alkylene carbonate (alkylene group having 4 to 8 carbon atoms); natural oil-based polyol such as castor oil; natural oil-based polyol And the like.

  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 number average functional group number of the polyol component (A) is preferably from 2.0 to 6.0, more preferably from 1.5 to 4.0, and still more preferably from the viewpoint of foam hardness and mechanical properties of the polyurethane foam. Is 1.7 to 3.5, particularly preferably 1.8 to 3.2.
The hydroxyl value (mgKOH / g) of (A) is preferably 20 to 500, more preferably 25 to 400, and particularly preferably 30 from the viewpoint of handling at the time of molding (viscosity of polyol component (A)) and moldability. ~ 300, most preferably 30-200.
The total amount of oxyethylene units in (A) is preferably from 0 to 95% by weight, more preferably from 1 to 85% by weight, particularly preferably from the viewpoint of curability and mechanical properties, based on the weight of (A). 1 to 75% by weight.

  The aldehyde content contained in (A) is 150 ppm or less based on the weight of (A). If it exceeds 150 ppm, the center of the foam causes scorch, which is not preferable. The aldehyde content is preferably 130 ppm or less, particularly preferably 80 ppm or less, and most preferably 60 ppm or less from the viewpoint of not generating scorch. Examples of the method for reducing the aldehyde content include a method for reducing the oxygen concentration in the gas phase during the production of (A) (Japanese Patent Laid-Open No. 6-157744, etc.).

The aldehyde content in the polyol (A) is measured as follows.
Weigh sample accurately in a glass bottle with a lid. The sampling amount is 50 g when the expected aldehyde content is less than 100 ppm, 30 g when it is 100 or more and less than 300 ppm, and 20 g or less when it is 300 ppm or more. When the aldehyde content is unknown, measurement is first performed with a sampling amount of 20 g, and when the measured value is less than 300 ppm, the measurement is performed again with the above sample amount. After sampling, 50 ml (25 ° C.) of hydroxylamine hydrochloride solution (50 g of hydroxylamine hydrochloride dissolved in 150 ml of pure water and added with isopropanol to 1 L) was added with a whole pipette, mixed well, sealed, and sealed. Leave at 30 ° C. for 30 minutes. After cooling to room temperature, 50 mL of methanol is added immediately before titration, and potentiometric titration is performed with an N / 10 methanolic KOH standard solution. At the same time, a blank test is performed.
Aldehyde content (ppm) = (W−X) × Y × 2900 / Z
Where, W: Titration ml number of N / 10 methanolic KOH standard solution required for this test X: Titration ml number of N / 10 methanolic KOH standard solution required for blank test Y: N / 10 methanolic KOH standard solution Titer Z: Sample collection amount (g)

  The method for producing a flexible polyurethane foam of the present invention comprises a polyol component (A) and a polyisocyanate component (E), an antioxidant (B), a catalyst (C), a foam stabilizer (D) and a foaming agent (F). To form a polyurethane foam.

  As the antioxidant (B), amine, piperidine, phenol, phosphate ester, phosphite, thioether, ascorbic acid and the like can be used.

Examples of the amine include compounds represented by the following general formula (1):
_{^{R 1 - (Ar) 1-}} m -NH-Ph- (NH) m -R 2 (1)
In the formula, Ph is a phenylene group, Ar is an arylene group, and m is 1 or 0. R ¹ and R ² are H or a hydrocarbyl group having 3 or more carbon atoms. When m is 0, R ¹ and R ² may be bonded via S to form a phenothiazine ring together with NH.

The hydrocarbyl group of R ¹ and R ² includes an alkyl group having 3 to 14 (preferably 3 to 8) carbon atoms, such as i-propyl group, n-, i- and t-butyl group, and i-hexyl group. And n- and sec-octyl groups; aryl groups having 6 to 30 carbon atoms, such as phenyl groups, (di) alkylphenyl groups (tolyl groups, etc.) and naphthyl groups (β-naphthyl groups, etc.); and 7-30 carbon atoms Aralkyl groups such as benzyl group and (di) alkylbenzyl group (α, α-dimethylbenzyl group and the like).
Arylene groups (Ar) include phenylene groups and naphthylene groups. The phenylene group of Ar and Ph includes a p-phenylene group.

Specific examples include the following.
1) When m is 1: R ¹ —NH—Ph—NH—R ²
N, N′-bishydrocarbylphenylenediamine, for example, N, N′-bisC 3-14 alkylphenylenediamine [N, N′-bis (t-butyl) -p-phenylenediamine, N, N′-bis ( sec-octyl) -p-phenylenediamine and the like] and N, N′-bis (β-naphthyl) phenylenediamine.
2) When m is 0: R ¹ —Ar—NH—Ph—R ²
Diarylamines such as diphenylamine, N-phenyl-2-naphthylamine, and dihydrocarbyl diphenylamine [diC3-14 alkyldiphenylamine (eg, dioctyldiphenylamine), bis (α, α-dimethylbenzyl) diphenylamine, etc.], and phenothiazine.

  As piperidine, 2- (3,5-di-t-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), bis (Tetramethylpiperidyl) sebacate etc. are mentioned.

  Phenol includes 2,6-di-tert-butyl-p-cresol, a condensate of 2,6-di-tert-butyl-p-cresol, 3,9-bis {2- [3- (3-tert- Butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5,5] undecane, octadecyl-3- (3,5- Di-tert-butyl-4-hydroxyphenyl) propionate, tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane and octadecyl-3 (3,5 -Di-tert-butyl-4-hydroxyphenyl) propionate and the like.

  Examples of phosphate esters include alkyl phosphate (C 1-18) esters such as trimethyl phosphate, tributyl phosphate, and trioctyl phosphate.

  As an antioxidant (B), from a scorch viewpoint, a piperidine, phosphate ester, phenol, and an amine are preferable, More preferably, it is a phenol and an amine. It is also preferable to use two or more of these in combination.

  The amount of (B) used is 100 to 9500 ppm based on the weight of the polyol component (A), and is preferably 500 to 8000 ppm, particularly preferably 1000 to 6000 ppm from the viewpoint of not generating scorch.

  As the catalyst (C), any catalyst that promotes the urethanization reaction can be used. A tertiary amine different from the amine of (B) {triethylenediamine, N-ethylmorpholine, diethylethanolamine, tetramethylethylenediamine, diaminobicyclo Octane, 1,2-dimethylimidazole, 1-methylimidazole, 1,8-diazabicyclo- [5,4,0] -undecene-7, bis (N, N-dimethylamino-2-ethyl) ether and N, N , N ′, N′-tetramethylhexamethylenediamine and the like} and metal carboxylates (potassium acetate, potassium octylate, stannous octylate, dibutylstannic dilaurate, lead octylate, etc.) and the like.

In the present invention, at least one catalyst (C1) having a value of [foaming reaction rate constant / resinization reaction rate constant] of 10 × 10 ^{−4 to} 9.0 × 10 ⁻¹ is used as the catalyst (C). And at least one catalyst (C2) that is 1.0 to 10.0.
(C1) includes stannous octylate.
(C2) includes bis (N, N-dimethylamino-2-ethyl) ether.

  The foaming reaction rate constant is a reaction rate constant that determines the rate of the foaming reaction between the polyisocyanate and water. In the present invention, the reaction rate constant of the foaming reaction between tolylene diisocyanate and water is used. On the other hand, the resinization reaction rate constant is a reaction rate constant that determines the rate of the resinization reaction between the polyol and the polyisocyanate. In the present invention, the reaction rate constant of the resinization reaction between tolylene diisocyanate and diethylene glycol is used. .

The amount of the catalyst (C) used is 0.01 to 5 with respect to 100 parts by weight of the polyol component (A) used in the production of the urethane foam from the viewpoint of improving mechanical properties (tensile strength, tear strength, compression hardness). 0.0 part by weight is preferable, and 0.1 to 2.0 parts by weight is more preferable.
The amount of the catalyst (C1) used is preferably 0.001 to 4.999 parts by weight with respect to 100 parts by weight of the polyol component (A) used in the production of urethane foam from the viewpoint of reactivity and curability of the polyurethane foam. More preferably, it is 0.01 to 1.99 parts by weight.
The amount of the catalyst (C2) used is preferably 0.001 to 4.999 parts by weight with respect to 100 parts by weight of the polyol component (A) used during the production of the urethane foam, from the viewpoint of reactivity and polyurethane foam curability. More preferably, it is 0.01 to 1.99 parts by weight.

  As the polyisocyanate component (E), all organic polyisocyanates used in the production of polyurethane foams can be used. Aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modifications thereof 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.

  As aromatic polyisocyanate, C6-C16 aromatic diisocyanate, C6-C20 aromatic triisocyanate, and crude products of these isocyanates (excluding carbon in NCO group; the following polyisocyanates are also the same) Etc. 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 polyisocyanate 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.

  Among these, aromatic polyisocyanates are preferable from the viewpoint of reactivity and mechanical properties of polyurethane foam, more preferably TDI, crude TDI, MDI, crude MDI and modified products of these isocyanates, particularly preferably TDI. It is.

As the foam stabilizer (D), any of those used for the production of polyurethane foam can be used. Dimethylsiloxane foam stabilizers [“SRX-253”, “PRX-607” manufactured by Toray Dow Corning Silicone Co., Ltd.], etc. ] And polyether-modified dimethylsiloxane foam stabilizers [“L-540”, “SZ-1142”, “L-3601”, “SRX-294A” manufactured by Toray Dow Corning Silicone Co., Ltd.] and Degussa Japan Co., Ltd. Manufactured "B-4900" etc.]. From the viewpoint of the breathability of the polyurethane foam, “L-540”, “SRX-294A” and “PRX-607” are preferable.
The amount of (D) used is preferably 0.5 to 3 parts by weight, more preferably 1 to 2 parts by weight, based on 100 parts by weight of the polyol component (A), from the viewpoint of the breathability and moldability of the polyurethane foam. It is.

  Examples of the foaming agent (F) include water and low-boiling compounds having a boiling point of 0 to 50 ° C.

Low boiling point compounds include hydrogen atom-containing halogenated hydrocarbons and low boiling point hydrocarbons.
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), HFE (hydrofluoroether) (HFE-245pc, etc.), pentane and cyclopentane.
Among these, methylene chloride, HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc, and a mixture of two or more of these are preferable from the viewpoint of moldability. .

Among (F), the usage-amount of water is 4.0-8.0 weight part with respect to 100 weight part of polyol components (A) from a viewpoint of making foam density low and suppressing generation | occurrence | production of scorch. More preferably, it is 5.5 to 7.0 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, and still more preferably 6 to 14 parts per 100 parts by weight of (A) from the viewpoint of suppressing molding defects. Parts by weight.

In the production method of the present invention, if necessary, other additives described below may be used and reacted in the presence thereof.
Examples of other additives include known auxiliary components such as colorants (dyes and pigments), flame retardants (such as phosphate esters and halogenated phosphate esters), and antioxidants (such as triazole and benzophenone). Regarding the amount of these other additives used relative to 100 parts by weight of the polyol component (A), the colorant is preferably 1 part by weight or less, the flame retardant is preferably 5 parts by weight or less, more preferably 2 parts by weight or less. The anti-aging agent is preferably 1 part by weight or less, more preferably 0.5 part by weight or less.

  In the production method of the present invention, the isocyanate index (index) [(NCO group / active hydrogen atom-containing group) equivalent ratio × 100] in producing the polyurethane foam is preferably 70 to 130 from the viewpoint of moldability, Preferably it is 80-125, Most preferably, it is 90-120.

  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 (A), an antioxidant (B), a catalyst (C), a foam stabilizer (D), a foaming agent (F), and other additives as necessary are mixed. The mixture and the polyisocyanate component (E) are then rapidly mixed using a polyurethane foaming machine or a 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 present invention is particularly suitable as a method for obtaining a flexible polyurethane foam by continuous foaming from the viewpoint of achieving both reduction in density and suppression of scorch generation.

  The flexible polyurethane foam obtained by the method of the present invention is suitably used for vehicle seats, furniture, apparel, electrical equipment, electronic equipment or packaging, and more preferably for furniture, apparel, electrical It is suitably used for equipment, electronic equipment or packaging.

EXAMPLES Hereinafter, although an Example demonstrates this invention further, this invention is not limited by this.
In the following examples, the method for measuring the hydroxyl value of the polyol component and the primary OH conversion rate of the terminal hydroxyl group is as follows.
<Hydroxyl value>
The hydroxyl value (mgKOH / g) was measured by the method specified in JIS K0070 (1992 edition).
<Primary OH conversion rate>
In the present invention, the primary OH conversion rate of the terminal hydroxyl group is determined by ¹ H-NMR method after pretreatment of the sample in advance for esterification. 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 ¹ H-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 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 OH conversion rate of terminal hydroxyl group Signal from methylene group with primary OH group was observed near 4.3ppm, signal from methine group with secondary hydroxyl group was around 5.2ppm Since it is observed, the primary OH conversion rate of the terminal hydroxyl group is calculated by the following formula [1].
Primary OH conversion rate (%) = [r / (r + 2s)] × 100 [1]
However,
r: integrated value of a signal derived from a methylene group to which a primary OH 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 OH group is bonded in the vicinity of 5.2 ppm.

Examples 1-9 and Comparative Examples 1-10
According to the formulation shown in Table 1, foaming was carried out under the following foaming conditions to obtain a flexible polyurethane foam, and the physical properties of the foam after being left overnight were measured.

(Foaming conditions)
BOX SIZE: 250mm x 250mm x 250mm
Material: Wood Mixing method: Hand mixing Mixing time: 6 seconds Agitation blade rotation speed: 5000 rotations / minute

The materials used in Examples and Comparative Examples are shown below.
(1) Polyol component (A-1): Polyether polyol in which PO is added to glycerin using potassium hydroxide as a catalyst and potassium hydroxide is removed by a conventional method, 2,6-di-tert as an antioxidant -Containing 3000 ppm of butyl-p-cresol. Hydroxyl value = 56.1, primary OH conversion = 2%, aldehyde content 10 ppm.
[Production of (A-1)]
In a glass autoclave, PO was added stepwise to glycerin using potassium hydroxide as a catalyst [catalyst consumption 0.3 wt% (based on reaction product), reaction temperature 95 to 120 ° C., reaction pressure 3 kgf / cm ² or less ]. To 1000 parts by weight of the obtained crude polyoxyalkylene polyol, 4.4 parts by weight of water and 5 parts by weight of synthetic magnesium silicate were added and stirred at 80 ° C. for 30 minutes. Toyo Filter Paper No. A pressure filter with a diameter of 10 cm (manufactured by Yamashita Seisakusho) equipped with 2 is connected in series with a filter (manufactured by Advantech Toyo) with a 0.1 μm micro filter, and the polyoxyalkylene polyol after the above treatment is pressurized. Filtered at 1 kgf / cm ² . The filtrate was transferred to a flask and dehydrated under reduced pressure at 130 ° C. Then, it mix | blended so that the 2, 6- di-tert- butyl-p-cresol content might be 3000 ppm. The addition reaction of PO was carried out under a nitrogen stream in the absence of air, and from the treatment of the crude polyoxyalkylene polyol to the blending of 2,6-di-tert-butyl-p-cresol.
(A-2): Polyether polyol obtained by adding PO to glycerol using potassium hydroxide as a catalyst and removing potassium hydroxide by a conventional method, and 2,6-di-tert-butyl-p- as an antioxidant One containing 5000 ppm of cresol. Hydroxyl value = 56.1, primary OH conversion = 2%, aldehyde content 10 ppm.
[Production of (A-2)]
Manufactured in the same manner as in [Production of (A-1)] except that the 2,6-di-tert-butyl-p-cresol content was 5000 ppm.
(A-3): Polyether polyol obtained by adding PO to potassium glycerin as a catalyst and removing potassium hydroxide by a conventional method, and 2,6-di-tert-butyl-p- as an antioxidant One containing 3000 ppm cresol. Hydroxyl value = 56.1, primary OH conversion = 2%, aldehyde content 50 ppm.
[Production of (A-3)]
Except that all steps from the treatment of the crude polyoxyalkylene polyol to the blending of 2,6-di-tert-butyl-p-cresol were carried out under a mixed air stream of nitrogen: air = 4: 1 (volume ratio) [ It was produced in the same manner as in (Production of (A-1)).
(A-4): PO39.8 mol of PO was added to 1 mol of glycerin using 1 mol of glycerin, and then 13.6 mol of EO was added as a block, and the polyether polyol was removed from the potassium hydroxide by a conventional method. What contained 2,6-di-tert-butyl-p-cresol 3000 ppm as an inhibitor. Hydroxyl value = 56.1, EO unit content = 20 wt%, primary OH ratio = 70%, aldehyde content 10 ppm.
[Production of (A-4)]
In a glass autoclave, PO was added stepwise to glycerin using potassium hydroxide as a catalyst [catalyst consumption 0.3 wt% (based on reaction product), reaction temperature 95 to 120 ° C., reaction pressure 3 kgf / cm ² or less ]. Thereafter, EO was added stepwise by using potassium hydroxide as a catalyst [amount of catalyst used: 0.3 wt% (based on reaction product), reaction temperature: 95 to 120 ° C., reaction pressure: 3 kgf / cm ² or less]. To 1000 parts by weight of the obtained crude polyoxyalkylene polyol, 4.4 parts by weight of water and 5 parts by weight of synthetic magnesium silicate were added and stirred at 80 ° C. for 30 minutes. Toyo Filter Paper No. A pressure filter with a diameter of 10 cm (manufactured by Yamashita Seisakusho) equipped with 2 is connected in series with a filter (manufactured by Advantech Toyo) with a 0.1 μm micro filter, and the polyoxyalkylene polyol after the above treatment is pressurized. Filtered at 1 kgf / cm ² . The filtrate was transferred to a flask and dehydrated under reduced pressure at 130 ° C. Then, it mix | blended so that the 2, 6- di-tert- butyl-p-cresol content might be 3000 ppm. The addition reaction of PO and EO was carried out under a nitrogen stream in the absence of air and from the treatment of the crude polyoxyalkylene polyol to the blending of 2,6-di-tert-butyl-p-cresol.
(A-5): Potassium hydroxide was added to 1 mol of glycerin as a catalyst, and PO was added to 39.8 mol of PO, and then 13.6 mol of EO was added in a block, and the polyether polyol from which potassium hydroxide was removed by a conventional method was oxidized. What contained 2,6-di-tert-butyl-p-cresol 5000 ppm as an inhibitor. Hydroxyl value = 56.1, EO unit content = 20 wt%, primary OH ratio = 70%, aldehyde content 10 ppm.
[Production of (A-5)]
It was produced in the same manner as in [Production of (A-4)] except that the 2,6-di-tert-butyl-p-cresol content was 5000 ppm.
(A-6): 39.8 mol of PO was added to 1 mol of glycerol using potassium hydroxide as a catalyst, and then 13.6 mol of EO was added as a block, and the polyether polyol was removed from the potassium hydroxide by a conventional method. What contained 2,6-di-tert-butyl-p-cresol 5000 ppm as an inhibitor. Hydroxyl value = 56.1, EO unit content = 20 wt%, primary OH ratio = 70%, aldehyde content 50 ppm.
[Production of (A-6)]
Except that all steps from the treatment of the crude polyoxyalkylene polyol to the blending of 2,6-di-tert-butyl-p-cresol were carried out under a mixed air stream of nitrogen: air = 4: 1 (volume ratio) [ It was produced in the same manner as in (Production of (A-5)].
(A-7): Polyether polyol obtained by randomly adding PO and EO to glycerin using potassium hydroxide as a catalyst and removing potassium hydroxide by a conventional method, and 2,6-di-tert-butyl as an antioxidant -What contained 3000 ppm of p-cresol. Hydroxyl value = 56.1, total 7 wt% of EO units, primary OH ratio = 2%, aldehyde content 10 ppm.
[Production of (A-7)]
In a glass autoclave, a mixture of PO and EO was added stepwise to glycerin using potassium hydroxide as a catalyst [catalyst consumption 0.3 wt% (based on reaction product), reaction temperature 95-120 ° C., reaction pressure 3 kgf / Cm ² or less]. To 1000 parts by weight of the obtained crude polyoxyalkylene polyol, 4.4 parts by weight of water and 5 parts by weight of synthetic magnesium silicate were added and stirred at 80 ° C. for 30 minutes. Toyo Filter Paper No. A pressure filter with a diameter of 10 cm (manufactured by Yamashita Seisakusho) equipped with 2 is connected in series with a filter (manufactured by Advantech Toyo) with a 0.1 μm micro filter, and the polyoxyalkylene polyol after the above treatment is pressurized. Filtered at 1 kgf / cm ² . The filtrate was transferred to a flask and dehydrated under reduced pressure at 130 ° C. Then, it mix | blended so that the 2, 6- di-tert- butyl-p-cresol content might be 3000 ppm. The addition reaction of PO and EO was carried out under a nitrogen stream in the absence of air and from the treatment of the crude polyoxyalkylene polyol to the blending of 2,6-di-tert-butyl-p-cresol.
(A-8): Polyether polyol in which PO and EO are randomly added to glycerin using potassium hydroxide as a catalyst and potassium hydroxide is removed by a conventional method, and 2,6-di-tert-butyl as an antioxidant -What contained 5000 ppm of p-cresol. Hydroxyl value = 56.1, total 7 wt% of EO units, primary OH ratio = 2%, aldehyde content 10 ppm.
[Production of (A-8)]
It was produced in the same manner as in [Production of (A-7)] except that the 2,6-di-tert-butyl-p-cresol content was 5000 ppm.
(A-9): Polyether polyol obtained by randomly adding PO and EO to glycerin using potassium hydroxide as a catalyst and removing potassium hydroxide by a conventional method, and 2,6-di-tert-butyl as an antioxidant -What contained 5000 ppm of p-cresol. Hydroxyl value = 56.1, total 7 wt% of EO units, primary OH ratio = 2%, aldehyde content 50 ppm.
[Production of (A-9)]
Except that all steps from the treatment of the crude polyoxyalkylene polyol to the blending of 2,6-di-tert-butyl-p-cresol were carried out under a mixed air stream of nitrogen: air = 4: 1 (volume ratio) [ It was produced in the same manner as in (Production of (A-8)).
(A-10): Polyether polyol in which PO and EO are randomly added to glycerin using potassium hydroxide as a catalyst and potassium hydroxide is removed by a conventional method, and 2,6-di-tert-butyl as an antioxidant -What contained 3000 ppm of p-cresol. Hydroxyl value = 280.5, total 15% by weight of EO units, primary OH ratio = 70%, aldehyde content 10 ppm.
[Production of (A-10)]
In a glass autoclave, a mixture of PO and EO was added stepwise to glycerin using potassium hydroxide as a catalyst [catalyst consumption 0.3 wt% (based on reaction product), reaction temperature 95-120 ° C., reaction pressure 3 kgf / Cm ² or less]. To 1000 parts by weight of the obtained crude polyoxyalkylene polyol, 4.4 parts by weight of water and 5 parts by weight of synthetic magnesium silicate were added and stirred at 80 ° C. for 30 minutes. Toyo Filter Paper No. A pressure filter with a diameter of 10 cm (manufactured by Yamashita Seisakusho) equipped with 2 is connected in series with a filter (manufactured by Advantech Toyo) with a 0.1 μm micro filter, and the polyoxyalkylene polyol after the above treatment is pressurized. Filtered at 1 kgf / cm ² . The filtrate was transferred to a flask and dehydrated under reduced pressure at 130 ° C. Then, it mix | blended so that the 2, 6- di-tert- butyl-p-cresol content might be 3000 ppm. The addition reaction of PO and EO was carried out under a nitrogen stream in the absence of air and from the treatment of the crude polyoxyalkylene polyol to the blending of 2,6-di-tert-butyl-p-cresol.

(G-1): Polyether polyol obtained by adding PO to glycerin using potassium hydroxide as a catalyst and removing potassium hydroxide by a conventional method, and 2,6-di-tert-butyl-p- as an antioxidant Contains 500 ppm cresol. Hydroxyl value = 56.1, primary OH ratio = 2%, aldehyde content 200 ppm.
[Production of (G-1)]
In a glass autoclave, PO was added stepwise to glycerin using potassium hydroxide as a catalyst [catalyst consumption 0.3 wt% (based on reaction product), reaction temperature 95 to 120 ° C., reaction pressure 3 kgf / cm ² or less ]. To 1000 parts by weight of the obtained crude polyoxyalkylene polyol, 4.4 parts by weight of water and 5 parts by weight of synthetic magnesium silicate were added, and the mixture was stirred at 80 ° C. for 30 minutes. Toyo Filter Paper No. A pressure filter with a diameter of 10 cm (manufactured by Yamashita Seisakusho) equipped with 2 is connected in series with a filter (manufactured by Advantech Toyo) with a 0.1 μm micro filter, and the polyoxyalkylene polyol after the above treatment is pressurized. Filtered at 1 kg / cm ² . The filtrate was transferred to a flask and dehydrated under reduced pressure at 130 ° C. Thereafter, the mixture was blended so that the 2,6-di-tert-butyl-p-cresol content was 500 ppm. The addition reaction of PO was carried out under air in the absence of air and all steps from the treatment of the crude polyoxyalkylene polyol to the blending of 2,6-di-tert-butyl-p-cresol.
(G-2): Polyether polyol obtained by adding PO to glycerol using potassium hydroxide as a catalyst and removing potassium hydroxide by a conventional method, and 2,6-di-tert-butyl-p- as an antioxidant Contains 50 ppm cresol. Hydroxyl value = 56.1, primary OH conversion = 2%, aldehyde content 500 ppm.
[Production of (G-2)]
Except that all steps from the treatment of the crude polyoxyalkylene polyol to the blending of 2,6-di-tert-butyl-p-cresol were carried out under a mixed air stream of air: oxygen = 4: 1 (volume ratio) [ It was produced in the same manner as in (Production of (G-1)).

(2) Isocyanate component (E)
TDI: NCO% = 48.3 (trade name: Coronate T-80, manufactured by Nippon Polyurethane Industry Co., Ltd.)
(3) Catalyst (C1)
(C1-1): stannous octylate ([foaming reaction rate constant / resinization reaction rate constant] value 2.0 × 10 ⁻² , trade name: Neostan U-28, manufactured by Nitto Kasei Co., Ltd.)
(C1-2): 33 wt% ethylene glycol solution of triethylenediamine (value of [foaming reaction rate constant / resinization reaction rate constant] 1.0 × 10 ⁻¹ , trade name: TEDA-L33, Tosoh Corporation) Made)
(4) Catalyst (C2)
(C2-1): 70% by weight dipropylene glycol solution of bis (N, N-dimethylamino-2-ethyl) ether ([foaming reaction rate constant / resinization reaction rate constant] value 3.9, trade name) : TOYOCAT ET, manufactured by Tosoh Corporation)
(5) Foam stabilizer (D)
(D-1): “L-540” manufactured by Toray Dow Corning
(6) Foaming agent (F)
(F-1): Water <Test Example>
<1>: Core density (kg / m ³ ).
<2>: Breathability (cc / cm ² / sec)
<1> conformed to JIS K6400 (1997 edition). <2> was measured with a Frazier type air permeability tester.
The scorch (ΔYI) measured the central part of the urethane foam with a spectrocolorimeter “SD5000” (manufactured by Nippon Denshoku Industries Co., Ltd.), and determined the average value thereof (YI measured the blank and the sample twice, respectively). ). A value obtained by subtracting the sample YI from the blank YI was expressed as a ΔYI value.

  From the results shown in Table 1, when the production method of the present invention is used, a foam that does not generate scorch in the central portion of the flexible polyurethane foam can be obtained.

The flexible polyurethane foam produced by the method of the present invention is used for vehicle seats, furniture, building materials, bedding, apparel, electrical equipment, electronic equipment, packaging, and other uses (sanitary goods, cosmetics), etc. The polyurethane foam can be suitably used in any application.
Since the foam is less colored, it is particularly useful as clothing.

Claims (5)

A flexible polyurethane foam obtained by reacting a polyol component (A) and a polyisocyanate component (E) in the presence of an antioxidant (B), a catalyst (C), a foam stabilizer (D) and a foaming agent (F). The aldehyde content contained in (A) is 150 ppm or less based on the weight of (A), and the amount of (B) used is 100 to 9500 ppm based on the weight of (A) And (C) at least one catalyst (C1) having a value of [foaming reaction rate constant / resinization reaction rate constant] of 1.0 × 10 ^{−4 to} 9.0 × 10 ⁻¹ , The manufacturing method of the flexible polyurethane foam which uses the catalyst (C2) which is 1.0-10.0 with at least 1 sort (s). The production method according to claim 1, wherein the antioxidant (B) comprises at least one antioxidant selected from the group consisting of piperidine, phosphate ester, phenol and amine. The number average functional group number of the polyol component (A) is 2.0 to 6.0, the hydroxyl value is 20 to 500 (mgKOH / g), and the total amount of oxyethylene units is 0 to 95 weight based on the weight of (A). The method according to claim 1 or 2, wherein the production method is%. The flexible polyurethane foam obtained by the manufacturing method of the flexible polyurethane foam in any one of Claims 1-3. A molded product of flexible polyurethane foam for use in vehicle seats, furniture, apparel, electrical equipment, electronic equipment, or packaging obtained using the flexible polyurethane foam according to claim 4.