JP2015110753A - Polyol composition for producing flexible polyurethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition for producing flexible polyurethane foam capable of producing flexible polyurethane foam hardly diffusing aldehyde with good curability.SOLUTION: There is provided a polyol composition for producing flexible polyurethane foam which comprises a polyol component (A), an additive (B), a foaming agent (C), a catalyst (D) and a foam stabilizer (E), wherein (A) contains a polyether polyol (A0) having an average functional group number of 2 to 8, a hydroxyl value of 14 to 54 (mgKOH/g) and a content of oxyethylene units of 5 to 30 wt.% and (B) contains a urea compound (B1) represented by the following general formula (1).

Description

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

  In recent years, aldehydes (volatile organic compounds (VOC)) such as formaldehyde cause sick house syndrome and the like, and therefore, there is a demand in the residential field not to diffuse these compounds as much as possible. Such a situation is also the same in a vehicle room such as an automobile, and VOC countermeasures have become necessary.

  For example, soft urethane foam with high cushioning properties is used for the vehicle seat pad, but formaldehyde, acetaldehyde, etc. contained in the raw material for polyurethane foam after these urethane foam molding or generated during the urethanization reaction are padded. Therefore, it is required to reduce the generation of these aldehydes.

Conventionally, in order to prevent volatilization of aldehydes, a method of applying an aldehyde scavenger on the surface of a sheet pad (see Patent Document 1) is known.
Further, a method of mixing a hydrazine compound having an action of decomposing aldehydes with a polyol compound (see Patent Document 2) is known.

JP 2005-124743 A JP 2006-182825 A

However, in the method of Patent Document 1, it is necessary to apply an aldehyde scavenger to the sheet pad after foam molding, so that the workability is poor, and the curability of the sheet pad obtained by the method of Patent Document 2 is insufficient. There is a problem of becoming.
An object of this invention is to provide the polyol composition for flexible polyurethane foam manufacture which can manufacture the flexible polyurethane foam which an aldehyde does not spread | diffuse easily with sufficient curability.

  As a result of intensive studies on the polyol composition for flexible polyurethane foam that solves the above problems, the present inventors use a polyol composition for flexible polyurethane foam that combines a specific polyether polyol and a specific aldehyde scavenger. Thus, the present inventors have found that the curability is good and the diffusion of aldehydes is reduced, and the present invention has been achieved.

  That is, the present invention is a polyol composition for producing a flexible polyurethane foam comprising a polyol component (A), an additive (B), a foaming agent (C), a catalyst (D) and a foam stabilizer (E), A) contains a polyether polyol (A0) having an average number of functional groups of 2 to 8, a hydroxyl value of 14 to 54 (mg KOH / g), and an oxyethylene unit content of 5 to 30% by weight, and (B) A polyol composition for producing a flexible polyurethane foam, which contains a urea compound (B1) represented by the following general formula (1).

[In General Formula (1), R represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, and each may be the same or different, but at least one represents hydrogen; Represents an integer. ]

  The polyol composition for producing a flexible polyurethane foam of the present invention can suppress aldehyde diffusion. Therefore, the flexible polyurethane foam produced using the polyol composition for producing the flexible polyurethane foam of the present invention has little diffusion of aldehyde. Moreover, the curability at the time of foam production is also good.

  The polyol component (A) used in the polyol composition for producing a flexible polyurethane foam of the present invention has an average functional group number of 2 to 8 and a hydroxyl value of 14 to 54 (mgKOH / g) from the viewpoint of moldability and mechanical properties of the urethane foam. ), A polyether polyol (A0) having an oxyethylene unit content of 5 to 30% by weight.

(A0) has an average number of functional groups of 2 to 8, preferably 2 to 6, and more preferably 2 to 5 from the viewpoints of moldability and mechanical properties of urethane foam.
In the present invention, the number of functional groups of the polyether polyol [(A0) and (A1) described later] is considered to be the same as the number of functional groups of the active hydrogen-containing compound as a starting material.

The hydroxyl value of (A0) is 14 to 54 (mgKOH / g), preferably 17 to 50 (mgKOH / g), more preferably 20 to 45 (mgKOH), from the viewpoints of curability and mechanical properties of urethane foam. / G).
The hydroxyl value in the present invention is measured by a method defined in JIS K1557-1.
The content of the oxyethylene unit of (A0) is 5 to 30% by weight, preferably 5 to 25% by weight, more preferably 5 to 20% by weight, from the viewpoints of moldability and mechanical properties of the urethane foam. .

  As (A0), a compound containing at least two (preferably 2 to 8) active hydrogens (polyhydric alcohol, polyhydric phenol, amine, polycarboxylic acid, phosphoric acid, etc.) and alkylene oxide (hereinafter, And a compound having a structure to which AO is abbreviated).

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

  Examples of the polyvalent (2 to 8 valent) phenols include monocyclic polyphenols, bisphenols, phenol / formaldehyde condensates (novolaks), polyphenols, and combinations of two or more thereof. Examples of monocyclic polyphenols include pyrogallol, hydroquinone, and phloroglucin. Examples of bisphenol include bisphenol A, bisphenol F, and bisphenol sulfone. Examples of the polyphenol include those described in US Pat. No. 3,265,641.

Examples of the amine include those having 2 to 8 active hydrogens, and include ammonia, a linear or branched aliphatic amine, an aromatic amine, an alicyclic amine, and a heterocyclic amine.
Examples of the linear or branched aliphatic amine include alkanolamines having 2 to 20 carbon atoms (monoethanolamine, diethanolamine, triethanolamine, isopropanolamine, aminoethylethanolamine, etc.), alkylamines having 1 to 20 carbon atoms (n- Butylamine and octylamine), alkylene diamines having 2 to 6 carbon atoms (such as ethylene diamine, propylene diamine and hexamethylene diamine) and polyalkylene polyamines having 4 to 20 carbon atoms (having 2 to 6 carbon atoms in the alkylene group) Specific examples thereof include diethylenetriamine and triethylenetetramine.
Examples of the aromatic amine include aromatic mono- or polyamines having 6 to 20 carbon atoms (aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline, diphenyletherdiamine, and the like).
Examples of the alicyclic amine include alicyclic amines having 4 to 20 carbon atoms (such as isophorone diamine, cyclohexylene diamine, and dicyclohexyl methane diamine).
Examples of the heterocyclic amine include heterocyclic amines having 4 to 20 carbon atoms (piperazine, aminoethylpiperazine, and those described in Japanese Patent Publication No. 55-21044), and the like.

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 (phthalic acid, Terephthalic acid, isophthalic acid, trimellitic acid, etc.).
Two or more of these active hydrogen-containing compounds may be used in combination. Among these, polyhydric alcohols are preferable from the viewpoints of curability and mechanical properties of urethane foam.

The AO added to the active hydrogen-containing compound is preferably AO composed of 1,2-AO having 3 or more carbon atoms and ethylene oxide (hereinafter abbreviated as EO), and 1,2-AO having 3 or more carbon atoms is preferably 1 , 2-propylene oxide (hereinafter abbreviated as PO), 1,2-butylene oxide, styrene oxide and the like, among which PO is preferred from the viewpoint of productivity.
AO is preferably composed of only 1,2-AO having 3 or more carbon atoms and EO. However, addition of other AO in the range of 10% by weight or less (more preferably 5% by weight or less) in AO. It may be a thing. Other AOs are preferably those having 4 to 8 carbon atoms, such as 1,3-, 1,4- and 2,3-butylene oxides, and two or more thereof may be used.

  The addition method of AO may be either block addition or random addition, but at least the active hydrogen terminal of the polyol is preferably block addition.

  Catalysts used at the time of AO addition include alkali catalysts (KOH, CsOH, etc.), catalysts described in JP-A No. 2000-344881 [tris (pentafluorophenyl) borane, etc.], and JP-A No. 11-120300. (Such as magnesium perchlorate) may also be used (the same applies to the following AO adducts).

  The content of (A0) is preferably from 8 to 98% by weight, more preferably from 10 to 97% by weight, particularly preferably from the viewpoint of curability and mechanical properties of the urethane foam, based on the total weight of the polyol component (A). Is 12 to 95% by weight, most preferably 20 to 90% by weight.

  In the present invention, the polyol component (A) may contain other polyols or active hydrogen components in addition to the polyol (A0). The polyether polyol (A1) other than (A0), the polyester polyol (A2) ), Polyhydric alcohol (A3), polyols and monools (A4) other than those described above, and polymer polyol (A5), amine (A6) and mixtures thereof obtained by polymerizing vinyl monomers in these polyols Etc.

  The polyether polyol (A1) other than (A0) has a structure in which AO is added to a compound (polyhydric alcohol, polyhydric phenol, amine, polycarboxylic acid, phosphoric acid, etc.) containing at least two active hydrogens. These are compounds that do not fall under (A0), and may be used alone or in combination of two or more.

Examples of the compound containing active hydrogen include the same compounds as those in the polyether polyol (A0).
Among these, from the viewpoint of moldability, polyhydric alcohols are preferable, and from the viewpoint of curability and mechanical properties of urethane foam, more preferably aliphatic polyhydric alcohols and alicyclic polyhydric alcohols, particularly preferably aliphatic polyhydric alcohols. It is a monohydric alcohol.

AO added to the compound containing active hydrogen is preferably one having 2 to 8 carbon atoms from the viewpoint of moldability, and includes EO, PO, 1,2-, 1,3-, 1,4- and 2, Examples include 3-butylene oxide, styrene oxide, and combinations of two or more of these (block and / or random addition). Among these, from the viewpoint of curability, a combination of PO and PO and EO is preferable, and a combination of PO and EO is more preferable.
Catalysts used at the time of AO addition include alkali catalysts (KOH, CsOH, etc.), catalysts described in JP-A No. 2000-344881 [tris (pentafluorophenyl) borane, etc.], and JP-A No. 11-120300. A catalyst such as magnesium perchlorate may be used.

Examples of the polyester polyol (A2) include the following (1) to (5).
(1) Esters of polyhydric alcohols and polycarboxylic acids or ester-forming derivatives thereof Polyhydric alcohols are dihydric alcohols (ethylene glycol, diethylene glycol, 1,2- and 1,3-propylene glycol, 1,3- And 1,4-butanediol, 1,6-hexanediol and neopentyl glycol, etc.), polyether polyols (preferably diols), and mixtures thereof with trihydric or higher polyhydric alcohols (such as glycerin and trimethylolpropane). } Etc. Polycarboxylic acids or ester-forming derivatives thereof are acid anhydrides and lower alkyl (alkyl group carbon number: 1 to 4) esters, and are adipic acid, sebacic acid, maleic anhydride, phthalic anhydride and dimethyl terephthalate. Etc.
(2) Condensation reaction product with carboxylic anhydride and AO (3) AO (EO, PO, etc.) adduct of (1) and (2) above (4) Polylactone polyol For example, polyhydric alcohol as an initiator Examples thereof include those obtained by ring-opening polymerization of a lactone (such as ε-caprolactone).
(5) Polycarbonate polyol For example, the reaction material of the said polyhydric alcohol and alkylene carbonate is mentioned.

  As the polyhydric alcohol (A3), a dihydric alcohol having 2 to 20 carbon atoms {linear or branched aliphatic diol (ethylene glycol, propylene glycol, 1,3- and 1,4-butanediol, 1,6-hexane Diols and alkylene glycols such as neopentyl glycol; polyalkylene glycols such as diethylene glycol and dipropylene glycol) and alicyclic diols (cycloalkylene glycols such as cyclohexanediol and cyclohexanedimethanol)}, trivalent alcohols having 3 to 20 carbon atoms {Aliphatic triols (alkanetriols such as glycerin, trimethylolpropane, trimethylolethane and hexanetriol)}; 4 to 8 or more polyhydric alcohols having 5 to 20 carbon atoms {aliphatic polyols (pentaeth Alkane polyols such as sitolitol, sorbitol, mannitol, sorbitan, diglycerin and dipentaerythritol and intramolecular or intermolecular dehydrates of these or alkanetriol; and sugars such as sucrose, glucose, mannose, fructose and methylglucoside and their derivatives )} And the like. Two or more of these may be used in combination.

  Polyols and monools (A4) other than the above include polydiene polyols such as polybutadiene polyol and hydrogenated products thereof; acrylic polyols, JP-A 58-57413 and JP-A 58-57414, etc. Hydroxyl group-containing vinyl polymers described; natural fat-based polyols such as castor oil; modified natural fat-based polyols such as castor oil-modified products (polyhydric alcohol transesterification products, hydrogenated products, etc.); International Publication WO 98 / Terminal hydrogen radical functional group-containing active hydrogen compounds (including monools) described in Japanese Patent No. 44016; modified polyol obtained by jumping polyether polyol with alkylene dihalide such as methylene dihalide; OH terminal of polyether polyol A prepolymer; and the like.

The polymer polyol (A5) is obtained by polymerizing the ethylenically unsaturated monomer (p) in the presence of a radical polymerization initiator in at least one of (A0) and (A1) to (A4). In addition, a polymer in which the polymer (p) is stably dispersed in a polyol can be used. As (A5), those obtained by polymerizing (p) in (A0) or (A1) are preferred from the viewpoint of dispersion stability. Specific examples of the polymerization method include those described in US Pat. No. 3,383,351, Japanese Examined Patent Publication No. 39-25737, and the like.
In the present invention, (A0) and (A1) to (A4) used as a raw material for the polymer polyol (A5) are not included in (A0) and (A1) to (A4).

  As the radical polymerization initiator, one that generates a free radical and initiates polymerization can be used. 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), Azo compounds such as 2,2′-azobis (2-methylbutyronitrile); organic peroxides such as dibenzoyl peroxide, dicumyl peroxide, benzoyl peroxide, lauroyl peroxide and persuccinic acid; persulfates And inorganic peroxides such as perborate; In addition, these can use 2 or more types together.

Examples of the ethylenically unsaturated monomer (p) include unsaturated nitrile (p1), aromatic ring-containing monomer (p2), (meth) acrylic acid ester (p3), other ethylenically unsaturated monomers (p4) and their 2 A mixture of seeds or more may be mentioned.
Examples of (p1) include acrylonitrile and methacrylonitrile.
Examples of (p2) include styrene, α-methylstyrene, hydroxystyrene, chlorostyrene, and the like.
Examples of (p3) include those composed of C, H and O atoms, for example, (meth) acrylic acid alkyl ester (alkyl group having 1 to 24 carbon atoms) [methyl (meth) acrylate, butyl (meth) acrylate, nonyl (Meth) acrylate, decyl (meth) acrylate, dodecyl (meth) acrylate, eicosyl (meth) acrylate, docosyl (meth) acrylate, etc.], hydroxyalkyl (2 to 5 carbon atoms) (meth) acrylate [hydroxyethyl (meth) Acrylates and the like] and hydroxypolyoxyalkylene mono (meth) acrylates [alkylene group having 2 to 4 carbon atoms, polyoxyalkylene chain number average molecular weight of 200 to 1000, etc.].
(P4) includes ethylenically unsaturated carboxylic acids and derivatives thereof, specifically (meth) acrylic acid and (meth) acrylamide, etc .; aliphatic or alicyclic hydrocarbon monomers, specifically alkenes ( Ethylene, propylene, norbornene, etc.) and alkadienes (butadiene, etc.); fluorine-based vinyl monomers, specifically fluorine-containing (meth) acrylates (perfluorooctylethyl methacrylate, perfluorooctylethyl acrylate, etc.), etc .; chlorine -Based vinyl monomers, specifically vinylidene chloride, etc .; nitrogen-containing vinyl monomers other than those mentioned above, specifically nitrogen-containing (meth) acrylates (diaminoethyl methacrylate, morpholinoethyl methacrylate, etc.); and vinyl-modified silicones Etc.
Among these (p), from the viewpoint of moldability, (p1) and (p2) are preferable, and acrylonitrile and / or styrene are more preferable.

The weight ratio of (p1), (p2), (p3) and (p4) in the ethylenically unsaturated monomer (p) can be changed according to the required physical properties of the polyurethane and is particularly limited. An example is as follows.
On the basis of the total weight of (p), (p1) and / or (p2) is preferably 50 to 100% by weight, more preferably 80 to 100% by weight. The weight ratio of (p1) and (p2) is not particularly limited, but is preferably 100/0 to 20/80. (P3) is preferably 0 to 50% by weight, more preferably 0 to 20% by weight. (P4) is preferably 0 to 10% by weight, more preferably 0 to 5% by weight.

  From the viewpoint of moldability, the content of the polymer (p) in the polymer polyol (A5) is preferably 50% by weight or less, more preferably 3 to 30% by weight, based on the total weight of (A5). It is.

Examples of the amine (A6) include those having 2 to 8 or more active hydrogen atoms, ammonia; aliphatic amines having 2 to 20 carbon atoms (monoethanolamine, diethanolamine, triethanolamine). , Isopropanolamine and aminoethylethanolamine, etc.), alkylamines having 1-20 carbon atoms (n-butylamine, octylamine, etc.), alkylenediamines having 2-6 carbon atoms (ethylenediamine, propylenediamine, hexamethylenediamine, etc.), carbon Examples thereof include polyalkylene polyamines having 4 to 20 carbon atoms (dialkylene triamines having 6 to 6 carbon atoms in the alkylene group to hexaalkylene heptamine, diethylenetriamine, triethylenetetramine, etc.).
C6-C20 aromatic mono- or polyamines (aniline, phenylenediamine, tolylenediamine, xylylenediamine, diethyltoluenediamine, methylenedianiline, diphenyletherdiamine, etc.); C4-C20 alicyclic amines (Isophorone diamine, cyclohexylene diamine, dicyclohexyl methane diamine, etc.); C4-C20 heterocyclic amines (such as piperazine, aminoethylpiperazine, and those described in Japanese Patent Publication No. 55-21044) and two or more of these Combination use etc. are mentioned.

  Among these, polyether polyol (A1) is preferable from the viewpoint of moldability.

  The total content of (A1), (A2), (A3), (A4), (A5) and (A6) is based on the total weight of the polyol component (A). From the viewpoint, it is preferably 2 to 92% by weight, more preferably 3 to 90% by weight, particularly preferably 5 to 88% by weight, and most preferably 10 to 80% by weight.

The additive (B) used in the polyol composition for producing a flexible polyurethane foam of the present invention contains a urea compound (B1) represented by the following general formula (1) from the viewpoint of an aldehyde reducing effect.
The additive (B) in the present invention has a function as an aldehyde scavenger.

  In general formula (1), R represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, and each may be the same or different, but at least one represents hydrogen; n is 0 to 3 Represents an integer.

  In General Formula (1), R includes hydrogen, an alkyl group having 1 to 4 carbon atoms (such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a tert-butyl group) and a hydroxyl group. Of these, each may be the same or different, but any one represents hydrogen. From the viewpoint of aldehyde reduction, hydrogen, a methyl group, and a hydroxyl group are preferable, and hydrogen is more preferable.

  In the general formula (1), n represents an integer of 0 to 3, and 0 or an integer of 1 to 2 is preferable from the viewpoint of an aldehyde reduction effect, and more preferably 0.

  Examples of the urea compound (B1) represented by the general formula (1) include urea, N-methylurea, biuret, and carbonyldiurea, and urea is preferable from the viewpoint of the effect of reducing aldehyde.

  In this invention, it is preferable that an additive (B) contains an amino acid (B2) further from a viewpoint of an aldehyde reduction effect and sclerosis | hardenability.

Examples of (B2) include glycine, alanine, valine, leucine, isoleucine, asparagine, glutamine, aspartic acid, glutamic acid, lysine, arginine, phenylalanine, tyrosine, cysteine, methionine, serine, threonine, histidine, tryptophan and proline. .
Among these, glycine, aspartic acid, and proline are preferable from the viewpoint of an aldehyde reducing effect, and glycine and aspartic acid are more preferable.
In the case of containing (B1) and (B2), the content of (B1) and (B2) is 15 from the viewpoint of aldehyde reduction effect and curability, with (B1) being 15 on the basis of the total weight of (B). ~ 98 wt%, (B2) is preferably 2 to 85 wt%.

  In this invention, it is preferable that an additive (B) contains a polyhydric phenol (B3) further from a viewpoint of an aldehyde reduction effect and sclerosis | hardenability.

Examples of (B3) include polyhydric phenols having 2 to 20 functional groups and a molecular weight of 110 to 2000. Specifically, monocyclic polyhydric phenols such as pyrogallol, hydroquinone and phloroglucin; bisphenol A, bisphenol F and bisphenol sulfone. Bisphenols such as: condensates of phenol and formaldehyde (novolak); polyphenols described in US Pat. No. 3,265,641; polyphenol-containing plant extracts such as vistaaflavin A, and combinations of two or more thereof.
Among these, from the viewpoint of an aldehyde reduction effect, polyhydric phenols having 2 to 10 functional groups and 110 to 1000 molecular weight are preferable, and more preferred are polyhydric phenols having 2 to 5 functional groups and 110 to 500 molecular weight.
In the case of containing (B1) and (B3), the content of (B1) and (B3) is 15 from the viewpoint of aldehyde reduction effect and curability, based on the total weight of (B). ~ 98 wt%, (B3) is preferably 2 to 85 wt%.

In the case of containing (B1), (B2) and (B3), the contents of (B1), (B2) and (B3) are based on the total weight of (B) from the viewpoint of aldehyde reduction effect and curability. (B1) is preferably 8 to 96% by weight, (B2) is preferably 2 to 46% by weight, and (B3) is preferably 2 to 46% by weight.
The total content of (B1), (B2) and (B3) in the additive (B) is preferably 60% by weight or more, more preferably 80% by weight or more, and particularly preferably 100% by weight. .

  The total content of (B) is preferably from 0.01 to 3% by weight, more preferably from 0.05 to 3%, based on the total weight of the polyol component (A), from the viewpoints of aldehyde reduction effect and moderate curability. 3% by weight, particularly preferably 0.1 to 3% by weight.

  As an additive (B), what contains the urea compound (B1) represented by the said General formula (1), an amino acid (B2), and a polyhydric phenol (B3) is preferable.

The foaming agent (C) used in the polyol composition for producing the flexible polyurethane foam of the present invention preferably contains water, and is preferably only water.
The water content is preferably 2 to 7% by weight, more preferably 2.5 to 6.8% by weight, based on the total weight of the polyol component (A), from the viewpoints of expansion ratio and foam disintegration. is there.
When the water content is 2% by weight or more, the expansion ratio is sufficient, and the filling in the mold is sufficient during foam molding. If it is 7% by weight or less, excessive foaming gas is not generated and the foam is difficult to collapse.
As the blowing agent (C), it is preferable to use only water, but if necessary, a hydrogen atom-containing halogenated hydrocarbon, a low-boiling hydrocarbon, liquefied carbon dioxide gas, or the like may be used in combination.

Examples of the hydrogen atom-containing halogenated hydrocarbon-based blowing agent include HCFC (hydrochlorofluorocarbon) (HCFC-123, HCFC-141b, HCFC-22, HCFC-142b, etc.); HFC (hydrofluorocarbon) (HFC-134a, HFC- 152a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa, HFC-365mfc, etc.).
Among these, HCFC-141b, HFC-134a, HFC-356mff, HFC-236ea, HFC-245ca, HFC-245fa and HFC-365mfc, and mixtures of two or more of these are preferred.
The content in the case of using a hydrogen atom-containing halogenated hydrocarbon is preferably 50% by weight or less, and more preferably 5% by weight or less, from the viewpoint of foaming ratio and foam disintegration, based on the total weight of the polyol component (A). 45% by weight.

The low boiling point hydrocarbon is a hydrocarbon having a boiling point of −5 to 70 ° C., and examples thereof include butane, pentane, cyclopentane, and mixtures thereof.
The content when using low-boiling hydrocarbons is preferably 30% by weight or less, more preferably 25% by weight or less, from the viewpoint of foaming ratio and foam disintegration, based on the total weight of the polyol component (A). is there.
The content in the case of using liquefied carbon dioxide is preferably 30% by weight or less, more preferably 25% by weight or less, from the viewpoint of foaming ratio and foam disintegration, based on the total weight of the polyol component (A). .

As the catalyst (D) used in the polyol composition for producing the flexible polyurethane foam of the present invention, a 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 and stannous octoate, etc.) and organic A metal compound (dibutyltin dilaurate etc.) is mentioned.
The content of the catalyst (D) is preferably 0.1 to 0.8% by weight, more preferably 0.15 to 0.005% from the viewpoint of the reactivity of the urethane foam, based on the total weight of the polyol component (A). 7% by weight.

As the foam stabilizer (E) used in the polyol composition for producing the flexible polyurethane foam of the present invention, those used for the production of polyurethane foam can be used, and examples thereof include a silicone foam stabilizer.
Silicone foam stabilizers include polyether-modified dimethylsiloxane foam stabilizers [“SZ-1328”, “SZ-1346” and “SF-2962” manufactured by Toray Dow Corning Co., Ltd.] and Momentive Performance Materials. "L-3640" and "L-540" manufactured by the company, etc.], dimethylsiloxane foam stabilizer ["SRX-253" manufactured by Toray Dow Corning Co., Ltd.] and the like.
The amount of the foam stabilizer (E) used is preferably 0.5 to 3% by weight, more preferably 0.8 to 2.5% by weight from the viewpoint of moldability, based on the total weight of the polyol component (A). It is.

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 from the viewpoint of curability and mechanical properties of the urethane foam, based on the total weight of the polyol component (A). From the viewpoint of the mechanical properties of the urethane foam, 5% by weight or less is preferable, more preferably 2% by weight or less. The anti-aging agent is preferably 1% by weight or less, more preferably from the viewpoint of the mechanical properties of the curable urethane foam. Is 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 from the viewpoint of curability and mechanical properties of the urethane foam.

The polyol composition for producing a flexible polyurethane foam of the present invention is reacted with the polyisocyanate component (F) to obtain a polyurethane foam.
As the polyisocyanate component (F), from the viewpoint of moldability of the polyurethane foam, 20% by weight or more of 2,4- and 2,6-tolylene diisocyanate (hereinafter referred to as TDI) based on the total weight of (F). 1) one or more polyisocyanates (hereinafter referred to as TDI-based polyisocyanates) selected from these crude products and modified products thereof, and other polyisocyanates of 80% by weight or less. Is preferred. The content of the TDI polyisocyanate is more preferably 25 to 95% by weight. Examples of the modified product include urethane group, carbodiimide group, allophanate group, urea group, burette group, isocyanurate group and oxazolidone group-containing modified product.

  As other polyisocyanates, organic polyisocyanates having 2 or more valences (preferably 2 to 8 valences) used for polyurethane foams can be used, and aromatic polyisocyanates other than TDI polyisocyanates, linear or branched aliphatic polyisocyanates. Examples thereof include isocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, the modified products described above).

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 4,4′-diphenylmethane diisocyanate (hereinafter abbreviated as MDI), polymethylene polyphenylene polyisocyanate (crude MDI), and naphthylene. -1,5-diisocyanate, triphenylmethane-4,4 ′, 4 ″ -triisocyanate 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, 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 other isocyanates, aromatic polyisocyanates are preferable from the viewpoint of moldability of polyurethane foam, and more preferably MDI, crude MDI, and modified products of these isocyanates.

In the polyisocyanate component (F), two or more isocyanates and modified products thereof may be used in combination.
The isocyanate group content (NCO%) as the whole polyisocyanate component (F) is preferably 40 to 50% from the viewpoint of the moldability of the polyurethane foam.

  The isocyanate index [(NCO group / active hydrogen atom-containing group) × 100] in the production of the polyurethane foam is preferably from 70 to 125, more preferably from 75 to 120, and particularly preferably from the viewpoint of moldability of the polyurethane foam. ~ 115. The active hydrogen atom-containing group includes those derived from water as a foaming agent.

  An example of a method for producing a polyurethane foam is as follows. First, a predetermined amount of a polyol component (A), an additive (B), a foaming agent (C), a catalyst (D) and a foam stabilizer (E), and other auxiliary components as necessary are mixed. Subsequently, this mixture and a polyisocyanate component (F) are rapidly mixed using a polyurethane foaming machine or a stirrer. The obtained mixed solution is poured into a mold (for example, 15 to 70 ° C.) and demolded after a predetermined time to obtain a flexible polyurethane foam.

  The polyol composition of the present invention, that is, a mixture containing the polyol component (A), the additive (B), the foaming agent (C), the catalyst (D) and the foam stabilizer (E), and, if necessary, other auxiliary components It is preferable that the mixture containing the mixture does not separate into two phases, that is, a phase containing (A) and a phase containing water after the mixture is allowed to stand at 25 ° C. for 30 days. Not separating into two phases is achieved by relatively increasing the amount of the polyether polyol (A0) in the polyol component (A), and the preferred content of (A0) is as described above.

  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 terminal primary hydroxylation rate is as follows.
<Hydroxyl value>
The hydroxyl value (mgKOH / g) was measured by the method specified in JIS K1557-1.
<Terminal primary hydroxylation rate>
In the present invention, the terminal primary hydroxylation rate is calculated by the ¹ H-NMR method after pre-treating the sample in advance. Details of the ¹ H-NMR method will be specifically described below.
Sample preparation method Approximately 30 mg of a measurement sample is weighed into a sample tube for ¹ H-NMR having a diameter of 5 mm, and 0.5 ml of deuterated solvent is added and dissolved. Thereafter, 0.1 ml of trifluoroacetic anhydride is added, and the mixture is allowed to stand at 25 ° C. for about 5 minutes. 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 terminal primary hydroxylation rate Signals derived from methylene groups with terminal primary hydroxyl groups are observed near 4.3 ppm, signals derived from methine groups with terminal secondary hydroxyl groups are observed near 5.2 ppm Therefore, the terminal primary hydroxylation rate is calculated by the following formula [1].
Terminal primary hydroxylation rate (%) = [r / (r + 2s)] × 100 [1]
However,
r: integrated value of a signal derived from a methylene group to which a terminal 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 terminal secondary hydroxyl group is bonded in the vicinity of 5.2 ppm.

Examples 1-16 and Comparative Examples 1-3
The polyol composition (polyol premix) and the polyisocyanate component shown in Table 1 were each charged into a raw material tank of a high-pressure urethane foaming machine (manufactured by Polyurethane Engineering), and the liquid temperature was adjusted to 25 ° C. Thereafter, in a high-pressure urethane foaming machine, the polyol premix and the polyisocyanate component having an isocyanate index shown in Table 1 were mixed by high-pressure discharge at 15 MPa, and the temperature was adjusted to 65 ° C. 400 mm (length) × 400 mm (length) It was poured into an aluminum mold having a width of 100 mm (height) and molded with a curing time of 6 minutes.
Table 1 shows the measurement results of the physical property values and the aldehyde diffusion amount test results of each foam. The core density is a density measured by cutting out from the center of the foam into a size of 100 mm × 100 mm × 50 mm.

Abbreviations of each component in Table 1 are as follows.
[Polyether polyol (A0)]
(A0-1): 18.4 mol of pentaerythritol was added with 118.4 mol of PO using cesium hydroxide as a catalyst, and after removing cesium hydroxide by a conventional method, the same as in Example 1 of JP-A-2000-344881 Then, 16.0 mol of PO was added using tris (pentafluorophenyl) borane as a catalyst, and 13.6 mol of EO was added as a block using potassium hydroxide as a catalyst, and the catalyst components were removed by a conventional method. Polyol (A0-2) having a hydroxyl value of 30.0 (mg KOH / g), an end content of ethylene oxide of 8% by weight and a terminal primary hydroxylation rate of 85%: PO 71 with 1 mol of glycerin and potassium hydroxide as a catalyst. After addition of 8 mol, 15.8 mol of EO was added as a block using potassium hydroxide as a catalyst, and potassium hydroxide was added by a conventional method. A polyol (A0-3) having a hydroxyl value of 34.0 (mgKOH / g), an ethylene oxide end content of 14% by weight and a terminal primary hydroxylation rate of 75%, obtained by removing 1 mol of pentaerythritol After adding 141.8 mol of PO with potassium hydroxide as a catalyst, 25.5 mol of EO was further blocked with potassium hydroxide as a catalyst, and the potassium hydroxide was removed by a conventional method. Polyol having 24.0 (mgKOH / g), terminal content of ethylene oxide of 12% by weight and terminal primary hydroxylation rate of 75%

[Polyol component (A) other than (A0)]
(A5-1): Polymer polyol (polymer) obtained by copolymerizing acrylonitrile and styrene (weight ratio: 70/30) in polyols (A0-2) and (A0-3) (weight ratio: 96/4) Content 33.5% by weight), hydroxyl value = 22.0 (mg KOH / g)
(A1-1): Sorbitol ethylene oxide adduct, hydroxyl value = 1247 (mgKOH / g), ethylene oxide end content 33% by weight
(A1-2): propylene oxide-ethylene oxide adduct of glycerin, hydroxyl value = 24.0 (mgKOH / g), end content of ethylene oxide 70% by weight
(A6-1): Triethanolamine, hydroxyl value = 1130 (mgKOH / g)

[Additive (B)]
(B1-1): Urea (B1-2): N-methylurea (B2-1): Glycine (B2-2): Aspartic acid (B3-1): Hydroquinone (B3-2): Vistaaflavin A
(B'-1): Carbodihydrazide

[Foaming agent (C)]
(C-1): Water

[Urethaneization catalyst (D)]
(D-1): 33% by weight dipropylene glycol solution of triethylenediamine [“DABCO-33LV” manufactured by Japan Air Products Japan Ltd.]
(D-2): 70% by weight dipropylene glycol solution of bis-N, N-dimethylaminoethyl ether [“TOYOCAT ET” manufactured by Tosoh Corporation]

[Foam stabilizer (E)]
(E-1): Polyether-modified dimethylsiloxane foam stabilizer [“SZ-1328” manufactured by Toray Dow Corning Co., Ltd.]

[Polyisocyanate component (F)]
(F-1): TDI / MDI polyisocyanate [“CEF-215” manufactured by Nippon Polyurethane Industry Co., Ltd.]

<Physical property test>
<1>: Core density (kg / m ³ )
<2>: Hardness (25% ILD) (N / 314 cm ² )
<3>: Rebound resilience (%)
<1> to <3> conformed to JIS K6400.

<Geltime>
Free foaming was performed, the pachinko balls were dropped from above the foam at regular time intervals, and the time when the first ball that did not reach the bottom of the foam was dropped was defined as the gel time.

<Measurement of aldehyde diffusion amount>
About each obtained flexible polyurethane foam molded object, the diffusion amount of formaldehyde (henceforth FA) and acetaldehyde (henceforth AA) was measured. In the measurement, a rectangular parallelepiped test piece having a length of 100 mm, a width of 80 mm, and a thickness of 100 mm was cut out from each of the molded bodies, and the sample was placed in a sampling bag, and the back was replaced with high-purity nitrogen gas. Heating was performed in an oven at 65 ° C. for 2 hours, and 3 L of gas in the bag was collected in DNPH cartridge (GL Pak mini AERO: manufactured by GL Sciences). The gas collected by the DNPH card ridge was eluted with 5 mL of acetonitrile. This solution was subjected to quantitative analysis of FA and AA using high performance liquid chromatography (Prominence series: manufactured by Shimadzu Corporation).
(Measurement condition)
Column used: SUMPAX ODS C-05-4615 (manufactured by Sumika Chemical Analysis Center)
Detector: UV detector (measurement wavelength: 360 nm)
Mobile phase: acetonitrile: water = 45: 55 vol%
Flow rate: 0.8ml
Column temperature: 40 ° C
Injection volume: 20 μl

  As is clear from the results in Table 1, the Examples of the present invention have a very small amount of aldehyde diffusion as compared with the Comparative Example, and the curability is superior to that of Comparative Example 3. Further, even when the amount of the urethanization catalyst used is smaller, excellent curability is shown.

The polyol composition for producing a flexible polyurethane foam of the present invention has good curability when foam is foam-molded, and a sheet pad using the foam composition is useful as a sheet pad that can reduce diffusion of aldehydes.

Claims (4)

A polyol composition for producing a flexible polyurethane foam comprising a polyol component (A), an additive (B), a foaming agent (C), a catalyst (D) and a foam stabilizer (E), wherein (A) is an average It contains a polyether polyol (A0) having 2 to 8 functional groups, a hydroxyl value of 14 to 54 (mgKOH / g), and an oxyethylene unit content of 5 to 30% by weight, and (B) is represented by the following general formula (1 The polyol composition for flexible polyurethane foam manufacture containing the urea compound (B1) represented by this.

[In General Formula (1), R represents hydrogen, an alkyl group having 1 to 4 carbon atoms or a hydroxyl group, and each may be the same or different, but at least one represents hydrogen; Represents an integer. ]   The polyol composition according to claim 1, wherein the content of the additive (B) is 0.01 to 3 wt% based on the weight of the polyol component (A).   The polyol composition according to claim 1 or 2, wherein the additive (B) contains an amino acid (B2). The polyol composition according to any one of claims 1 to 3, wherein the additive (B) contains a polyhydric phenol (B3).