JP2013241572A - Polyol composition for production of soft polyurethane foam, and method for producing polyurethane using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To solve the problem in which the mechanical physical properties of soft polyurethane foams produced using conventional polyols are insufficient.SOLUTION: A polyol composition (PL) for production of soft polyurethane foam contains the following polyol (a) and a strength improver (b), and has an EO unit content based on the weight of the polyol composition (PL)of 13-50 wt.%. Polyol (a): A polyoxyalkylene polyol that is an AO additive of an active hydrogen-containing compound (H), in which 40% or more of hydroxyls located at terminals thereof is composed of primary hydroxyl-containing groups, and hydroxyl value x, total degree of undersaturation y, and the EO unit content z satisfy a specific relationship. Strength improver (b): At least one compound which is selected from the group consisting of an ester compound, a thioester compound, a phosphate compound and an amide compound, and includes, as an essential component, a divalent or more aromatic polyvalent carboxylic acid.

Description

  The present invention relates to a polyol composition for producing flexible polyurethane foam and a method for producing polyurethane using the same.

When a polyurethane foam is produced, vibration characteristics are improved by including in the polyol component a specific polyol that satisfies the specific relationship between the average number of moles of ethylene oxide added per active hydrogen and the primary OH conversion rate of the terminal hydroxyl group. It is known that a flexible polyurethane foam can be produced (Patent Document 1).
On the other hand, there has been a strong demand for cost reduction in recent years, and there is a demand for lowering the density of flexible polyurethane foam for weight reduction. For example, in a vehicle application, it is required to reduce the density of a flexible polyurethane foam for weight reduction corresponding to fuel consumption regulations.
In order to meet the demand for lower density, the amount of water used as a foaming agent tends to increase further. Increasing the amount of water used (Non-Patent Document 1, etc.) can increase the amount of carbon dioxide generated during foam production and is effective in reducing the density of flexible polyurethane foam. As the hardness decreases, the foam hardness decreases. As a specific technique for improving the hardness of the flexible polyurethane foam, there is a method of increasing the amount of the crosslinking agent to be used (Non-Patent Document 1), etc., but in such a method, the elongation and tensile strength of the flexible polyurethane foam are reduced. There remains a problem such as insufficient mechanical properties, and a flexible polyurethane foam is desired in which the hardness is improved and the mechanical properties are maintained.

JP-A-2005-290202

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

However, the flexible polyurethane foam produced using the above conventional polyol has a problem that the mechanical properties are insufficient.
An object of the present invention is to provide a polyol that solves these problems.

［一般式（Ｉ）中、Ｒ¹は、水素原子、又は炭素数１〜１２のアルキル基、シクロアルキル基若しくはフェニル基を表す。炭素数１〜１２のアルキル基、シクロアルキル基又はフェニル基は、ハロゲン原子又はアリール基で置換されていてもよい。］
ｙ≦２８．３×ｘ^-2×（１００−ｚ）／１００ （１）
［数式（１）中、ｘは単位ｍｇＫＯＨ／ｇで表される水酸基価、ｙは単位ｍｅｑ／ｇで表される総不飽和度を表す。ｚは、（ａ）の重量を基準とするエチレンオキサイド単位含有量であり、０〜５０重量％である。］
強度向上剤（ｂ）：エステル化合物、チオエステル化合物、リン酸エステル化合物及びアミド化合物からなる群より選ばれる少なくとも１種以上の化合物であって、２価以上の芳香族多価カルボン酸を必須構成成分とする化合物。
また、本発明のポリウレタンの製造方法は、ポリオール成分とイソシアネート成分とを反応させてポリウレタンを製造する方法において、ポリオール成分が上記ポリオール組成物（ＰＬ）をポリオール成分の重量に対して１０〜１００重量％含有することを要旨とする。 That is, the polyol (PL) for polyurethane production of the present invention is a polyol composition containing the following polyol (a) and a strength improver (b), and is based on the weight of the polyol composition (PL). The gist is that the ethylene oxide unit content is 13 to 50% by weight.
Polyol (a): an alkylene oxide adduct of the active hydrogen-containing compound (H), wherein 40% or more of the hydroxyl groups located at the terminals are primary hydroxyl group-containing groups represented by the following general formula (I), A polyoxyalkylene polyol in which the valence x, the total degree of unsaturation y, and the ethylene oxide unit content z satisfy the relationship of formula (1).

[In General Formula (I), R ¹ represents a hydrogen atom or an alkyl group, cycloalkyl group, or phenyl group having 1 to 12 carbon atoms. The alkyl group, cycloalkyl group or phenyl group having 1 to 12 carbon atoms may be substituted with a halogen atom or an aryl group. ]
y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)
[In Formula (1), x represents the hydroxyl value represented by the unit mgKOH / g, and y represents the total degree of unsaturation represented by the unit meq / g. z is the ethylene oxide unit content based on the weight of (a), and is 0 to 50% by weight. ]
Strength improver (b): at least one compound selected from the group consisting of ester compounds, thioester compounds, phosphate ester compounds and amide compounds, which is an essential constituent component of a divalent or higher aromatic polyvalent carboxylic acid A compound.
The polyurethane production method of the present invention is a method for producing a polyurethane by reacting a polyol component and an isocyanate component, wherein the polyol component contains the polyol composition (PL) in an amount of 10 to 100 weights based on the weight of the polyol component. % Content.

  The polyurethane obtained by using the polyol composition (PL) for producing a flexible polyurethane foam of the present invention has improved polyurethane mechanical properties such as good foam hardness.

1 is a view showing a reaction apparatus of Production Example 1. FIG. 6 is a view showing a reaction apparatus of Production Example 5. FIG.

The polyol composition (PL) for producing a flexible polyurethane foam in the present invention contains the following polyol (a) and the following strength improver (b).
Polyol (a): an alkylene oxide (hereinafter abbreviated as AO) adduct of an active hydrogen-containing compound (H), wherein 40% or more of the hydroxyl groups located at the terminals are represented by the following general formula (I) It is a polyoxyalkylene polyol which is a hydroxyl group-containing group.

[In General Formula (I), R ¹ represents a hydrogen atom or an alkyl group, cycloalkyl group, or phenyl group having 1 to 12 carbon atoms. The alkyl group, cycloalkyl group or phenyl group having 1 to 12 carbon atoms may be substituted with a halogen atom or an aryl group. ]
Strength improver (b): at least one compound selected from the group consisting of ester compounds, thioester compounds, phosphate ester compounds and amide compounds, and an aromatic polyvalent carboxylic acid having a valence of 2 or more as an essential component A compound.

The polyol (a) is an AO adduct of the active hydrogen-containing compound (H).
The active hydrogen compound (H) includes a hydroxyl group-containing compound, an amino group-containing compound, a thiol group-containing compound, a phosphoric acid compound; a compound having two or more active hydrogen-containing functional groups in the molecule; and two or more of these A mixture is mentioned.

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

  Examples of the amino group-containing compound include amines, polyamines, amino alcohols and the like. Specifically, ammonia; monoamines such as alkylamines having 1 to 20 carbon atoms (hereinafter abbreviated as C) (butylamine and the like) and anilines; aliphatic polyamines such as ethylenediamine, hexamethylenediamine and diethylenetriamine; piperazine and N- Heterocyclic polyamines such as aminoethylpiperazine; Alicyclic polyamines such as dicyclohexylmethanediamine and isophoronediamine; Aromatic polyamines such as phenylenediamine, tolylenediamine and diphenylmethanediamine; Monoethanolamine, diethanolamine and triethanolamine, etc. Alkanolamines; polyamide polyamines obtained by condensation of dicarboxylic acids with excess polyamines; polyether polyamines; hydrazines (hydrazines and monoalkylhydrazines) ), Dihydrazide (dihydrazide succinate dihydrazide and terephthalic acid, etc.), guanidine (butyl guanidine and 1-cyanoguanidine, etc.); dicyandiamide; and mixtures of two or more thereof.

Examples of the thiol group-containing compound include polythiol compounds, and examples include divalent to octavalent polyvalent thiols. Specific examples include ethylenedithiol and 1,6-hexanedithiol.
Examples of phosphoric acid compounds include phosphoric acid, phosphorous acid, and phosphonic acid.

  Of these active hydrogen-containing compounds (H), from the viewpoint of reactivity, a hydroxyl group-containing compound and an amino group-containing compound are preferable, and water, alcohol, and amine are particularly preferable.

  Examples of AO to be added to the active hydrogen-containing compound (H) include C2-6 AO such as ethylene oxide (hereinafter abbreviated as EO), 1,2-propylene oxide (hereinafter abbreviated as PO), 1,3- Examples include propylene oxide, 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.

  The AO adduct of the active hydrogen-containing compound (H) includes a polyoxyalkylene polyol represented by the following general formula (II).

In general formula (II), R ² is an m-valent group obtained by removing m active hydrogens from the active hydrogen-containing compound (H), m is the number of active hydrogens that (H) has, A number of 100.
m is preferably 50 or less, more preferably 10 or less, from the viewpoint of properties such as the viscosity of (a).

  In the general formula (II), Z represents a C2-12 alkylene group or cycloalkylene group represented by the following general formula (III) or (IV). The C2-12 alkylene or cycloalkylene group may be substituted with a halogen atom or an aryl group.

In general formulas (III) and (IV), R ³ represents a hydrogen atom or a C1-10 alkyl group, cycloalkyl group or phenyl group. The C1-10 alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group.

  Specific examples of Z include ethylene group, propylene group, butylene group, chloropropylene group, phenylethylene group, 1,2-cyclohexylene group and the like, and combinations of two or more thereof. From the viewpoint of properties such as the viscosity of (a), a propylene group, a butylene group and an ethylene group are preferred. In consideration of ensuring hydrophobicity in (a), a propylene group, a butylene group or the like may be used, or an ethylene group and another alkylene group may be used in combination.

  In the general formula (II), A represents a C3-12 alkylene group or cycloalkylene group represented by the following general formula (V) or (VI). The C3-12 alkylene group or cycloalkylene group may be substituted with a halogen atom or an aryl group.

In the general formulas (V) and (VI), R ⁴ represents a C1-10 alkyl group, cycloalkyl group or phenyl group. The C1-10 alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group.

  Specific examples of A include a propylene group, a butylene group, a chloropropylene group, a phenylethylene group, a 1,2-cyclohexylene group, and a combination of two or more thereof. Of these, a propylene group and a butylene group are preferable from the viewpoint of properties such as the viscosity of (a).

  When there are a plurality of Z or A, each may be the same or different.

In general formula (II), p and r are integers of 0-200. q is an integer of 1 to 200.
From the viewpoint of the viscosity of the polyol (a), p + q + r is preferably an integer of 1 to 400, and more preferably 200 or less.

  Among those represented by the general formula (II), those in which r is 0 represent that EO is not added to the terminal portion of the polyol (a).

Among those represented by the general formula (II), 40% or more of the structure of A located at the terminal in the part of (AO) _{q in} the general formula (II) is represented by the general formula (VI). The structure is preferable, more preferably 60% or more, and still more preferably 65% or more. Within this range, the moisture resistance of the flexible urethane foam becomes good.

The polyol (a) is a primary hydroxyl group-containing group in which 40% or more of the terminal hydroxyl groups are represented by the above general formula (I).
For example, when (a) is represented by the above general formula (II), the hydroxyl group-containing group located at the terminal includes a primary hydroxyl group-containing group represented by the above general formula (I) and r = 0. Two types of secondary hydroxyl group-containing groups represented by the following general formula (X) can be considered, but (a) is a hydroxyl group located at the terminal regardless of the value of r in the above general formula (II). 40% or more is the primary hydroxyl group-containing group represented by the general formula (I).
In (a), the ratio of the primary hydroxyl group-containing group represented by the general formula (I) to the total hydroxyl groups at the terminals (this is the primary hydroxyl group ratio in the present specification. The same applies hereinafter. Is 40% or more based on the amount of all terminal hydroxyl groups of the polyol (a), and is preferably 60% or more, more preferably 65% or more from the viewpoint of the reactivity of (a). When the primary hydroxyl group ratio is less than 40%, the reactivity as a polyol component is insufficient.

R < ¹ > in said general formula (I) represents a hydrogen atom or a C1-12 alkyl group, a cycloalkyl group, or a phenyl group. The C1-12 alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group. R ⁹ in the general formula (X) represents a C1-12 alkyl group, cycloalkyl group or phenyl group. The C1-12 alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group.

Specific examples of R ¹ include a hydrogen atom; a linear alkyl group such as a methyl group, an ethyl group, and a propyl group; a branched alkyl group such as an isopropyl group; a substituted phenyl group such as a phenyl group and a p-methylphenyl group; A substituted alkyl group such as a methyl group, a bromomethyl group, a chloroethyl group and a bromoethyl group; a substituted phenyl group such as a p-chlorophenyl group and a p-bromophenyl group; a cyclic alkyl group such as a cyclohexyl group; and a combination of two or more of these Is mentioned. Specific examples of R ⁹ include groups other than a hydrogen atom among the groups exemplified for R ¹ .

In the present invention, the primary hydroxyl group ratio is determined by ¹ H—N after pre-treatment of the sample in advance of esterification.
Measure and calculate by MR method.

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

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

The polyol (a) needs to satisfy Formula (1) from the viewpoint of the mechanical properties of polyurethane.
y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)
[In Formula (1), x represents the hydroxyl value represented by the unit mgKOH / g, and y represents the total degree of unsaturation represented by the unit meq / g. z is the EO unit content based on the weight of (a), and is 0 to 50% by weight. ]

  In the above formula (1), the range of x is preferably 5 to 280 mgKOH / g, more preferably 10 to 115 mgKOH / g, and still more preferably 25 to 75 mgKOH / g. If x is 5 mgKOH / g or more, the viscosity of the polyoxyalkylene polyol is low and easy to handle, and if it is 280 mgKOH / g or less, the elongation property of the synthesized polyurethane is good. In addition, x is calculated | required by JISK-1557.

y is a total unsaturation degree (meq / g) of a polyol (a), and is calculated | required by JISK-1557.
The range of y is preferably 0 to 0.04, more preferably 0 to 0.03, and still more preferably 0 to 0.02, from the viewpoint of mechanical properties of polyurethane.

  Z is an EO unit content (% by weight) based on the weight of the polyol (a). The range of z is 0-50, preferably 0-25, particularly preferably 0-20. When z exceeds 50, the polyurethane moisture resistance is deteriorated.

In addition, Numerical formula (1) can also represent the hydroxyl value x also by the hydroxyl equivalent w, In that case, the hydroxyl equivalent w, the total unsaturation degree y, and EO unit content z satisfy | fill the relationship of Numerical formula (2). The hydroxyl group equivalent w is a value obtained by dividing the number average molecular weight of the polyol (a) by the number average hydroxyl number of (a).
y ≦ (9.0 × 10 ⁻⁹ ) w ² × (100−z) / 100 (2)

As described above, the relationship between the hydroxyl value x, the total unsaturation y, and the EO unit content z of the polyol (a) preferably satisfies the relationship of the mathematical formula (1).
y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)
The polyol (a) is characterized by having sufficient reactivity with an isocyanate and hydrophobicity. The polyurethane obtained using (a) has a high reactivity when the polyol is produced, and the mechanical properties (hardness, elongation at break, tensile strength, tear strength) and moisture resistance of the polyurethane are good.

The polyol (a) more preferably satisfies the relationship of the mathematical formula (3).
y ≦ 18.9 × x ⁻² × (100−z) / 100 (3)
The amount of unsaturated monool in the polyol (a) satisfying the mathematical formula (3) is reduced as compared with the case where the mathematical formula (1) is satisfied. The mechanical properties of the polyurethane produced using such a polyol (a) are as follows: Further improvement.

In the above formula, the right side is a value calculated from the hydroxyl value x and the EO unit content z. The right side decreases as the hydroxyl value x increases, that is, decreases as the molecular weight per hydroxyl group in (a) decreases. Further, the right side becomes smaller as the EO unit content z becomes larger.
The left side of the above formulas (1) and (3) is the total degree of unsaturation y.
By the way, the unsaturated group of the polyoxyalkylene polyol is formed by a transfer reaction of AO other than EO (especially PO) in this production process. Therefore, as the EO unit content in the polyoxyalkylene polyol decreases, the degree of unsaturation Tends to increase, and as the molecular weight increases, the degree of unsaturation y tends to increase. Therefore, a polyoxyalkylene polyol having a small EO unit content or a large molecular weight tends to have difficulty satisfying the formulas (1) and (3).
That is, the formula (1) or (3) indicates a region where the total degree of unsaturation y is smaller than the hydroxyl value x and the EO unit content z. In addition, the said Formula (1) and (3) represents the range where the effect of this invention found experimentally is acquired.

  The number average molecular weight of the polyol (a) is appropriately selected depending on the use of the polyol (PL) for producing polyurethane, for example, the required physical properties of the thermosetting resin such as polyurethane to be produced, and is not particularly limited. Therefore, 400 to 100,000 is preferable, and 400 to 20,000 is preferable.

  Specific examples of the polyol (a) include water EO adduct, water PO adduct, glycerin EO adduct, glycerin PO adduct, water EO / PO copolymer adduct, water PO / butylene oxide. Examples thereof include a copolymerization adduct, an EO / PO copolymerization adduct of glycerin, a copolymerization adduct of EO / PO / butylene oxide with water, and a copolymerization adduct of EO / PO / butylene oxide with glycerin.

The active hydrogen-containing compound (J) represented by the following general formula (XI) can be produced by a generally known method, for example, ring opening addition of C2-12 AO to the active hydrogen-containing compound (H). It can manufacture by superposing | polymerizing and the catalyst of this superposition | polymerization is not specifically limited.
The polyol (a) can be obtained by ring-opening addition polymerization of C3-12AO to (J) in the presence of a catalyst to obtain an active hydrogen compound (K) represented by the following general formula (XII). Further, if necessary, EO may be subjected to ring-opening addition polymerization at the end of (K). The method for the ring-opening addition weight of EO to (K) may be the conditions known in the art, and the catalyst is not particularly limited. When EO is not subjected to addition polymerization at the end of (K), (K) is (a), and the hydroxyl value x and total unsaturation y of (a) obtained satisfy the relationship of the formula (1). Is preferred.

In the general formula (XI), R ² , Z, p, and m are the same as those in the general formula (II), and the above can be exemplified in the same manner.
In general formula (XII), R ² , Z, A, p, q, and m are the same as in general formula (II), and the above-described products can be exemplified similarly.

  Specific examples of the active hydrogen-containing compound (J) include those similar to those described above as the active hydrogen-containing compound (H) when p is 0.

When p is 1 or more, examples thereof include compounds obtained by adding C2-12 AO to the above-mentioned p = 0, that is, (H). The catalyst used in the addition reaction is not limited.
For example, specific examples of (J) include adducts such as EO, PO, and butylene oxide to (H), and more specifically, an EO adduct of water, a PO adduct of water, and glycerin. EO adduct, glycerin PO adduct, ammonia EO adduct, ammonia PO adduct, water EO / PO copolymer adduct, water PO / butylene oxide copolymer adduct, glycerin EO / PO co Polymerization adduct, EO / butylene oxide copolymerization adduct of glycerol, PO / butylene oxide copolymerization adduct of glycerin, EO / PO copolymerization adduct of ammonia, EO / PO / butylene oxide copolymerization adduct of water and Examples include EO / PO / butylene oxide copolymerization adduct of glycerin and EO / PO / butylene oxide copolymerization adduct of ammonia.

Examples of the active hydrogen-containing compound (K) include compounds obtained by addition polymerization of C3-12 AO to the active hydrogen-containing compound (J). Since the polyol (a) can be easily obtained, the catalyst used in this addition polymerization is preferably the following catalyst.
For example, (K) includes adducts such as PO and butylene oxide to (J).

  From the viewpoint of reactivity, the polyol (a) preferably has a total content of one or more of zinc, iron, cobalt, chromium, and manganese of 2 ppm or less, more preferably 1 ppm or less. is there.

  The catalyst is a compound represented by the following general formula (VII-1), (VII-2) or (VII-3). Using this, ring-opening addition polymerization of C3-12 AO yields a ring-opening polymer with good yield, and a polyoxyalkylene polyol having a high primary hydroxyl group ratio of terminal hydroxyl groups is obtained.

  In the general formula (VII-1), (VII-2) or (VII-3), X represents a boron atom or an aluminum atom, respectively. From the viewpoint of reactivity, a boron atom is preferable.

R ⁵ in the general formula (VII-1), (VII-2) or (VII-3) is represented by the (substituted) phenyl group represented by the following general formula (VIII) or the following general formula (IX). When there are a plurality of R ⁵ groups, the plurality of R ⁵ groups may be the same or different.

Y in the general formula (VIII) represents a hydrogen atom, a C1-4 alkyl group, a halogen atom, a nitro group, or a cyano group, and may be the same or different. Of these, a hydrogen atom, a halogen atom and a cyano group are preferable, and a halogen atom and a cyano group are more preferable.
Moreover, k represents the number of 0-5.
Specific examples of the phenyl group or substituted phenyl group represented by the general formula (VIII) include a phenyl group, a pentafluorophenyl group, a p-methylphenyl group, a p-cyanophenyl group, and a p-nitrophenyl group. A phenyl group, a pentafluorophenyl group and a p-cyanophenyl group are preferable, and a phenyl group and a pentafluorophenyl group are more preferable.

R ⁶ , R ⁷ and R ^{8 in the} general formula (IX) each independently represent a C1-4 alkyl group, and may be the same or different. Specific examples include a methyl group, an ethyl group, a propyl group, and an isopropyl group. Specific examples of the tertiary alkyl group represented by the general formula (IX) include a t-butyl group and a t-pentyl group.

  Specific examples of the catalyst include triphenylborane, diphenyl-t-butylborane, tri (t-butyl) borane, triphenylaluminum, tris (pentafluorophenyl) borane, and tris (pentafluorophenyl) aluminum.

  AO is added to the active hydrogen-containing compound (J) in the presence of a catalyst to obtain an active hydrogen compound (K). The number of moles of AO to be added is the active hydrogen of the active hydrogen-containing compound (J). The amount is preferably from 1 to 200 mol, more preferably from 1 to 100 mol, and it is appropriately selected depending on the molecular weight of the ring-opening polymer to be produced and its use.

  Although the usage-amount of a catalyst is not specifically limited, 0.0001-10 weight% is preferable with respect to the ring-opening polymer to manufacture, More preferably, it is 0.0005-1 weight%.

  When an active hydrogen compound (K) represented by the above general formula (XII) is obtained by adding AO to the active hydrogen-containing compound (J) in the presence of a catalyst, the boiling point at a pressure of 0.1 MPa is 150. It is preferable to continuously or intermittently remove the by-product low-boiling compound (t) having a temperature of not more than 0 ° C. because the polyol (a) satisfying the above-described formula (1) is easily obtained. The removal method may be carried out by any of the commonly known methods. For example, a method of removing (t) from the reaction mixture by heating and / or decompressing, a method of removing the gas phase in the reaction vessel from the reaction vessel using a gas-phase circulation pump, and removing the (t) with an adsorbent, a reaction A method in which the gas phase in the tank is extracted from the reaction tank using a gas-phase circulation pump (t) is reacted with a catalyst to separate it as a high-boiling compound, and the gas phase in the reaction tank is extracted using a gas-phase circulation pump. For example, there is a method of extracting (t) from the reaction tank and separating it by distillation.

  Specific examples of the by-product low boiling point compound (t) having a boiling point of 150 ° C. or less at a pressure of 0.1 MPa include formaldehyde (boiling point−19 ° C.), acetaldehyde (boiling point 20 ° C.), propionaldehyde (boiling point 48 ° C.), and allyl alcohol. And compounds having 0 to 2 mol of AO added thereto. (T) is often generated in an amount of 0.0001 to 10% by weight based on the weight of the polyol (a) when adding AO.

  When AO is added to the active hydrogen-containing compound (J), the active hydrogen-containing compound (J), AO, and a catalyst may be charged and reacted together, or the active hydrogen-containing compound (J) and AO may be dropped and reacted with the mixture with the catalyst, or AO and the catalyst may be dropped and reacted with the active hydrogen-containing compound (J). From the viewpoint of controlling the reaction temperature, a method in which AO is dropped into a mixture of the active hydrogen-containing compound (J) and the catalyst, or AO and the catalyst are dropped into the active hydrogen-containing compound (J) is preferable.

  The reaction temperature for adding AO to the active hydrogen-containing compound (J) is preferably 0 ° C to 250 ° C, more preferably 20 ° C to 180 ° C.

  The produced polyol (a) contains a catalyst, and the decomposition and / or removal treatment of the catalyst is performed as necessary depending on the use.

  As a decomposition method, there is a method of adding a basic substance such as water and / or an alcohol compound and, if necessary, an alkali compound. As the alcohol compound, the aforementioned alcohol and / or phenol can be used. Examples of the alkali compound include alkali metal hydroxides (potassium hydroxide, sodium hydroxide, cesium hydroxide, etc.), alkali metal alcoholates (potassium methylate, sodium methylate, etc.) and mixtures of two or more of these. Of these, alkali metal hydroxides are preferred from the viewpoint of productivity. In the decomposition, the decomposition temperature is preferably 10 to 180 ° C, more preferably 80 to 150 ° C. The decomposition may be performed in a sealed state, may be performed while exhausting by connecting to a vacuum source, or may be performed while continuously adding water or an alcohol compound. Water or alcohol to be added may be added in a liquid state, or may be added in a vapor or solid state. The amount of water and / or alcohol compound used is preferably 0.1 to 100% by weight, more preferably 1 to 20% by weight, based on the weight of the addition product. The amount of the alkali compound used is preferably 0.1 to 10% by weight, more preferably 0.3 to 2% by weight, based on the weight of the addition product.

  As a removing method, any known method may be used. For example, hydrotalcite-based adsorbents {KYOWARD 500, KYOWARD 1000, KYOWARD 2000 etc. (all manufactured by Kyowa Chemical Industry Co., Ltd.)} and filter aids such as diatomaceous earth {Radiolite 600, Radiolite 800 and Radiolite 900 (Both manufactured by Showa Chemical Co., Ltd.)} and the like can be used. The filtration may be either pressure filtration or vacuum filtration, but pressure filtration is preferred because it is easy to prevent oxygen contamination. The material of the filter is not particularly limited. For example, paper, polypropylene, polytetrafluoroethylene, polyester, polyphenylene sulfide, acrylic, and meta-aramid are exemplified, and paper is preferable. The retained particle diameter of the filter is preferably 0.1 to 10 μm, more preferably 1 to 5 μm.

  Even if the catalyst remains in the polyol (a), the reactivity of the polyol and isocyanate in the subsequent urethanization reaction is not greatly adversely affected as compared with the conventional alkaline catalyst. However, it is preferable to decompose and / or remove the remaining catalyst from the viewpoint of preventing coloring.

When the polyol (PL) for polyurethane production contains the polyol (a), it also includes containing the polymer polyol (W) obtained by polymerizing the vinyl monomer (g) in (a).
The polymer polyol (W) is a polymer polyol in which polymer particles (P) are dispersed in (a).
The polymer polyol (W) can be produced by polymerizing the vinyl monomer (g) in (a) by a known method. For example, in (a), a vinyl monomer (g) is polymerized in the presence of a radical polymerization initiator, and the obtained polymer (g) is stably dispersed. Specific examples of the polymerization method include those described in US Pat. No. 3,383,351 and Japanese Examined Patent Publication No. 39-25737.
(G) is preferably styrene and / or acrylonitrile.

  The strength improver (b) is at least one compound selected from the group consisting of an ester compound, a thioester compound, a phosphate ester compound, and an amide compound, and an essential constituent of a divalent or higher aromatic polyvalent carboxylic acid It is a compound as a component. (B) is at least one selected from the group consisting of a divalent or higher aromatic polyvalent carboxylic acid and an active hydrogen-containing compound (for example, a hydroxyl group-containing compound, a thiol group-containing compound, a phosphoric acid compound, and an amino group-containing compound). Compound).

A divalent or higher aromatic polyvalent carboxylic acid means a compound that satisfies the following (1) to (3). (1) One molecule has one or more aromatic rings.
(2) The number of carboxyl groups in one molecule is 2 or more.
(3) The carboxyl group is directly bonded to the aromatic ring.

The number of aromatic rings contained in one molecule of an aromatic polyvalent carboxylic acid having a valence of 2 or more is 1 or more, preferably 1 to 4, more preferably from the viewpoint of the mechanical properties of the polyurethane and the compatibility with the polyol. Is one.
The number of carboxyl groups that one molecule of the aromatic polyvalent carboxylic acid having 2 or more valences is 2 or more, and 2 to 4 are preferable from the viewpoint of mechanical properties of polyurethane and handling (viscosity) during molding, More preferably, it is 3-4, and further more preferably 3.

As the aromatic polyvalent carboxylic acid having 2 or more valences, phthalic acid, isophthalic acid, terephthalic acid, 2,2′-bibenzyldicarboxylic acid, trimellitic acid, hemilitic acid, trimesic acid, pyromellitic acid and naphthalene-1, Aromatic polycarboxylic acids having 8 to 18 carbon atoms such as 4-dicarboxylic acid, naphthalene-2,3,6 tricarboxylic acid, diphenic acid, 2,3-anthracene dicarboxylic acid, 2,3,6-anthracentricarboxylic acid and pyrene dicarboxylic acid Examples include acids.

  As the aromatic polyvalent carboxylic acid having two or more valences, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid and naphthalene-1,4 dicarboxylic acid are preferable and more preferable from the viewpoint of mechanical properties of polyurethane. Is trimellitic acid and pyromellitic acid, and more preferably trimellitic acid.

Examples of the hydroxyl group-containing compound include monohydric alcohols, divalent to octavalent polyhydric alcohols, phenols and polyhydric phenols. Specifically, monohydric alcohols such as methanol, ethanol, butanol, octanol, benzyl alcohol, naphthylethanol; ethylene glycol, propylene glycol, 1,3 and 1,4-butanediol, 1,6-hexanediol, 1, Dihydric alcohols such as 10-decanediol, diethylene glycol, neopentyl glycol, cyclohexanediol, cyclohexanedimethanol, 1,4-bis (hydroxymethyl) cyclohexane and 1,4-bis (hydroxyethyl) benzene; glycerin and trimethylolpropane Trihydric alcohols such as pentaerythritol, sorbitol, mannitol, sorbitan, diglycerin, dipentaerythritol, sucrose, glucose, mannose, fructose, methyl 4- to 8-valent alcohols such as lucoside and derivatives thereof; phenol, phloroglucin, cresol, pyrogallol, catechol, hydroquinone, bisphenol A, bisphenol F, bisphenol S, 1-hydroxynaphthalene, 1, 3, 6 , 8-tetrahydroxynaphthalene, anthrol, phenols such as 1,4,5,8-tetrahydroxyanthracene and 1-hydroxypyrene; polybutadiene polyol; castor oil-based polyol; (co) heavy of hydroxyalkyl (meth) acrylate Examples thereof include polyfunctional (eg, 2-100 functional group) polyols such as coalesced and polyvinyl alcohol, condensates 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 thiol group-containing compound include monofunctional phenylthiol, alkylthiol, and polythiol compounds. Examples of the polythiol include divalent to octavalent polyvalent thiols. Specific examples include ethylenedithiol and 1,6-hexanedithiol.

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

  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; and dicarboxylic acids Polyamide polyamine obtained by condensation with excess polyamine; polyether polyamine; hydrazine (such as hydrazine and monoalkylhydrazine), dihydrazide ( Etc. Haq acid dihydrazide and dihydrazide terephthalic acid), guanidine (butyl guanidine and 1-cyanoguanidine, etc.); dicyandiamide; and the like.

  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.

  Moreover, as an active hydrogen containing compound, the AO adduct of the said active hydrogen containing compound can also be used.

  Examples of the AO added to the active hydrogen-containing compound include AO having 2 to 6 carbon atoms such as EO, PO, 1,3-propyloxide, 1,2-butylene oxide, 1,4-butylene oxide, and the like. Of these, PO, EO, and 1,2-butylene oxide are preferable from the viewpoints of properties and reactivity. When two or more types of AO are used (for example, PO and EO), block addition or random addition may be used, or a combination thereof may be used.

  Furthermore, as the active hydrogen-containing compound, the activity obtained by the condensation reaction of the active hydrogen-containing compound and a polycarboxylic acid [aliphatic polyvalent carboxylic acid or divalent or higher aromatic polyvalent carboxylic acid (same as above)]. Hydrogen-containing compounds (polyester compounds) can be used. In the condensation reaction, one type of active hydrogen-containing compound and polycarboxylic acid may be used, or two or more types may be used in combination.

The aliphatic polycarboxylic acid means a compound that satisfies the following (1) and (2).
(1) One molecule has two or more carboxyl groups.
(2) The carboxyl group is not directly bonded to the aromatic ring.

  Aliphatic polycarboxylic acids include succinic acid, adipic acid, sebacic acid, maleic acid and fumaric acid.

  In addition, when carrying out the condensation reaction between a divalent or higher aromatic polyvalent carboxylic acid and an active hydrogen-containing compound, an anhydride or lower alkyl ester of a divalent or higher aromatic polyvalent carboxylic acid can also be used. .

  The strength improver (b) is preferably a compound represented by the following general formula (XIII) from the viewpoint of improving the mechanical properties of polyurethane.

[In the general formula (XIII), R ¹⁰ represents a residue obtained by removing one active hydrogen from an active hydrogen-containing compound. The plurality of R ¹⁰ may be the same or different. ; Q represents the residue remove | excluding the carboxyl group from aromatic polycarboxylic acid more than trivalence. The aromatic ring of Q is composed of carbon atoms. The substituent of the aromatic ring may be a hydrogen atom or another substituent, but at least one substituent is a hydrogen atom. A is an integer satisfying 2 ≦ a ≦ (the number of aromatic ring substituents−2). T represents a residue obtained by removing m active hydrogens from an active hydrogen-containing compound having a valence of at least m. M represents an integer of 1 to 10; ]

R ¹⁰ is a residue obtained by removing one active hydrogen from an active hydrogen-containing compound. From the viewpoint of handling a strength improver and improving the mechanical properties (elongation, tensile strength, compression hardness) of polyurethane, this active hydrogen. The containing compound is preferably a hydroxyl group-containing compound, an amino group-containing compound, an AO adduct thereof, or a polyester compound obtained by a condensation reaction of an active hydrogen-containing compound and a polycarboxylic acid, more preferably methanol, ethanol, butanol, or ethylene. Glycol, propylene glycol, glycerin, pentaerythritol, sorbitol, sucrose, benzyl alcohol, phenol, methylamine, dimethylamine, ethylamine, diethylamine, butylamine, dibutylamine, phenylamine, diphenylamine, their EO and / or O adduct and condensation products of these active hydrogen compounds and phthalic acid and / or isophthalic acid are preferred.

  In general formula (XIII), Q represents a residue obtained by removing a carboxyl group from a trivalent or higher aromatic polycarboxylic acid. The aromatic ring of Q is composed of carbon atoms. The substituent of the aromatic ring may be a hydrogen atom or another substituent, but at least one substituent is a hydrogen atom. That is, the aromatic ring of Q has at least one hydrogen atom bonded to the carbon atom constituting the aromatic ring.

  Other substituents are alkyl group, vinyl group, allyl group, cycloalkyl group, halogen atom, amino group, carbonyl group, carboxyl group, hydroxyl group, hydroxyamino group, nitro group, phosphino group, thio group, thiol group Aldehyde group, ether group, aryl group, amide group, cyano group, urea group, urethane group, sulfone group, ester group and azo group. From the viewpoint of improving the mechanical properties of polyurethane (elongation, tensile strength, tear strength, compression hardness) and cost, other substituents include alkyl groups, vinyl groups, allyl groups, amino groups, amide groups, urethane groups, and ureas. Groups are preferred.

  Regarding the arrangement of substituents on Q, from the viewpoint of improving the mechanical properties of polyurethane, two carbonyl groups are adjacent to each other, and hydrogen is used as a substituent between the third carbonyl group and the first or second carbonyl group. A structure in which is arranged is preferable.

  Examples of the trivalent or higher aromatic polycarboxylic acid constituting Q include trimellitic acid, hemilitic acid, trimesic acid, pyromellitic acid, naphthalene-2,3,6 tricarboxylic acid, and 2,3,6-anthracentricarboxylic acid. And an aromatic polycarboxylic acid having 8 to 18 carbon atoms.

  From the viewpoint of handling the strength improver and improving the mechanical properties (tensile strength, tear strength, compression hardness) of the polyurethane, the aromatic polycarboxylic acid used for Q is preferably a monocyclic compound, more preferably trimellitic acid and It is pyromellitic acid.

  A in the general formula (XIII) is an integer satisfying 2 ≦ a ≦ the number of aromatic ring substituents−2. The number of aromatic ring substituents is the number of substituents bonded to the carbon atoms constituting the aromatic ring. For example, in a monocyclic aromatic ring composed of 6 carbons, the number of aromatic ring substituents is 6, and a can be 2 to 4. When the aromatic ring is a monocyclic aromatic ring, a is preferably 2 or 3 from the viewpoint of improving the mechanical properties (tensile strength, tear strength, compression hardness) of the polyurethane.

T in general formula (XIII) represents the residue remove | excluding m active hydrogen from the active hydrogen containing compound more than m valence. The active hydrogen-containing compound referred to here includes the active hydrogen-containing compound represented by R ¹⁰ described above.
In general formula (XIII), m represents an integer of 1 to 10.
From the viewpoint of handling the strength improver and improving the mechanical properties (tensile strength, tear strength, compression hardness) of the polyurethane foam, T is a hydroxyl group-containing compound, an amino group-containing compound, an AO adduct thereof, and a polycarboxylic acid. It is preferable to use a condensate with an acid, and m is preferably 1 to 8.
Further, the formula amount of T is preferably 48 to 3000, more preferably 60 to 2500, from the viewpoint of improving the mechanical properties of polyurethane and compatibility with polyol.

The hydroxyl value (mgKOH / g) of the strength improver (b) is preferably from 0 to 700, more preferably from 0 to 650, and still more preferably from 0 to 700, from the viewpoint of handling (viscosity) and tensile strength during molding. 600.
In the present invention, the hydroxyl value is measured in accordance with JISK-1557.
Further, when the hydroxyl value of (b) is 0 and is represented by the general formula (XIII), it means that all R ¹⁰ , Q and T in the general formula (XIII) do not have a hydroxyl group.

The aromatic ring concentration (mmol / g) of the strength improver (b) is preferably 0.1 to 10.0, more preferably 0.2 to 9 from the viewpoint of improving the mechanical properties (elongation and tensile strength) of the polyurethane. .5, and further preferably 0.3 to 9.0.
The aromatic ring concentration in (b) means the number of moles of aromatic rings in 1 g of the strength improver (b).
The content of the strength improver (b) is preferably 0.1 to 30.0% by weight based on the weight of the polyol composition (PL) from the viewpoint of improving the mechanical properties (elongation and tensile strength) of the polyurethane. More preferably, it is 0.5 to 29.5% by weight, and further preferably 0.9 to 29.0% by weight.

The content of Q derived from an aromatic polycarboxylic acid having a valence of 3 or more is from the viewpoint of improving mechanical properties (tensile strength, tear strength, compression hardness) based on the number average molecular weight of the strength improver (b). It is preferably 5 to 50%, more preferably 4 to 47%, and still more preferably 6 to 45%.
The carbonyloxy group (—COO—) concentration (mmol / g) of the strength improver (b) is 0.5 to 0.5 from the viewpoint of handling at the time of molding (viscosity of the polyol component (b)), tensile strength, and elongation properties. 15 is preferred, more preferably 1.0 to 12, and even more preferably 1.5 to 10.

  In the polyol composition (P), in addition to the polyol (a) and the strength improver (b), a polyol (c) may be contained if necessary. The polyol (c) is a known polyol such as a polyhydric alcohol, a polyether polyol or a polyester polyol, or an active hydrogen-containing compound other than the polyol (a) and the strength improver (b).

  (C) is an AO adduct (c1) of an aliphatic amine, an AO adduct (c2) of an aromatic amine, an AO adduct (c3) of a polyhydric alcohol or polyhydric phenol, and a polyester polyol (c4). You may use together.

Examples of the aliphatic amine of (c1) include primary and / or secondary amines, and the number of primary and / or secondary amino groups is preferably 1 to 4, more preferably 1 to 3. Yes, the number of active hydrogens derived from amino groups is preferably 2-8, more preferably 2-4.
Specific examples of (c1) include alkanolamines, C1-20 alkylamines, C2-6 alkylenediamines, and polyalkylene polyamines having 2 to 6 C alkylene groups (polymerization degree 2 to 8). (C1) is preferably alkanolamine or alkylenediamine.
As the AO to be added in (c1), from the viewpoint of the mechanical properties of the flexible polyurethane foam, those containing PO and / or EO as a main component and optionally containing other AO of 20% by weight or less are preferable, particularly preferably PO and It is a combined use of PO and EO.

Examples of the aromatic amine (c2) include C6-20 aromatic amines, and aniline, phenylenediamine and tolylenediamine are preferred.
As the AO to be added in (c2), from the viewpoint of the physical properties of the polyurethane resin, those containing PO and / or EO as the main component and optionally containing other 20% or less of other AO are preferable, and particularly preferably PO and PO. It is combined use with EO.

Examples of the polyhydric alcohol (c3) include C2-18 (preferably 2-12) dihydric alcohol [ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4- and 1,3-butanediol. , 1,6-hexanediol and neopentyl glycol, etc.], C3-18 (preferably 3-12) 3-5 valent polyhydric alcohol [alkane polyol and its intramolecular or intermolecular dehydrate, such as glycerin, Trimethylolpropane, pentaerythritol, sorbitan, diglycerin; sugars and derivatives thereof, for example, α-methylglucoside, xylitol, glucose, fructose; etc.] and C5-18 (preferably 5-12) 6-10 valence or More polyhydric alcohol [6-10 valent al Intramolecular or intermolecular dehydrates of polyhydric alkane polyols such as dipentaerythritol; saccharides and derivatives thereof such as sorbitol, mannitol, sucrose; and the like, and combinations of two or more of these .
Examples of the polyhydric phenol of (c3) include (divalent polyhydric phenols [monocyclic polyhydric phenols (hydroquinone, etc.), bisphenols (bisphenol A, bisphenol F, etc.), etc.]], 3-5 valent polyhydric phenols [mono Ring polyhydric phenols (pyrogallol, phloroglucin, etc.), formalin low condensates of phenolic compounds (3-5 valences) (number average molecular weight 1000 or less) (novolak resins, intermediates of resol), etc.], 6-10 valences or more Polyphenols [formalin low condensate of phenolic compound (6 valences or more) (number average molecular weight 1000 or less) (novolak resin, intermediate of resol), etc.], condensate of phenol and alkanolamine (Mannich polyol), and A combination of two or more of these may be mentioned.
As the AO to be added in (c3), from the viewpoint of the mechanical properties of the flexible polyurethane foam, those containing PO and / or EO as a main component and optionally containing other 20% or less of other AO are preferable, and particularly preferably PO and It is a combined use of PO and EO.

  As the polyester polyol of (c4), a polyhydric hydroxyl group-containing compound (such as the above-mentioned polyhydric alcohol), an aromatic polycarboxylic acid (such as those described above) and an aliphatic polycarboxylic acid (such as adipic acid), their anhydrides and Condensation-reactive organisms with ester-forming derivatives (phthalic anhydride, dimethyl terephthalate, etc.) such as lower alkyl (alkyl group C is 1 to 4) ester; carboxylic anhydride and AO of the polyhydric alcohol These AO (EO, PO, etc.) addition reaction products; polylactone polyols (for example, those obtained by ring-opening polymerization of lactones (ε-caprolactone, etc.) using the polyhydric alcohol as an initiator); And polycarbonate polyol (for example, a reaction product of the polyhydric alcohol and alkylene carbonate). It is.

  The hydroxyl value (mgKOH / g) of the polyol (c) is preferably 10 to 2000, more preferably 20 to 1900, from the viewpoint of mechanical properties of the flexible polyurethane foam.

The EO unit content based on the total weight of the polyol composition (PL) of the present invention is 13 to 50% by weight, more preferably 13 to 40% by weight, and most preferably, from the viewpoint of mechanical properties and moldability. Is 13 to 20% by weight.
Any of (a), (b), and (c) may be included in the EO unit, and the EO unit defined here is the total amount of EO units that (PL) has.

  The content of the polyol (a), the strength improver (b) and the polyol (c) based on the weight of the polyol composition (PL) is from 1 to 80 weights of the polyol (a) from the viewpoint of the mechanical properties of the flexible polyurethane foam. %, Strength improver (b) 0.1 to 50% by weight, polyol (c) 0.1 to 80% by weight, more preferably (a) 5 to 60% by weight, (b) 1 to 40% % Weight%, (c) 0.2-60% weight.

  The polyol (PL) for polyurethane production of the present invention only needs to contain the polyol (a) and the strength improver (b), and the production method includes a method of mixing (a) and (b). It is done.

The polyol composition (PL) for producing a flexible polyurethane foam of the present invention can be used for a flexible polyurethane foam, and is particularly preferably used as a cushion material for a vehicle seat.
That is, when a flexible polyurethane foam is produced by reacting a polyol component and an isocyanate component, if necessary, in the presence of an additive, (PL) is used as at least a part of the polyol component.
As a method for producing a flexible polyurethane foam using (PL), in the method for producing a flexible polyurethane foam by reacting a polyol component and an isocyanate component, the polyol component comprises the above-mentioned composition for producing flexible polyurethane foam (PL) as a polyol component. The manufacturing method of the polyurethane which contains 10 to 100 weight% with respect to the weight of is included.

  As an isocyanate component, what is conventionally used for polyurethane manufacture can be used. Examples of such isocyanates include aromatic polyisocyanates, aliphatic polyisocyanates, alicyclic polyisocyanates, araliphatic polyisocyanates, and modified products thereof (for example, urethane groups, carbodiimide groups, allophanate groups, urea groups, burettes). Group, an isocyanurate group, or an oxazolidone group-containing modified product) and a mixture of two or more thereof.

Examples of the aromatic polyisocyanate include C (excluding carbon in the NCO group; the same as the following isocyanates) 6 to 16 aromatic diisocyanates, C6 to 20 aromatic triisocyanates, and crude products of these isocyanates. . Specific examples include 1,3- and / or 1,4-phenylene diisocyanate, 2,4- and / or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4′- and / or 4, 4'-diphenylmethane diisocyanate (MDI), polymethylene polyphenyl isocyanate (crude MDI), and the like.
Examples of the aliphatic polyisocyanate include C6-10 aliphatic diisocyanate. Specific examples include 1,6-hexamethylene diisocyanate and lysine diisocyanate.

Examples of the alicyclic polyisocyanate include C6-16 alicyclic diisocyanate. Specific examples include isophorone diisocyanate (IPDI), 4,4′-dicyclohexylmethane diisocyanate, norbornane diisocyanate, and the like.
Examples of the araliphatic polyisocyanate include C8-12 araliphatic diisocyanate. Specific examples include xylylene diisocyanate, α, α, α ′, α′-tetramethylxylylene diisocyanate, and the like.
Specific examples of the modified polyisocyanate include urethane-modified MDI and carbodiimide-modified MDI.

When producing a flexible polyurethane foam, if necessary, the reaction may be carried out in the presence of an additive described below.
In the case of producing a flexible polyurethane foam, a foaming agent is used.
As the foaming agent, known foaming agents can be used, and examples thereof include water, hydrogen atom-containing halogenated hydrocarbons, low boiling point hydrocarbons, and liquefied carbon dioxide gas, and two or more kinds may be used in combination.
Specific examples of the hydrogen atom-containing halogenated hydrocarbon include methylene chloride and HCFC (hydrochlorofluorocarbon) type (for example, HCFC-123 and HCFC-141b); HFC (hydrofluorocarbon) type (for example, HFC-245fa). And HFC-365mfc).
The low boiling point hydrocarbon is a hydrocarbon having a normal boiling point of −5 to 70 ° C., and specific examples thereof include butane, pentane, and cyclopentane.

When the foaming agent is water, the amount of the foaming agent used relative to 100 parts of the polyol component is preferably 0.1 to 30 parts, and more preferably 1 to 20 parts. The hydrogen atom-containing halogenated hydrocarbon is preferably 50 parts or less, more preferably 10 to 45 parts. The low boiling point hydrocarbon is preferably 40 parts or less, more preferably 10 to 30 parts. The amount of liquefied carbon dioxide is preferably 30 parts or less, and more preferably 1 to 25 parts.
In addition, in the above and the following, a part means a weight part.

  Further, for example, foam stabilizers (dimethylsiloxane, polyether-modified dimethylsiloxane, etc.), urethanization catalysts {tertiary amine catalysts (triethylenediamine, N-ethylmorpholine, diethylethanolamine, N, N, N ′, N '-Tetramethylhexamethylenediamine, tetramethylethylenediamine, diaminobicyclooctane, 1,2-dimethylimidazole, 1-methylimidazole and 1,8-diazabicyclo- [5,4,0] -undecene-7), and / or Or metal catalysts (stannic octylate, dibutylstannic dilaurate, lead octylate, etc.), colorants (dyes and pigments), plasticizers (phthalate esters, adipates, etc.), organic fillers (synthesis short) Fibers, hollow microspheres made of thermoplastic or thermosetting resin, etc.), flame retardants Esters and halogenated phosphoric acid esters, etc.), antioxidant (triazole and benzophenone), antioxidants (which can be reacted in the presence of a hindered phenol and hindered amine and the like) and the like known additives.

  With respect to the amount of these additives used relative to 100 parts of the polyol component, the foam stabilizer is preferably 10 parts or less, more preferably 0.5 to 5 parts. The urethanization catalyst is preferably 10 parts or less, more preferably 0.2 to 5 parts. The colorant is preferably 1 part or less. The plasticizer is preferably 10 parts or less, more preferably 5 parts or less. The organic filler is preferably 50 parts or less, more preferably 30 parts or less. The flame retardant is preferably 30 parts or less, more preferably 5 to 20 parts. The anti-aging agent is preferably 1 part or less, more preferably 0.01 to 0.5 part. The antioxidant is preferably 1 part or less, and more preferably 0.01 to 0.5 part. The total amount of additives used is preferably 50 parts or less, more preferably 0.2 to 30 parts.

  The isocyanate index (NCO INDEX) [(NCO group / active hydrogen atom-containing group) equivalent ratio × 100] in the production of the flexible polyurethane foam of the present invention is preferably 80 to 150, more preferably 85 to 135, particularly Preferably it is 90-130.

  The content of the polyol composition (PL) for producing a flexible polyurethane foam in the polyol component is preferably 10 to 100% by weight, more preferably, based on the weight of the polyol component, from the viewpoint of the mechanical properties of the flexible polyurethane foam. It is 20 to 80% by weight, and further preferably 30 to 60% by weight.

Moreover, the conditions which make a polyol component and an isocyanate component react may be the well-known conditions normally used.
As an example, first, a predetermined amount of a polyol component and, if necessary, an additive are mixed. The mixture is then rapidly mixed with the isocyanate component using a polyurethane low pressure or high pressure injection foamer or stirrer. The obtained mixed liquid is poured into a sealed mold or an open mold (made of metal or resin), subjected to urethanization reaction, cured for a predetermined time, and demolded to obtain polyurethane.

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

Production Example 1 [Production of polyol a-1]
As in the embodiment shown in FIG. 1, a stainless steel autoclave as a reaction vessel (1) with a stirring device having a capacity of 2500 ml, a temperature control device, a raw material supply line (5), and magnesium oxide (granule, diameter 2 to 0. Reaction tower (2) packed with 400 parts (1 mm) (stainless steel cylindrical tube, inner diameter 5.5 cm, two 30 cm lengths are used), and distillation tower (3) (theoretical plate number 30, stainless steel cylindrical tube, An inner diameter of 5.5 cm and a length of 2 m was connected by circulation lines (6), (7), and (8).
After charging 267 g of a pentaerythritol PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane into the reaction vessel (1), the autoclave {reaction vessel (1)} and the reaction tower (2) and The pressure in the circulation lines (6), (7), (8) was reduced to 0.005 MPa. Gas phase in the autoclave {reaction vessel (1)} using a diaphragm pump while continuously pouring PO into the liquid phase through the raw material supply line (5) while maintaining the reaction temperature to be kept at 50-60 ° C. At a flow rate of 5 L / min, reaction tank (1) → circulation line (6) → reaction tower (2) → circulation line (7) → distillation tower (3) → circulation line (8) → reaction tank (1) It was circulated in order. While controlling the reaction tower (2) at 75 ° C. and 0.08 to 0.15 MPa, the by-product low-boiling compound is continuously brought into contact with magnesium oxide to form a high-boiling compound. In the distillation tower (3) It was removed from the system by separating from PO. The separated high boiling point compound was extracted from the bottom line (4) of the distillation column (3). When the amount of liquid in the autoclave {reactor (1)} reaches 1840 ml, the PO is stopped, the gas phase circulation is terminated, the mixture is aged at 70 ° C. for 4 hours, 170 g of water is added and 130 to 140 ° C. is added for 1 hour. Heated. After the water was distilled off at normal pressure over 2 hours, 2 g of potassium hydroxide was added, and the remaining water was distilled off under reduced pressure while maintaining the pressure at 30-50 torr while introducing steam at 130-140 ° C. Subsequently, 160 g of EO was added through the raw material supply line (5) while maintaining the reaction temperature at 130 to 140 ° C. over 2 hours, followed by aging for 2 hours. After cooling to 90 ° C., 12 g of Kyoward 600 (manufactured by Kyowa Chemical Co., Ltd .; synthetic silicate) and 40 g of water were added and treated for 1 hour. After taking out from the autoclave {reaction tank (1)}, it was filtered using 1 micron filter paper and dehydrated under reduced pressure to obtain a liquid POEO adduct (a-1) of pentaerythritol. The pentaerythritol PO adduct (hydroxyl value 280) is synthesized by a known method, that is, after adding a predetermined amount of PO to propylene glycol using potassium hydroxide as a catalyst, water and synthetic silicic acid are used for catalyst removal. Salt (Kyowa Chemical Co., Ltd. Kyoward 600) was added, heat-treated, filtered, and dehydrated under reduced pressure.

Production Example 2 [Production of polyol a-2]
Liquid pentaerythritol was synthesized in the same manner as in Production Example 1 except that 466 g of pentaerythritol PO adduct (hydroxyl value 160) was used instead of 267 g of pentaerythritol PO adduct (hydroxyl value 280). A POEO adduct (a-2) was obtained. The pentaerythritol PO adduct (hydroxyl value 160) was synthesized by a known method, that is, after adding a predetermined amount of PO to propylene glycol using potassium hydroxide as a catalyst, water and synthetic silicic acid were used for catalyst removal. Salt (Kyowa Chemical Co., Ltd. Kyoward 600) was added, heat-treated, filtered, and dehydrated under reduced pressure.

Production Example 3 [Production of polyol a-3]
Liquid pentaerythritol was synthesized in the same manner as in Production Example 1 except that 200 g of pentaerythritol PO adduct (hydroxyl value 280) was used instead of 400 g of pentaerythritol PO adduct (hydroxyl value 280). A POEO adduct (a-3) was obtained.

Production Example 4 [Production of polyol a-4]
Liquid pentaerythritol was synthesized in the same manner as in Production Example 3 except that 350 g of pentaerythritol PO adduct (hydroxyl value 160) was used instead of 200 g of pentaerythritol PO adduct (hydroxyl value 280). A POEO adduct (a-4) was obtained. The same PO adduct (hydroxyl value 160) of pentaerythritol as in Production Example 2 was used.

Production Example 5 [Production of polyol n-1]
As shown in FIG. 2, 61 g of glycerin and 4.0 g of potassium hydroxide were charged in a stainless steel autoclave as a reaction vessel (1) with a 2500 ml stirring device, a temperature control device, and a raw material supply line (5). Thereafter, PO was added through the raw material supply line (5) while controlling the reaction temperature so as to maintain 90 to 100 ° C. However, PO was continuously introduced over 6 hours. The autoclave {reaction tank (1)} was charged until the amount of the liquid in the autoclave {reaction tank (1)} reached 2000 ml, and then aged at 100 ° C. for 3 hours. Next, 30 g of synthetic silicate (KYOWARD 600, manufactured by Kyowa Chemical) and 40 g of water were added and treated at 90 ° C. for 1 hour. After taking out from the autoclave {reaction tank (1)}, it was filtered through a 1 micron filter and dehydrated for 2 hours to obtain a liquid glycerin PO adduct (n-1).

The analysis results of the polyoxyalkylene polyols of Production Examples 1 to 4 are shown in Table 1.
The verification result about Formula 1 (following, Formula (4)) of patent document 4 (patent 3688667 gazette) which the polyoxyalkylene polyol which is a prior art is satisfied was also described.

^{y ≦ (1.9 × 10- 8)} w 2 (4)
Formula (4) is a formula that represents the relationship between the hydroxyl equivalent weight w and the degree of unsaturation y, and corresponds to the formulas (1) and (3) in the present invention, that is, the hydroxyl value x and the degree of unsaturation in (S). When transformed into the relational expression of y, the mathematical expression (4 ′) is obtained.
y ≦ 60 × x− ² (4 ′)

  The analysis results of the polyoxyalkylene polyol of Production Example 5 are shown in Table 2. The verification results for the above formula (4) are also described.

A method for measuring the hydroxyl value and the degree of unsaturation of the produced polyoxyalkylene polyol and these units are shown below.
Hydroxyl value: Conforms to JIS K1557, unit is mgKOH / g
Unsaturation degree: Conforms to JIS K1557, unit is meq / g

In Tables 1 and 2, the hydroxyl equivalent is defined by the following mathematical formula (5). Specifically, the hydroxyl value x is measured and determined by 56100 / hydroxyl value x.
(Hydroxyl equivalent) = (Number average molecular weight) / (Average number of hydroxyl groups) (5)

Production Example 6 [Production of Strength Improvement Agent b-1]
In a 1000 ml stainless steel autoclave equipped with a stirrer and a temperature controller, 1 mol of glycerin PO adduct (number average molecular weight 5000, hydroxyl value 34.0), 3 mol of phthalic anhydride and alkali catalyst (N-ethylmorpholine) 0 0.020 mol was charged, and half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 3 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a strength improver (b-1). The measured values of (b-1) are as follows. Hydroxyl value (mgKOH / g) = 30.2, aromatic ring concentration (mmol / g) = 0.5

Production Example 7 [Production of Strength Improvement Agent b-2]
In an autoclave similar to Production Example 6, 1 mol of glycerin PO adduct (number average molecular weight 6000, hydroxyl value 28.0), 3 mol of phthalic anhydride and 0.020 mol of an alkali catalyst (N-ethylmorpholine) were charged. Half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 3 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a strength improver (b-2). The measured values of (b-2) are as follows. Hydroxyl value (mgKOH / g) = 25.6, aromatic ring concentration (mmol / g) = 0.5

Production Example 8 [Production of Strength Improvement Agent b-3]
In an autoclave similar to Production Example 6, 1 mol of glycerin PO adduct (number average molecular weight 6000, hydroxyl value 28.0), 3 mol of phthalic anhydride and 0.020 mol of an alkali catalyst (N-ethylmorpholine) were charged. Half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 3 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a strength improver (b-3). The measured values of (b-3) are as follows. Hydroxyl value (mgKOH / g) = 21.8, aromatic ring concentration (mmol / g) = 1.2

Production Example 9 [Production of Strength Improvement Agent b-4]
1 mol of glycerin PO adduct (number average molecular weight 5000, hydroxyl value 34.0), 1 mol of polyethylene glycol (number average molecular weight 200, hydroxyl value 561), trimellitic anhydride instead of 3 mol of phthalic anhydride and 3 mol of EO A strength improver b-4 was obtained in the same manner as in Production Example 6 except that 2 mol and 4 mol of EO were used. The measured values of (b-4) are as follows. Hydroxyl value (mgKOH / g) = 295.3, aromatic ring concentration (mmol / g) = 2.6

Production Example 10 [Production of Strength Improvement Agent b-5]
1 mol of glycerin PO adduct (number average molecular weight 5000, hydroxyl value 34.0), 1 mol of propylene glycol POEO adduct (number average molecular weight 900, hydroxyl value 124) instead of 3 mol of phthalic anhydride and 3 mol of EO, anhydrous A strength improver b-5 was obtained in the same manner as in Production Example 6 except that 2 mol of trimellitic acid and 4 mol of EO were used. The measured values of (b-5) are as follows. Hydroxyl value (mgKOH / g) = 152.8, aromatic ring concentration (mmol / g) = 1.5

Production Example 11 [Production of Strength Improvement Agent b-6]
Polytetramethylene glycol (PTMG-1000 manufactured by Mitsubishi Chemical Corporation; number average molecular weight 1000, hydroxyl value 112) is 1 in a reactor equipped with a stirrer, temperature controller, pressure controller, cooler, trap, and liquid circulation pump. Mole, 1 mol of trimellitic anhydride, 0.02 mol of N-ethylmorpholine as a catalyst, and 5 mol of toluene as a solvent were charged, and half-esterification was performed at 80 ± 10 ° C. and 0.1 MPa for 2 hours in a nitrogen atmosphere. Thereafter, 2 mol of benzyl chloride was added as an R1 constituent raw material and reacted for 6 hours while controlling to 95 ± 5 ° C. and 0.06 MPa. During the reaction, volatile toluene and water were condensed with a cooler, and toluene separated by the trap was returned to the reactor again. After the reaction, the catalyst and the solvent were distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver b-6. The measured values of (b-6) are as follows. Hydroxyl value (mgKOH / g) = 0, aromatic ring concentration (mmol / g) = 3.4

Production Example 12 [Production of Strength Improvement Agent b-7]
In an autoclave similar to Production Example 6, 1 mol of glycerin PO adduct (number average molecular weight 1500, hydroxyl value 112.0), 9 mol of phthalic anhydride and 0.020 mol of an alkali catalyst (N-ethylmorpholine) were charged. Half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 9 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After cooling to room temperature, charging with 3 mol of trimellitic anhydride and esterifying at 0.20 MPa and 120 ± 10 ° C. for 1 hour, 6 mol of EO is 120 ± 10 ° C. and the pressure is 0.5 MPa or less. While being controlled, the solution was dropped over 2 hours and then aged at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a strength improver (b-7). The measured values of (b-7) are as follows. Hydroxyl value (mgKOH / g) = 82.7, aromatic ring concentration (mmol / g) = 2.9.

Production Example 13 [Production of Strength Improvement Agent b-8]
In an autoclave similar to Production Example 6, 1 mol of glycerin PO adduct (number average molecular weight 6000, hydroxyl value 28.0), 1 mol of phthalic anhydride and 0.020 mol of an alkali catalyst (N-ethylmorpholine) were charged. Half esterification was performed by reacting at 0.20 MPa and 120 ± 10 ° C. for 1 hour in a nitrogen atmosphere. Thereafter, 1 mol of EO was added dropwise over 5 hours while controlling the pressure to be 120 ± 10 ° C. and a pressure of 0.50 MPa or less, followed by aging at 120 ± 10 ° C. for 1 hour. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a strength improver (b-8). The measured values of (b-8) are as follows. Hydroxyl value (mgKOH / g) = 27.2, aromatic ring concentration (mmol / g) = 0.2

  The analysis results of the strength improvers of Production Examples 6 to 13 are shown in Table 3.

In Table 3, the aromatic ring concentration (mmol / g) in the strength improver is defined by the following formula (6).
(Aromatic ring concentration in strength improver) = (Aromatic ring weight in strength improver) / (Aromatic ring molecular weight) / (Strength improver weight) (6)

<Examples 1 to 13 and Comparative Examples 1 to 4>
According to the foaming formulation shown in Table 4, a flexible polyurethane foam was foamed in a mold under the following foaming conditions to form a foam, then taken out of the mold and allowed to stand for a whole day and night, and various physical properties of the flexible polyurethane foam were measured. The measured values of physical properties are also shown in Table 4, respectively.

(Foaming conditions)
Mold size: 40cm x 40cm x 10cm (height)
Mold temperature: 65 ° C
Mold material: Aluminum Mixing method: High pressure urethane foaming machine (manufactured by Polymer Engineering) Mixing polyol premix and isocyanate at 15 MPa

  The raw materials of the flexible polyurethane foam in Examples 1 to 13 and Comparative Examples 1 to 4 are as follows.

1. Polyol Polyol (c-1): Polyoxyethylene polyoxypropylene polyol having an average number of functional groups of 3.0, a hydroxyl value of 28, and an EO unit content of 27%, obtained by randomly adding PO and EO to glycerin.
Polyol (c-2): Polyoxyethylene polyoxypropylene polyol having an average number of functional groups of 3.0, a hydroxyl value of 34, and an EO unit content of 20%, obtained by randomly adding PO and EO to glycerin.
Polyol (c-3): Polyoxyethylene polyoxypropylene polyol having an average functional group number of 3.0, a hydroxyl value of 24, and an EO unit content of 70%, obtained by randomly adding PO and EO to glycerin.
Polyol (c-4): glycerin, average functional group number 3.0, hydroxyl value 1829
Polymer polyol (c-5): In a polyoxyethylene polyoxypropylene polyol having an average functional group number of 3.0, a hydroxyl value of 34, and a total of EO units of 14% obtained by block addition of PO and EO to glycerin Polymer polyol (polymer content 30%) having a copolymerization of styrene and acrylonitrile (weight ratio: 30/70) hydroxyl value 24
2. Urethane catalyst (e)
Urethane catalyst (e-1): “TOYOCAT ET” manufactured by Tosoh Corporation (70% by weight dipropylene glycol solution of bis (dimethylaminoethyl) ether)
Urethane catalyst (e-2): “DABCO-33LV” (33% by weight dipropylene glycol solution of triethylenediamine) manufactured by Air Products Japan Co., Ltd.
3. Foaming agent (f)
3. Foaming agent (f): water Foam stabilizer (g)
Foam stabilizer (g): “TEGOSTAB B8737” manufactured by EVONIK
5. Isocyanate "CE-729" manufactured by Nippon Polyurethane Industry Co., Ltd. (TDI-80 (2,4- and 2,6-TDI, ratio of 2,4-isomer is 80% / crude MDI (average functional group number: 2. 9) = 80/20 (weight ratio))

-The measurement method and unit of foam physical properties are shown below.
Core density: Conforms to JIS K6400, unit is kg / m ³
Hardness (25% -ILD): Conforms to JIS K6400, unit is N / 314 cm ²
Tensile strength: Conforms to JIS K6400, unit is kgf / cm ²
Tear strength: Conforms to JIS K6400, unit is kgf / cm
Elongation: Conforms to JIS K6400, unit is%

・ Methods and units for testing vibration characteristics of foam properties are shown below.
Based on the test method of JASO B407, the resonance frequency (Hz) and the resonance magnification (times) at this time were evaluated to obtain vibration characteristics.

  In Table 4, the urethane foams of Examples 1 to 13 of the present invention have improved foam physical properties, particularly tensile strength, tear strength, and vibration characteristics, as compared with the urethane foams of Comparative Examples 1 to 3 obtained by the prior art.

  The flexible polyurethane foam of the present invention has better ride comfort and superior hardness foam strength than conventional ones. Therefore, it is useful as a high vibration absorbing cushion material for a vehicle seat. In addition, the flexible polyurethane foam obtained by the production method of the present invention can be widely used for other uses in which a flexible polyurethane foam is usually used. For details of the use, for example, “Nikkan Kogyo Shimbun,” "Polyurethane resin handbook", pages 191 to 195 (1987).

1: Reaction tank 2: Reaction tower 3: Distillation tower 4: Bottom line 5: Raw material supply line 6: Circulation line 7: Circulation line 8: Circulation line

Claims (11)

A polyol composition comprising the following polyol (a) and a strength improver (b), wherein the ethylene oxide unit content based on the weight of the polyol composition (PL) is 13 to 50% by weight Polyol composition for the production of polyurethane foam (PL).
Polyol (a): an alkylene oxide adduct of the active hydrogen-containing compound (H), wherein 40% or more of the hydroxyl groups located at the terminals are primary hydroxyl group-containing groups represented by the following general formula (I), A polyoxyalkylene polyol in which the valence x, the total degree of unsaturation y, and the ethylene oxide unit content z satisfy the relationship of formula (1).

[In General Formula (I), R ¹ represents a hydrogen atom or an alkyl group, cycloalkyl group, or phenyl group having 1 to 12 carbon atoms. The alkyl group, cycloalkyl group or phenyl group having 1 to 12 carbon atoms may be substituted with a halogen atom or an aryl group. ]
y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)
[In Formula (1), x represents the hydroxyl value represented by the unit mgKOH / g, and y represents the total degree of unsaturation represented by the unit meq / g. z is the ethylene oxide unit content based on the weight of (a), and is 0 to 50% by weight. ]
Strength improver (b): at least one compound selected from the group consisting of ester compounds, thioester compounds, phosphate ester compounds and amide compounds, which is an essential constituent component of a divalent or higher aromatic polyvalent carboxylic acid A compound. The polyol composition according to claim 1, wherein the content of the strength improver (b) is 0.1 to 30% by weight based on the weight of the polyol composition (PL). The polyol composition according to claim 1 or 2, wherein the polyol (a) is represented by the following general formula (II).

[In the general formula (II), R ² is an m-valent group obtained by removing m active hydrogens from the active hydrogen-containing compound (H); Z is represented by the following general formula (III) or (IV): It is a C2-C12 alkylene group or cycloalkylene group which may be substituted with a halogen atom or an aryl group. A is an alkylene group or cycloalkylene group having 3 to 12 carbon atoms which may be substituted with a halogen atom or an aryl group, represented by the following general formula (V) or (VI). When there are a plurality of Z or A, each may be the same or different; m is an integer of 2 to 100; p is an integer of 0 to 200, q is an integer of 1 to 200; r is an integer of 0 to 200 It is. ]

[In General Formulas (III) and (IV), R ³ represents a hydrogen atom, an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group which may be substituted with a halogen atom or an aryl group. In general formulas (V) and (VI), R ⁴ represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group or a phenyl group which may be substituted with a halogen atom or an aryl group. ] 4. The polyol composition according to claim 3, wherein 40% or more of the structure of A located at the terminal in the part of (AO) _{q in} the general formula (II) is a structure represented by the general formula (VI). . The polyol composition according to any one of claims 1 to 4, wherein x is 10 to 115 mgKOH / g. The polyol composition according to any one of claims 1 to 5, wherein 60% or more of the hydroxyl group-containing groups located at the terminals of the polyol (a) are primary hydroxyl group-containing groups represented by the general formula (I). The polyol composition according to any one of claims 1 to 6, further comprising a polyol (c) other than the polyol (a) and the strength improver (b). The polyol composition according to claim 7, wherein the polyol (c) is an active hydrogen-containing compound having a hydroxyl value (mgKOH / g) of 10 to 2000. Based on the weight of the polyol composition (PL), the content of the polyol (a) is 1 to 80% by weight, the content of the strength improver (b) is 0.1 to 50% by weight, and the polyol The polyol composition according to claim 7 or 8, wherein the content of (c) is 0.1 to 80% by weight. In the method for producing a polyurethane by reacting a polyol component and an isocyanate component, the polyol component contains 10 to 100% by weight of the polyol composition according to any one of claims 1 to 9 based on the weight of the polyol component. Manufacturing method. The cushion material for vehicle seats which consists of a flexible polyurethane foam obtained by the manufacturing method of Claim 10.

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