JP2013014658A - Polyol composition for producing polyurethane foam and method for producing polyurethane foam using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition solving such a problem that the polyurethane foam produced by using the conventional polyol is unsatisfactory in mechanical properties and moisture resistance.SOLUTION: The polyol composition (PL) for producing polyurethane foam contains a polyol (A) and a compound (B) having a cyclic structure in a main chain thereof. A method for producing polyurethane foam comprises a step of reacting a polyol component with an isocyanate component. The polyol composition (PL) is included by 10-100 wt.% based on the weight of the polyol component.

Description

  The present invention relates to a polyol composition that is suitable as a raw material for polyurethane foam and imparts excellent mechanical properties to polyurethane foam.

When producing a urethane foam with a specific polyol that satisfies the specific relationship between the average added mole number of ethylene oxide per active hydrogen and the primary OH conversion rate of the terminal hydroxyl group, good vibration characteristics 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 polyurethane foam produced using the conventional polyol has a problem that the mechanical properties and moisture resistance are insufficient.
An object of the present invention is to provide a polyol composition that solves these problems.

That is, the gist of the polyol composition (PL) for producing a polyurethane foam of the present invention comprises the polyol (A) and the compound (B) having a cyclic structure in the main chain.
The method for producing a polyurethane foam of the present invention is a method for producing a polyurethane foam by reacting a polyol component and an isocyanate component, wherein the polyol component contains the polyol composition (PL) in an amount of 10 to 10% by weight of the polyol component. The gist is to contain 100% by weight.

The polyurethane foam obtained using the polyol composition (PL) for producing the polyurethane foam of the present invention has the following effects.
(1) The polyurethane foam manufactured using the polyol composition (PL) for polyurethane foam production improves the mechanical properties of polyurethane and increases the hardness of the foam.

1 is a view showing a reaction apparatus of Production Example 1. FIG. It is a figure which shows the reaction apparatus of manufacture example 2 and 6. It is a figure which shows the reaction apparatus of manufacture example 3. FIG. 6 is a view showing a reaction apparatus of Production Example 4. FIG. It is a figure which shows the reaction apparatus of the manufacture example 17. FIG.

The polyol composition (PL) for producing a polyurethane foam in the present invention comprises the following polyol (A) and a compound (B) having a cyclic structure in the main chain.
Examples of the polyol (A) include an alkylene oxide 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 the alkylene oxide (hereinafter abbreviated as 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 referred to as PO). And 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.

  The number average functional group number of the polyol (A) is preferably 2 to 8, more preferably 2 to 6, and particularly preferably 3 to 4 from the viewpoint of foam formability. Even if the number of functional groups outside this range is included, the number average functional group number may be 2 to 8.

The hydroxyl value of the polyol (A) is preferably 20 to 1000 (mg KOH / g), more preferably 20 to 700, and particularly preferably 20 to 500 from the viewpoint of foam formability.
As the polyol (A), from the viewpoint of reactivity as a polyol component, it is an alkylene oxide adduct of the active hydrogen-containing compound (H), and 40% or more of the hydroxyl groups located at the terminals are represented by the following general formula (1). Polyoxyalkylene polyol (a), which is a primary hydroxyl group-containing group, is preferred.

[In General Formula (1), R ¹ represents a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, a cycloalkyl group, or a phenyl group. 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. ]

  In (a), the alkylene oxide adduct of the active hydrogen-containing compound (H) includes a polyoxyalkylene polyol represented by the following general formula (7).

In the general formula (7), R ²¹ is an s-valent group obtained by removing s active hydrogens from the active hydrogen-containing compound (H), s is the number of active hydrogens that (H) has, A number of 100.
From the viewpoint of properties such as the viscosity of (a), s is preferably 50 or less, and more preferably 10 or less.

  In the general formula (7), Z represents a C2-12 alkylene group represented by the following general formula (8) or (9). The alkylene group may be substituted with a halogen atom or an aryl group.

In general formulas (8) and (9), R ²² represents a hydrogen atom, or a C1-10 alkyl group, cycloalkyl group, or phenyl group. The alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group.

  Specific examples of Z include an ethylene group, a propylene group, a butylene group, a chloropropylene group, a phenylethylene group, and a combination of two or more thereof. Among these, properties such as the viscosity of (a) From the viewpoint, a propylene group, a butylene group, and an ethylene group are preferable. 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 (7), A represents a C3-12 alkylene group represented by the following general formula (10) or (11). The alkylene group may be substituted with a halogen atom or an aryl group.

In the general formula (10) and (11), R ²³ represents an alkyl group, a cycloalkyl group or a phenyl group C1-10. The alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group.

  Specific examples of A in the general formula (7) include a propylene group, a butylene group, a chloropropylene group, a phenylethylene 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 (7), 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 (7), 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 (7), 40% or more of the structure of A located at the terminal in the part of (AO) _{q in} the general formula (7) is represented by the general formula (11). The structure is preferable, more preferably 60% or more, and still more preferably 65% or more. Within this range, the moisture resistance of the urethane foam is good.

The polyol (a) is a primary hydroxyl group-containing group in which 40% or more of the hydroxyl groups located at the terminals are represented by the general formula (1).
For example, when (a) is represented by the above general formula (7), the hydroxyl group-containing group located at the end includes a primary hydroxyl group-containing group represented by the above general formula (1) and r = 0. Two types of secondary hydroxyl group-containing groups represented by the following general formula (12) can be considered, but (a) is a hydroxyl group located at the terminal regardless of the value of r in the general formula (7). 40% or more is the primary hydroxyl group-containing group represented by the general formula (1).
In (a), the ratio of the primary hydroxyl group-containing group represented by the general formula (1) to the total hydroxyl groups at the ends (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 the above general formula (1) represents a hydrogen atom or a C1-12 alkyl group, cycloalkyl group or phenyl group. The alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group.
R ²⁴ in the general formula (12) represents an alkyl group, a cycloalkyl group or a phenyl group C1-12. The 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 ²⁴ include groups other than a hydrogen atom among the groups exemplified for R ¹ .

In the present invention, the primary hydroxyl group ratio is measured and calculated by a ¹ H-NMR method after pre-treatment of the sample in advance.

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

<Calculation method of primary hydroxyl group ratio>
By the pretreatment method described above, the terminal hydroxyl group of the 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) preferably satisfies 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 ethylene oxide 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 the ethylene oxide 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 ethylene oxide 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 among the hydroxyl value x, the total unsaturation y, and the ethylene oxide 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 ethylene oxide 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 ethylene oxide 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 produced by a transfer reaction of alkylene oxide (especially propylene oxide) other than ethylene oxide in this production process. Therefore, the smaller the ethylene oxide content in the polyoxyalkylene polyol, the less the unsaturated group. The degree of saturation y tends to increase, and the degree of unsaturation y tends to increase as the molecular weight increases. Therefore, a polyoxyalkylene polyol having a small ethylene oxide 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 ethylene oxide content z. In addition, said Formula (1) and (3) represents the preferable range in which 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 composition (PL) for polyurethane foam production, for example, the required physical properties of the polyurethane foam to be produced, and is not particularly limited, but from the viewpoint of the physical properties of the polyurethane foam, 400-100,000 are preferable, Preferably it is 400-20,000.

  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 (13) can be produced by a generally known method. For example, a C2-12 alkylene oxide is opened to the active hydrogen-containing compound (H). It can manufacture by addition polymerization and the catalyst of this polymerization is not specifically limited.
The polyol (a) is obtained by ring-opening addition polymerization of C3-12 alkylene oxide to (J) in the presence of the catalyst (C) to obtain an active hydrogen compound (K) represented by the following general formula (14). Can be obtained. Moreover, you may carry out 0-50 weight% ring-opening addition polymerization of EO at the terminal of (K) as needed. 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 terminal of (K), (K) is (a). As described above, it is preferable that the hydroxyl value x and the total degree of unsaturation y of (a) obtained satisfy the relationship of Formula (1).

In the general formula (13), R ²¹ , Z, p, and s are the same as those in the general formula (7), and the above can be exemplified in the same manner.
In the general formula (14), R ²¹ , Z, A, p, q, and s are the same as those in the general formula (7), 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 a C2-12 alkylene oxide to the above-described 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 ethylene oxide adduct, ammonia propylene oxide adduct, water EO / PO copolymer adduct, water PO / butylene oxide copolymer adduct, glycerin EO / PO copolymer adduct, glycerin EO / butylene oxide copolymer adduct, glycerin PO / butylene oxide copolymer adduct, ammonia ethylene oxide / propylene oxide copolymer adduct, water EO / PO / butylene oxide co-adduct Polymerization adduct and copolymerization adduct of EO / PO / butylene oxide of glycerin, ammonia Copolymer adducts of EO · PO · butylene oxide.

Examples of the active hydrogen-containing compound (K) include compounds obtained by addition polymerization of C3-12 alkylene oxide 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 (C).
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. .

  The catalyst (C) is a compound represented by the following general formula (15-1), (15-2) or (15-3). Using this, ring-opening addition polymerization of C3-12 alkylene oxide 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 formulas (15-1), (15-2), and (15-3), X represents a boron atom or an aluminum atom, respectively. From the viewpoint of reactivity, a boron atom is preferable.

R ²⁵ in the general formula (15-1), (15-2) or (15-3) is represented by the (substituted) phenyl group represented by the following general formula (16) or the following general formula (17). that represents a tertiary alkyl group, if R ²⁵ is plural, R ²⁵ may each be the same or different.

Y in the general formula (16) represents a hydrogen atom, a C1-4 alkyl group, a halogen atom, a nitro group, or a cyano group, which 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, t represents the number of 0-5.
Specific examples of the phenyl group or substituted phenyl group represented by the general formula (16) 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 ²⁶ , R ²⁷ or R ^{28 in the} general formula (17) each independently represents 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 (17) include a t-butyl group and a t-pentyl group.

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

  In the presence of the catalyst (C), the alkylene oxide is added to the active hydrogen-containing compound (J) to obtain the active hydrogen compound (K). It is preferably 1 to 200 mol, more preferably 1 to 100 mol per active hydrogen of J), 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 (C) 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 the active hydrogen-containing compound (K) represented by the general formula (14) is obtained by adding alkylene oxide to the active hydrogen-containing compound (J) in the presence of the catalyst (C), the pressure is 0.1 MPa. It is preferable to continuously or intermittently remove the by-product low-boiling compound (t) having a boiling point of 150 ° C. or lower 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 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 the catalyst (C) may be charged together and reacted, or the active hydrogen-containing compound ( A) may be dropped to react with the mixture of J) and catalyst (C), or AO and the catalyst (C) may be dropped to react with the active hydrogen-containing compound (J). From the viewpoint of controlling the reaction temperature, AO is dropped into a mixture of the active hydrogen-containing compound (J) and the catalyst (C), or AO and the catalyst (C) are dropped into the active hydrogen-containing compound (J). Is preferred.

  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 polyol (a) produced by the above-exemplified method contains the catalyst (C), and the catalyst (C) is decomposed and / or removed as necessary depending on its 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. Furthermore, the thing of 1-5 micrometers is preferable.

  Even if the catalyst (C) remains in the polyol (a), the reactivity between the polyol and the 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 composition (PL) for producing polyurethane foam contains the polyol (A), it also contains the polymer polyol (W) obtained by polymerizing the vinyl monomer (g) in (A). It is.
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), the vinyl monomer (g) is polymerized in the presence of a radical polymerization initiator, and the obtained polymer (g) is stably dispersed. Specific examples of the polymerization method include those described in US Pat. No. 3,383,351 and Japanese Examined Patent Publication No. 39-25737. (G) is preferably styrene and / or acrylonitrile.

In the present invention, the compound (B) having a cyclic structure in the main chain is preferably at least one compound (b) selected from the following compounds (b1) to (b3) from the viewpoint of foam physical properties.
Compound (b1): A fluorene compound represented by the following general formula (2).
Compound (b2): a polyol having a structure represented by the following general formula (3) at both ends, and at least one of the repeating units constituting the structure being a ring structure represented by the following general formula (4) (B2-1) or at both ends each independently has a structure represented by the following general formula (5), and at least one of the repeating units constituting the structure is a ring structure represented by the following general formula (6) A certain polyol (b2-2).
Compound (b3): a polyol having a liquid crystalline skeleton in the molecule.

  The compound (b1) is a fluorene compound having at least a 9,9-bis [hydroxy or hydroxy (poly) alkoxy-phenyl] fluorene skeleton, and is a fluorene compound represented by the following general formula (2).

一般式（２）中、Ｒ²は置換基を示し、Ｒ³はアルキレン基を示し、Ｒ⁴は置換基を示し、ｍは０以上の整数、ｋは０〜４の整数、ｎは０〜４の整数を示す。）で表されるフルオレン化合物である。

In General Formula (2), R ² represents a substituent, R ³ represents an alkylene group, R ⁴ represents a substituent, m is an integer of 0 or more, k is an integer of 0 to 4, and n is 0 to 0. An integer of 4 is shown. The fluorene compound represented by this.

In the general formula (2), the substituent represented by the group R ² is a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.) or an alkyl group. Examples of the alkyl group include C1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group. In addition, when k is plural (two or more), the groups R ² may be different from each other or the same. In addition, the groups R ² substituted on the two benzene rings constituting the fluorene may be the same or different. Further, the bonding position (substitution position) of the group R ² with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

The alkylene group represented by the group R ³ is not particularly limited, and examples thereof include C2-10 alkylene groups (C2-C2 such as ethylene group, trimethylene group, propylene group, butane-1,2-diyl group and hexylene group). 6 alkylene group, preferably a C2-4 alkylene group, more preferably a C2-3 alkylene group), and the like, and an ethylene group is particularly preferable. The groups R ³ may be the same or different alkylene groups (that is, when m is plural, the groups R ³ may be the same or different). That is, when m is 2 or more, the polyalkoxy (polyoxyalkylene) group [— (OR ³ ) m—] may be composed of the same oxyalkylene group, and a plurality of oxyalkylene groups (for example, oxy Ethylene group and oxypropylene group). The groups R ³ may be the same alkylene group in the same benzene ring.

The number (added mole number) m of the oxyalkylene group (OR ³ ) may be an integer of 0 or more, and is preferably selected from a range of 1 or more [for example, about 1 to 15 (for example, 1 to 10)]. For example, 1-8 (for example, 1-6), preferably 1-4, more preferably 1-2, especially 1].

In addition, in the said General formula (2), the substitution position of group-[(OR < ³ >) _m- OH] substituted on a benzene ring is not specifically limited, Although it can select from 2-6 position of a phenyl group, 3 or The 4-position (particularly the 4-position) is preferred.

Examples of the substituent represented by the group R ⁴ include alkyl groups (C1-20 alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, s-butyl and t-butyl groups, preferably C1-8 alkyl group, more preferably C1-6 alkyl group), cycloalkyl group (C5-10 cycloalkyl group such as cyclopentyl group and cyclohexyl group, preferably C5-8 cycloalkyl group, more preferably C5-6 cycloalkyl groups), aryl groups (C6-10 aryl groups such as phenyl groups) and aralkyl groups (C6-10 aryl-C1-4 alkyl groups such as benzyl and phenethyl groups), etc. Hydrocarbon group; alkoxy group (methoxy group, ethoxy group, propoxy group, n-butoxy group, isobutoxy group, t-butoxy group, etc. 1-20 alkoxy groups, preferably C1-8 alkoxy groups, more preferably C1-6 alkoxy groups), cycloalkoxy groups (C5-10 cycloalkyloxy groups such as cyclohexyloxy groups), aryloxy groups ( Ether groups such as C6-10 aryloxy groups such as phenoxy groups), aralkyloxy groups (C6-10 aryl-C1-4 aralkyloxy groups such as benzyloxy groups); acyl groups (C1-6 such as acetyl groups) Acyl group); alkoxycarbonyl group (C1-4 alkoxycarbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom and chlorine atom etc.); nitro group; cyano group; substituted amino group (dialkylamino group etc.) It can be illustrated.

Preferred substituent R ⁴ is a hydrocarbon group [more preferably, an alkyl group (next more preferably a C1-6 alkyl group), a cycloalkyl group (more preferably a C5-8 cycloalkyl group), an aryl group A group (more preferably, a C6-10 aryl group), an aralkyl group (more preferably, a C6-8 aryl-C1-2 alkyl group) and the like] and an alkoxy group (more preferably a C1-4 alkoxy group). It is.

The substituent R ⁴ may be substituted alone or in combination of two or more in the benzene ring. Further, the substitution number n of the substituent R ⁴ may be 0 to 4, preferably 0 to 1, and more preferably 0.

Incidentally, the substitution position of R ⁴ be substituted on the benzene ring is not particularly limited, group - depending on the substitution position of _{^{[(OR 3) m -OH]}} , it can be appropriately selected.

  Specific examples of the compound represented by the general formula (2) include 9,9-bis (hydroxyphenyl) fluorene [a compound in which m is 0 in the formula (2), for example, 9,9-bis (4 9,9-bis (hydroxy-phenyl) fluorene such as -hydroxy-phenyl) fluorene], 9,9-bis (hydroxyalkoxy-phenyl) fluorene (a compound in which m is 1 in the formula (2)), 9-bis (hydroxy (poly) alkoxy-phenyl) fluorene (a compound in which m is 2 or more in the formula (2)) and the like are included.

  9,9-bis (hydroxyalkoxy-phenyl) fluorene includes 9,9-bis (hydroxyC2-4 alkoxy-phenyl) fluorene {9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene, 9,9-bis (hydroxy C2-4 alkoxy-phenyl) fluorene such as 9,9-bis [4- (2-hydroxypropoxy) phenyl] fluorene, and the like, preferably 9,9-bis [4- (2-hydroxyethoxy) phenyl) fluorene} and the like.

9,9-bis (hydroxy (poly) alkoxy-phenyl) fluorene corresponds to the 9,9-bis (hydroxyalkoxy-phenyl) fluorene, and m is 2 or more, for example, 9,9-bis (Hydroxydi C2-4 alkoxy-phenyl) fluorene {9,9-bis {4- [2- (2-hydroxyethoxy) ethoxy] -phenyl} fluorene, 9,9-bis {4- [2- (2 9,9-bis (hydroxydiC2-4alkoxy-phenyl) fluorene such as -hydroxypropoxy) propoxy] -phenyl} fluorene, preferably 9,9-bis [2- (2-hydroxyC2-3alkoxy) C2-3 alkoxy-phenyl] fluorene, more preferably 9,9-bis [2- (2-hydroxyC2-3 alkoxy) C2~3 alkoxy - include phenyl] fluorene} etc..
These fluorene compounds can be used alone or in combination of two or more.

  Although the manufacturing method of the said fluorene compound is not specifically limited, For example, as described in Japanese Patent No. 2559332, a method of reacting fluorenone with alcohol in the presence of an acid catalyst and thiols can be mentioned.

The compound (b2) is a polyol compound composed of a repeating unit having an alicyclic or heterocyclic skeleton having a specific structure.
Compound (b2): a polyol having a structure represented by the following general formula (3) at both ends, and at least one of the repeating units constituting the structure being a ring structure represented by the following general formula (4) (B2-1) or at both ends each independently has a structure represented by the following general formula (5), and at least one of the repeating units constituting the structure is a ring structure represented by the following general formula (6) A certain polyol (b2-2).

  Here, the polyol (b2-1) containing a repeating unit represented by the following general formula (4) is a carbon-carbon double bond of the polyol (b2-2) containing a repeating unit represented by the following general formula (6). It is hydrogenated.

Specific examples of R ^{5 to} R ¹² in the general formula (4) will be described below. The following general formula (18) is an example of (b2-1), and includes only both ends of general formula (3) and the repeating unit of general formula (4).

[In the formula, R ^{5 to} R ¹² are each independently a halogen atom, a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (two or more of R ^{5 to} R ¹² are linked. A cyano group, a hydroxyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a formyl group, a carboxyl group (an acid anhydride may be formed from two carboxyl groups) or silyl. Represents a group. u and v independently represent an integer of 0 to 5, and w is an arbitrary natural number. ]
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like. A ring having two or more of R ^{5 to} R ¹² linked to each other as an alkyl group, a cycloalkyl group such as cyclopentyl or cyclohexyl, an aryl group such as phenyl, tolyl, mesityl, or naphthyl; Substituents, that is, a 3 to 6-membered spiro ring in which R ⁵ and R ⁶ , R ⁷ and R ⁸ or R ⁹ and R ¹⁰ are linked, share the carbon atom represented by α and β in the general formula (20) And a substituted alkyl group such as hydroxymethyl, hydroxyethyl, chloromethyl, methoxymethyl, and acetoxymethyl.

Further, examples of R ^{5 to} R ¹² include cyano group; alkoxyl group such as methoxy, ethoxy, propoxy, isobutoxy, tert-butoxy; acyl group such as acetoxy, propionyloxy; formyl group; carboxyl group or its methyl, ethyl , Esters such as propyl, butyl and phenyl (alkoxycarbonyl group) or acid anhydrides formed from two carboxyl groups; silyl groups such as trimethylsilyl.

Of these R ^{5 to} R ^12, a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms are preferable, and a hydrogen atom or an alkyl group having 1 to 6 carbon atoms is more preferable. A in the general formula (4) is a hydrocarbon group having a substituent R ⁵ or R ⁶ or an oxygen atom, but is preferably a hydrocarbon group, and more preferably a methylene group.

Next, R ^{13 to} R ²⁰ in the general formula (6) will be specifically described below. The following general formula (19) is an example of (b2-2), and is composed of only both ends of the general formula (5) and the repeating unit of the general formula (6).

[Wherein, R ^{13 to} R ²⁰ are independently a halogen atom, a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ are respectively And independently of each other may be an alkylidene group, or two or more of R ^{13 to} R ²⁰ may be linked to form a ring.), Cyano group, hydroxyl group, alkoxyl group, alkoxycarbonyl group, acyl group , A formyl group, a carboxyl group (an acid anhydride may be formed from two carboxyl groups) or a silyl group. u and v independently represent an integer of 0 to 5, and w is an arbitrary natural number. ]
Examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Examples of the hydrocarbon group having 1 to 20 carbon atoms which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl, hexyl, octyl, decyl, dodecyl, octadecyl and the like. Alkyl groups, cyclocycloalkyl groups such as cyclopentyl and cyclohexyl, aryl groups such as phenyl, tolyl, xylyl, mesityl and naphthyl, and alkylidene groups independently formed from the respective groups of R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ As an alkylidene group such as methylene (= CH ₂ ), ethylidene, propylidene, isopropylidene, or a ring in which two or more of R ^{13 to} R ²⁰ are connected, a substituent bonded to one common carbon atom, R ¹³ and R ^14, R ¹⁵ and R ¹⁶ or R ¹⁷ and R ¹⁸ spiro ring of 3 to 6-membered ring linked, formula (2 ) Alpha in, 5-8 membered ring fused rings that share a carbon atom represented by beta, hydroxymethyl, hydroxyethyl, chloromethyl, methoxymethyl, and the like substituted alkyl groups such as acetoxymethyl is.

Further, examples of R ^{13 to} R ²⁰ include a cyano group; an alkoxyl group such as methoxy, ethoxy, propoxy, isobutoxy, tert-butoxy; an acyl group such as acetoxy, propionyloxy; a formyl group; a carboxyl group or a methyl group thereof, ethyl, Examples include esters (alkoxycarbonyl group) such as propyl, butyl, and phenyl, or acid anhydrides formed from two carboxyl groups; silyl groups such as trimethylsilyl. Of these R ^{13 to} R ^20, a hydrogen atom and a hydrocarbon group having 1 to 6 carbon atoms are preferable, and a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, or an alkylidene group is more preferable. A in the general formula (6) is a hydrocarbon group having a substituent R ¹³ or R ¹⁴ or an oxygen atom, but is preferably a hydrocarbon group, and more preferably a methylene group.

  The polyol (b2-2) (for example, the general formula (19)) is prepared by adding a cyclic unsaturated compound and functional groups (hydroxyl group, acyloxy group, etc.) at both ends by the method described in JP-A No. 2003-26752. It is produced by performing ring-opening polymerization from the chain unsaturated compound having a catalyst using a catalyst and, if necessary, converting the functional group to a hydroxyl group.

  The polyol (b2-1) having the general formula (4) as a repeating unit can be obtained by hydrogenating the polyol (b2-2) having the general formula (6) as a repeating unit in the main chain. In addition, after ring-opening polymerization to polyol (b2-2), when the functional groups at both ends of the chain unsaturated compound as a raw material are an acyloxy group and an aroyloxy group, after hydrogenating the ring-opening polymer Hydrolysis, saponification or transesterification can also be obtained as a polyol (b2-2).

  As a hydrogenation method of the polyol (b2-2), basically, all methods capable of hydrogenating a carbon-carbon double bond can be mentioned. For example, a stoichiometric method using a metal hydride, a metal hydrogen complex compound, a reagent such as borane or hydrazine, or a catalytic method using hydrogen is used. Among these methods, hydrogenation reaction using hydrogen and a catalyst is desirable from the viewpoints of economy and mass productivity. However, when it is necessary to leave a substituent such as an aldehyde or nitrile group without hydrogenation, a method of selectively hydrogenating only a carbon-carbon double bond is used instead of hydrogenation with hydrogen. There is a need.

As a hydrogenation catalyst for polyol (b2-2) with hydrogen gas, palladium, platinum, ruthenium, rhodium, etc. supported on activated carbon, alumina, silica, etc., Raney metal catalyst such as nickel, ruthenium, etc., palladium oxide, oxidation Metal oxide catalysts such as platinum, Ni (CH ₃ COCHCOCH ₃ ) ₂ / (C ₂ H ₅ ) ₃ Al, (C ₅ H ₅ ) ₂ TiCl ₂ / (C ₂ H ₅ ) ₂ AlCl, [(C ₆ H ₅ ) ₃ P] ₃ RhCl, [(C ₆ H ₅ ) ₃ P] ₃ RuCl ₂ , [(C ₆ H ₅ ) ₃ P] ₃ RuH ₂ , [(C ₆ H ₅ ) ₃ P] ₃ (CO) Homogeneous systems such as ruthenium and osmium metathesis catalysts used once in the ring-opening polymerization of norornenes to produce polyols (b2-2) such as RuCl ₂ and [(C ₆ H ₅ ) ₃ P] ₃ (CO) RuHCl Catalyst can be used .

  The compound (b3) is a polyol compound having a liquid crystalline skeleton in the molecule. For example, the liquid crystalline skeleton has a structure represented by the following general formulas (20) and (21).

In the general formulas (20) and (21), M represents a mesogenic group.
Specific examples of the mesogenic group represented by M include groups represented by the following general formulas (a) to (m).

In the general formulas (a) to (m), R ^{29 to} R ³² represent a halogen atom, an alkyl group, or an alkoxy group, preferably a halogen atom or an alkyl group. R ^{33 to} R ³⁴ represent a halogen atom, an alkyl group or an alkoxy group, and preferably an alkyl group. R ^{35 to} R ³⁷ represent a halogen atom, an alkyl group or an alkoxy group, preferably an alkyl group.
The halogen atom represented by R ^{29 to} R ³⁷ is preferably a fluorine atom, a chlorine atom or a bromine atom, particularly preferably a chlorine atom or a bromine atom.

The alkyl group represented by R ^{29 to} R ³⁷ may have a substituent, preferably has 1 to 12 carbon atoms, and particularly preferably has 1 to 6 carbon atoms.
The alkoxy group represented by R ^{29 to} R ³⁷ may have a substituent, preferably has 1 to 12 carbon atoms, and particularly preferably has 1 to 6 carbon atoms.

In the above formulas (a) to (m), a to d represent an integer of 0 to 2, preferably 0 or 1. ef represents an integer of 0 to 2, and is preferably 0. g to i represent an integer of 0 to 4, preferably 0.
In the above formulas (a) to (m), Y _{1 to} Y ₃ are a single bond, —CH═CH—, an ethenylene group, —COO—, —O · CO—, —CONH—, —NHCO—, —N = N-, -N (→ O) = N-, -CH = N- or -N = CH-, preferably a single bond, ethenylene, -COO-, -O.CO-, -CONH- or- NHCO-, particularly preferably a single bond, -COO- or -CONH-.

In the above formulas (a) to (m), Z ₁ is a single bond, —CH═CH—, ethenylene group, —COO—, —O · CO—, —CONH—, —NHCO—, —N═N—. , —N (→ O) ═N—, —CH═N— or —N═CH—, preferably a single bond, ethenylene, —COO—, —O · CO—, —CONH— or —NHCO—. And particularly preferably a single bond or an ethenylene group.
As described above, among the mesogenic groups represented by M, the groups represented by the above (a), (b), (c), (d) and (e) are preferable, and (a), (b ) And (c).

In General Formula (20), A ₁ and A ₂ represent an alkyl chain (CH ₂ ) _m (m represents an integer of 2 to 20).

In the general formula (21), A ₃ and A ₄ represent an alkyl chain (CH ₂ ) _n (n represents an integer of 2 to 5), and x and y represent an integer of 0 or more.

The content of the compound (B) based on the weight of the polyol composition (PL) is preferably 0.1 to 90% by weight, more preferably 0.5 to 80% by weight, from the viewpoint of tensile strength and elongation physical properties. Particularly preferred is 1 to 60% by weight. In the present invention, even when the polymer polyol to be used contains the compound (B), it is handled as the polyol composition (PL) containing the compound (B).
In addition, in this invention, what corresponds to a compound (B) shall be handled as a compound (B), and shall not be handled as a polyol (A).

  In the polyol composition (PL), the foaming agent (D) described later is preferably contained, and the content of (D) is based on the tensile strength and the total weight of the polyol (A) and the compound (B). From the viewpoint of elongation physical properties, 0.1 to 50 parts by weight is preferable, more preferably 1 to 45 parts by weight, next more preferably 1 to 40 parts by weight, particularly preferably 1 to 30 parts by weight, and most preferably 1 to 30 parts by weight. 25 parts by weight.

  The polyol composition (PL) for producing the polyurethane foam of the present invention only needs to contain the polyol (A) and the compound (B), and the production method is a method of mixing (A) and (B). Etc.

The polyol composition (PL) for producing a polyurethane foam of the present invention can be used for various applications, but is preferably used for producing a foamed or non-foamed polyurethane.
That is, when producing a foamed or non-foamed polyurethane 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 polyurethane foam using (PL) for the production of a polyurethane foam, in the method for producing a polyurethane foam by reacting a polyol component and an isocyanate component, the polyol component comprises the polyol composition (PL) as a polyol component. A method for producing a polyurethane foam containing 10 to 100% by weight based on the weight 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.

In the production of polyurethane foam, the reaction may be carried out in the presence of the additives described below (foaming agent (D), foam stabilizer, etc.) as necessary.
As the foaming agent (D), known foaming agents can be used, and examples thereof include water, hydrogen atom-containing halogenated hydrocarbons, low-boiling hydrocarbons, and liquefied carbon dioxide gas, and two or more of them 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.

The amount of the foaming agent (D) used is preferably 0.1 to 50 parts by weight, more preferably 1 to 45 parts by weight, and still more preferably 1 to 40 parts by weight, particularly preferably 1 with respect to 100 parts by weight of the polyol component. -30 parts by weight, most preferably 1-25 parts by weight.
When the foaming agent (D) is water, the amount of the foaming agent (D) used relative to 100 parts by weight of the polyol component is preferably 0.1 to 30 parts by weight, more preferably 1 to 20 parts by weight. The hydrogen atom-containing halogenated hydrocarbon is preferably 50 parts by weight or less, more preferably 10 to 45 parts by weight. The low boiling point hydrocarbon is preferably 40 parts by weight or less, more preferably 10 to 30 parts by weight. The liquefied carbon dioxide gas is preferably 30 parts by weight or less, more preferably 1 to 25 parts by weight.

  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.

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

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

  The content of the polyol composition (PL) for producing polyurethane foam in the polyol component is preferably from 10 to 100% by weight, more preferably from the viewpoint of the tensile strength of the polyurethane foam, based on the weight of the polyol component. Is 20 to 80% by weight, more 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. 1 mm) of reaction tower (2) (stainless steel cylindrical tube, inner diameter 5.5 cm, two lengths of 30 cm are used) and distillation tower (3) (theoretical plate number 30, stainless steel cylindrical tube, inner diameter 5) 0.5 cm, 2 m in length) were connected by circulation lines (6), (7), (8).
After charging 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane in the reaction tank (1), autoclave {reaction tank (1)}, reaction tower (2) and circulation The lines (6), (7), and (8) were depressurized to 0.005 MPa. While controlling PO so that the reaction temperature is maintained at 50 to 60 ° C. through the raw material supply line (5), the gas phase in the reaction tank (1) is reduced to 5 L / L using a diaphragm pump. At a flow rate of min, circulate in the order of reaction tank (1) → circulation line (6) → reaction tower (2) → circulation line (7) → distillation tower (3) → circulation line (8) → reaction tank (1). It was. 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 2000 ml, the PO is stopped, the gas phase circulation is terminated, the mixture is aged at 70 ° C. for 4 hours, 200 g of water is added, and 130 to 140 ° C. is added for 1 hour. Heated. After heating for 1 hour, the water was distilled off at atmospheric pressure over 2 hours, and then the remaining water was distilled off under reduced pressure over 3 hours while maintaining the pressure at 30 to 50 torr while passing steam. An adduct (a-1) was obtained.
The glycerin PO adduct used as a raw material was synthesized by a known method. That is, after adding a predetermined amount of propylene oxide to glycerin using potassium hydroxide as a catalyst, water and synthetic silicate were used for catalyst removal. (KYOWARD 600 manufactured by Kyowa Chemical Co., Ltd.) was added and subjected to heat treatment, followed by filtration and dehydration under reduced pressure.

Production Example 2 [Production of polyol a-2]
As in the embodiment shown in FIG. 2, a stainless steel autoclave as a reaction vessel (1) with a 2500 ml capacity stirring device, a temperature control device, a raw material supply line (5), and a distillation column (3) (theoretical plate number: 50 plates) And a stainless steel cylindrical tube having an inner diameter of 5.5 cm and a length of 3 m) were connected by circulation lines (6) and (8).
After charging 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane in the reaction tank (1), autoclave {reaction tank (1)}, reaction tower (2) and circulation The lines (6) and (8) were depressurized to 0.005 MPa. While controlling PO so that the reaction temperature is maintained at 50 to 60 ° C. through the raw material supply line (5), the gas phase in the reaction tank (1) is reduced to 5 L / L using a diaphragm pump. It was made to circulate in order of reaction tank (1)-> circulation line (6)-> distillation tower (3)-> circulation line (8)-> reaction tank (1) with the flow rate of min. By-product low-boiling compounds were separated from PO in the distillation column (3) and removed from the system. The separated by-product low-boiling compound was extracted from the bottom line (4) of the distillation column (3). When the amount of liquid in the autoclave {reactor (1)} reaches 2000 ml, the PO is stopped, the gas phase circulation is terminated, the mixture is aged at 70 ° C. for 4 hours, 200 g of water is added, and 130 to 140 ° C. is added for 1 hour. Heated. After heating for 1 hour, the water was distilled off at atmospheric pressure over 2 hours, and then the remaining water was distilled off under reduced pressure over 3 hours while maintaining the pressure at 30 to 50 torr while passing steam. An adduct (a-2) was obtained.
The PO product of glycerin used as a raw material was the same as in Production Example 1.

Production Example 3 [Production of polyol a-3]
As in the embodiment shown in FIG. 3, a stainless steel autoclave as a reaction tank (1) with a 2500 ml stirring device, a temperature control device, a raw material supply line (5), and an adsorption tower packed with 500 parts of molecular sieve 4A ( 9) (Stainless steel cylindrical tube, inner diameter 5.5 cm, length 30 cm) were connected by circulation lines (6) and (8).
After charging 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane, autoclave {reaction vessel (1)}, adsorption tower (9) and lines (6), (8) The inside was depressurized to 0.005 MPa. While continuously feeding PO through the raw material supply line (5) while maintaining the reaction temperature at 50 to 60 ° C., the flow rate of the gas phase in the reaction tank (1) is 5 L / min using a diaphragm pump. Then, it was made to circulate in order of reaction tank (1)-> decompression line (6)-> adsorption tower (9)-> circulation line (8)-> reaction tank (1). While controlling the adsorption tower (9) to 25 ° C. and 0.1 to 0.3 MPa, the by-product low boiling point compound was continuously adsorbed on the molecular sieve and removed out of the system. When the amount of liquid in the autoclave {reactor (1)} reaches 2000 ml, the PO is stopped, the gas phase circulation is terminated, the mixture is aged at 70 ° C. for 4 hours, 200 g of water is added, and 130 to 140 ° C. is added for 1 hour. Heated. After heating for 1 hour, the water was distilled off at atmospheric pressure over 2 hours, and then the remaining water was distilled off under reduced pressure over 3 hours while maintaining the pressure at 30 to 50 torr while passing steam. An adduct (a-3) was obtained.
The PO product of glycerin used as a raw material was the same as in Production Example 1.

Production Example 4 [Production of polyol a-4]
As in the embodiment shown in FIG. 4, the vacuum line (10) was connected to 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). After charging 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane in an autoclave {reaction tank (1)}, the reaction temperature of PO is reduced through the raw material supply line (5). It added, controlling so that 50-60 degreeC might be maintained. However, PO was charged over 10 minutes, and then the pressure was reduced (0.01 MPa) from the pressure reduction line (10), and the process of distilling off the low-boiling volatile components for 15 minutes was repeated 20 times. When the autoclave {reaction vessel (1)} was charged until the amount of the solution in the autoclave {reactor (1)} reached 2000 ml, the PO was stopped and aged at 70 ° C. for 4 hours. After heating for 1 hour, the water was distilled off at atmospheric pressure over 2 hours, and then the remaining water was distilled off under reduced pressure over 3 hours while maintaining the pressure at 30 to 50 torr while passing steam. An adduct (a-4) was obtained.
The PO product of glycerin used as a raw material was the same as in Production Example 1.

Production Example 5 [Production of polyol a-5]
Instead of using 400 g of glycerin PO adduct (hydroxyl value 280), except that 666 g of glycerin PO adduct (hydroxyl value 168) is used, it was synthesized in the same manner as in Production Example 1, and a liquid glycerin PO adduct ( a-5) was obtained.
The glycerin PO adduct (hydroxyl value 168) used as a raw material was synthesized by a known method, that is, after adding a predetermined amount of propylene oxide to glycerin using potassium hydroxide as a catalyst, Water and synthetic silicate (KYOWARD 600 manufactured by Kyowa Chemical Co., Ltd.) are added, heat-treated, filtered and dehydrated under reduced pressure.

Production Example 6 [Production of polyol a-6]
As in the embodiment shown in FIG. 2, a stainless steel autoclave as a reaction vessel (1) with a 2500 ml capacity stirring device, a temperature control device, and 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 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane in the reaction tank (1), autoclave {reaction tank (1)}, reaction tower (2) and circulation The lines (6), (7), and (8) were depressurized 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 {reaction vessel (1)} reaches 1920 ml, PO charging is stopped, gas phase circulation is terminated, aging is performed 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, 80 g of EO was added through the raw material supply line (5) over 2 hours while controlling the reaction temperature to be maintained at 130 to 140 ° C., 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 then dehydrated under reduced pressure to obtain a liquid glycerin POEO adduct (a-6).
The PO product of glycerin used as a raw material was the same as in Production Example 1.

Production Example 7 [Production of polyol a-7]
A liquid glycerin POEO adduct (synthesized in the same manner as in Production Example 6 except that 666 g of glycerin PO adduct (hydroxyl value 168) was used instead of 400 g of glycerin PO adduct (hydroxyl value 280). a-7) was obtained.
The glycerin PO adduct used as a raw material was the same as in Production Example 5.

Production Example 8 [Production of polyol a-8]
Instead of using 400 g of the glycerin PO adduct (hydroxyl value 280), 267 g of the pentaerythritol PO adduct (hydroxyl value 280) was used, and when the amount of liquid in the autoclave {reaction vessel (1)} reached 1920 ml. Instead of “stopping PO charging”, “stop PO charging when the amount of liquid in the autoclave {reactor (1)} reaches 1840 ml”, and “EO 160 g” instead of “EO 80 g”. Except for this, it was synthesized in the same manner as in Production Example 6 to obtain a liquid pentaerythritol POEO adduct (a-8).
The pentaerythritol PO adduct (hydroxyl value 280) was synthesized by a known method. That is, after adding a predetermined amount of propylene oxide to propylene glycol using potassium hydroxide as a catalyst, it was synthesized with water to remove the catalyst. A silicate (KYOWARD 600 manufactured by Kyowa Chemical Co., Ltd.) is added and subjected to heat treatment, followed by filtration and dehydration under reduced pressure.

Production Example 9 [Production of polyol a-9]
Liquid pentaerythritol was synthesized in the same manner as in Production Example 8 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-9) was obtained.
Pentaerythritol PO adduct (hydroxyl value 160) was synthesized by a known method, that is, a predetermined amount of propylene oxide was added to propylene glycol using potassium hydroxide as a catalyst, and then synthesized with water to remove the catalyst. A silicate (KYOWARD 600 manufactured by Kyowa Chemical Co., Ltd.) is added and subjected to heat treatment, followed by filtration and dehydration under reduced pressure.

Production Example 10 [Production of polyol a-10]
Liquid pentaerythritol was synthesized in the same manner as in Production Example 8 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-10) was obtained.

Production Example 11 [Production of polyol a-11]
A liquid pentaerythritol POEO was synthesized in the same manner as in Production Example 10 except that 350 g of pentaerythritol PO adduct (hydroxyl value 160) was used instead of 200 g of pentaerythritol PO adduct (hydroxyl value 280). An adduct (a-11) was obtained.
The same product as in Production Example 9 was used as the PO adduct of pentaerythritol (hydroxyl value 160).

Production Example 12 [Production of polyol n-1]
As in the embodiment shown in FIG. 5, 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).

Production Example 13 [Production of polyol n-2]
A glycerin PO adduct (n-2) was obtained in the same manner as in Production Example 12 except that 72 g of propylene glycol was used instead of 61 g of glycerin.

The analysis results of the polyoxyalkylene polyols of Production Examples 1 to 11 are shown in Table 1.
The verification result about Formula 1 (following, Formula (4)) of the patent document (patent 3688667 gazette) which is a prior art 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 y, the mathematical expression (4 ′) is obtained.
y ≦ 60 × x− ² (4 ′)

  The primary hydroxyl group ratio (1) in Table 1 is the primary hydroxyl group ratio in the structure represented by the general formula (VI) (before EO addition), and the primary hydroxyl group ratio (2) is the primary polyol group. It is a hydroxyl group ratio.

  The analysis results of the polyoxyalkylene polyols of Production Examples 12 to 13 are shown in Table 2. The verification results for the above formula (4) are also described.

  The primary hydroxyl group ratio (2) in Table 2 is the primary hydroxyl group ratio of the polyol.

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 14 [Compound b1-1]
Compound b1-1 [9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene] was purchased from Tokyo Chemical Industry Co., Ltd. and used as it was. Hydroxyl value (mgKOH / g) = 256.3.

Production Example 15 [Production of Compound b1-2]
In a 1 L separable flask, 18 g of 9-fluorenone (0.1 mol, manufactured by Nacalai Tesque), o-phenylphenol (2-hydroxyethyl) ether [or 2-biphenylyl- (2-hydroxyethyl) ether] 64 .3 g (0.3 mol, manufactured by Meisei Chemical Co., Ltd.), 0.9 g of 3-mercaptopropionic acid and 52 g of xylene as a solvent were added, and the mixture was heated to 60 ° C. and completely dissolved. Thereafter, 20 g of sulfuric acid was gradually added, and the mixture was maintained at 60 ° C. and stirred for 5 hours. It was confirmed by HPLC that the conversion of 9-fluorenone was 99% or more. The obtained reaction solution was neutralized with 48% caustic soda water, washed several times with distilled water, and cooled to precipitate crystals. Further filtration and drying were performed to obtain 51 g of compound b1-2 [9,9-bis [4- (2-hydroxyethoxy) -3-phenylphenyl] fluorene]. Hydroxyl value (mgKOH / g) = 190.3.

Production Example 16 [Production of Compound b1-3]
In a 1000 ml stirrer and a temperature control device stainless steel autoclave, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene 0.1 mol (43.7 g) and alkali catalyst (N-ethylmorpholine) After charging 0.0020 mol, 0.8 mol of EO was added dropwise over 3 hours while controlling the pressure to be 80 ± 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 compound (b1-3). Hydroxyl value (mg KOH / g) = 213.3.

Production Example 17 [Production of Compound b2-1]
A 50 ml three-necked flask equipped with a condenser and a dropping funnel was purged with nitrogen, and 5.16 g (30 mmol) of 1,4-diacetoxy-2-butene and 10 ml of toluene were added. To this, 0.06 g (0.07 mmol) of the catalyst (Cl ₂ [P (C ₆ H ₁₁ ) ₃ ] ₂ Ru═CH—C ₆ H ₅ ) was dissolved and stirred with a mechanical stirrer. The flask was attached to an oil bath, the bath temperature was raised to 40 ° C., and a solution prepared by dissolving 9.0 g (75 mmol) of ethylidene norbornene separately prepared in 10 ml of toluene was dropped from the dropping funnel over 1 hour. After completion of dropping, the reaction was carried out at 40 ° C. for 2 hours. The solution after the reaction was cooled to room temperature. This reaction solution and 0.03 g of the catalyst (HClRu (CO) [P (C ₆ H ₅ ) ₃ ] ₃ ) are placed in a 100 ml stainless steel autoclave and subjected to a hydrogenation reaction at a hydrogen pressure of 6 MPa and a temperature of 155 ° C. for 4 hours with stirring. went. After completion of the reaction, the reaction solution was cooled, and this reaction solution was dropped into 200 ml of methanol to precipitate a solid content. This solid content was dissolved in 20 ml toluene and dropped into 200 ml of methanol to precipitate the solid content, which was repeatedly purified three times. The purified solid was vacuum dried. It was a slightly viscous yellowish transparent viscous solid.
When GPC of this solid substance was measured, Mn in terms of polystyrene was 4700, and Mw / Mn was 2.4.
The hydrogenation rate was 99% from the integration ratio of each peak in proton NMR measurement. The molecular weight Mn calculated from the results of proton NMR was 3600.
Moreover, the molecular weight Mn measured by the vapor pressure osmosis method was 3500, which was in good agreement with the molecular weight measured by proton NMR. From this result, it was found that the compound produced had an acetoxyl group introduced at both ends. Next, the ester moieties at both ends were converted to diols by transesterification. The viscous solid (total amount other than that used for analysis) was dissolved in 30 ml of toluene, and 1 g of 28% sodium methoxide / methanol solution and 10 ml of methanol were added and refluxed for 5 hours. The solution after completion of the reaction was poured into 100 ml of methanol and decanted. Further, the operation of dissolving in cyclohexane and adding methanol to cause precipitation was repeated three times. The solid was vacuum dried at 75 ° C. for 2 days. A soft solid was obtained.
From the result of proton NMR, it was confirmed that the acetoxyl group was transesterified and 100% hydroxylated. The molecular weight calculated from proton NMR was 3,500. This substance was designated as compound (b2-1). Hydroxyl value (mgKOH / g) = 32.3.

Production Example 18 [Production of Compound b3-1]
Sodium hydroxide (5.6 g, 0.140 mol) was dissolved in ethanol (80 ml) and 4,4′-biphenol (6.5 g, 0.035 mol) was added with stirring. After refluxing for 1 hour, 8-bromo-1-octanol (29.3 g, 0.140 mol) was slowly dropped from the dropping funnel, and the reaction mixture was refluxed with stirring for 24 hours. After completion of the reaction, the contents were cooled and placed in water to form a precipitate, which was filtered and washed with water. The crude product was purified by recrystallization from ethanol and DMF (3: 1) three times to obtain compound (b3-1). Hydroxyl value (mgKOH / g) = 253.5.

Production Example 19 [Production of Compound b3-2]
To a 2 L three-necked flask, 54.45 g (0.406 mol) of terephthalaldehyde, 100 g (0.812 mol) of 4-amino-m-cresol, 800 ml of ethanol, and 1 g of zinc chloride as a catalyst were added. Thereafter, a cooling tube was attached and reacted at 80 ° C. for 5 hours. The obtained reaction product was subjected to suction filtration, and the yellow crystals remaining on the filter paper were washed 5 times with 20 g of ethanol, followed by ¹ H-NMR measurement, and terephthalylidene-bis- (4-amino-3-methylphenol). It was confirmed. The yield was 85%.
Next, 0.1 mol (34.4 g) of the obtained terephthalylidene-bis- (4-amino-3-methylphenol) and an alkali catalyst (N-ethyl) were added to a 1000 ml stirring device and a stainless steel autoclave of a temperature control device. (Morpholine) After charging 0.0020 mol, 0.8 mol of EO was added dropwise over 3 hours while controlling the pressure to be 80 ± 10 ° C. and a pressure of 0.50 MPa or less, and then aged at 120 ± 10 ° C. for 1 hour. did. After completion of aging, the alkali catalyst was removed under reduced pressure at 0.1 MPa for 1 hour to obtain a compound (b3-2). Hydroxyl value (mgKOH / g) = 161.0.

Production Example 20 [Production of Compound b3-3]
Synthesis of 4,4′-di (3-methyl-4-hydroxyphenyl) bicyclohexene-3;
24,4,4 ′, 4′-tetra (3-methyl-4-hydroxyphenyl) bicyclohexane (235.5 g), tetraethylene glycol (256.9 g) and 48% aqueous sodium hydroxide solution (2.7 g) were added to a reaction vessel (1 L capacity 4 The reaction vessel was purged with nitrogen and the pressure inside the reaction vessel was reduced to about 3 Kpa, and a thermal decomposition reaction was carried out at a temperature of 198 ° C. for 2 hours and 30 minutes.
After completion of the reaction, 128 g of pure water and 50% aqueous acetic acid solution were added to the resulting reaction mixture to neutralize it to about PH6 to obtain a slurry.
202 g of methanol was added to the above slurry obtained in this way for crystallization, followed by filtration to obtain 67.4 g of a pale red yellow solid.
Next, 67.4 g of the obtained light red-yellow solid and 277 g of water were charged into a 500 ml four-necked flask and purged with nitrogen. After stirring at a temperature of 82 ° C. for 2 hours, the slurry was cooled, filtered, Drying was performed to obtain 49.5 g of 4,4′-di (3-methyl-4-hydroxyphenyl) bicyclohexene-3 having a purity of 98.0% (according to high performance liquid chromatography analysis) as a pale yellowish white solid. .
80.0 g of 4,4′-di (3-methyl-4-hydroxyphenyl) bicyclohexene-3 obtained above, 8.0 g of 5% carbon-supported palladium catalyst (product with a water content of 50%), α -202.3 g of methylstyrene and 160.0 g of tetraethylene glycol were charged into a reaction vessel (a 3 L four-necked flask), the inside of the reaction vessel was purged with nitrogen, the temperature was raised, and the temperature was about 160 ° C for 6 hours. A dehydrogenation reaction was performed. After completion of the reaction, 1147 g of dimethylformamide was added to the reaction mixture and filtered at 67 ° C., and the catalyst was gradually added. Then, the catalyst-filtered solution was cooled to 20 ° C., and the precipitated crystals were filtered and dried to obtain 3,3 ′ ″-dimethyl-4, having a purity of 98.9% (according to high performance liquid chromatography analysis). 52.9 g of 4 ′ ″-dihydroxy-P-quaterphenyl was obtained as a pale yellow white solid.
Next, the obtained 3,3 ′ ″-dimethyl-4,4 ″ ′-dihydroxy-P-quaterphenyl 0.1 mol (36.8 g) was added to a stainless steel autoclave with a 1000 ml stirring device and a temperature control device. ) And an alkali catalyst (N-ethylmorpholine) 0.0020 mol, and then dropwise added over 3 hours while controlling 0.8 mol of EO at 80 ± 10 ° C. and a pressure of 0.50 MPa or less, Aging was performed 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 compound (b3-3). Hydroxyl value (mgKOH / g) = 155.7.

Production Example 21 [Production of Strength Improvement Agent f-1]
In a stainless steel autoclave with a 1000 ml stirring device and temperature controller, polyethylene glycol (PEG-200 manufactured by Sanyo Chemical Industries, Ltd .; number average molecular weight 200, hydroxyl value 560) is 1 mol, trimellitic anhydride 2 mol, N as a catalyst -Ethylmorpholine 0.02 mol, THF 2 mol as a solvent was charged, and half esterification was performed at 80 ± 10 ° C for 2 hours under nitrogen atmosphere. Thereafter, 4 mol of EO was added dropwise over 2 hours while controlling to 80 ± 10 ° C. and 0.5 MPa or less, followed by aging for 3 hours. After aging, the catalyst and the solvent were distilled off at 80 ± 10 ° C. and 10 kPa to obtain a strength improver (f-1). The measured values of (f-1) are as follows. Hydroxyl value (mgKOH / g) = 295.3, aromatic ring concentration (mmol / g) = 2.6.

<Examples 1-29 and Comparative Examples 1-2>
In accordance with the foaming formulation shown in Tables 3 to 5, polyurethane slab foam was foamed under the following foaming conditions, and after standing overnight, various properties of the polyurethane slab foam were measured. The measured values of physical properties are also shown in Tables 3 to 5, respectively.

(Foaming conditions)
BOX SIZE: 30cm x 30cm x 30cm Empty box Material: Wood Mixing method: Hand mixing

The raw materials of the polyurethane slab foam in the examples and comparative examples are as follows.
1. Urethane catalyst (c)
Urethane catalyst (c-1): “Neostan U-28” (Stanus octoate) manufactured by Nitto Kasei Co., Ltd.
Urethane catalyst (c-2): “TOYOCAT ET” manufactured by Tosoh Corporation (70% by weight dipropylene glycol solution of bis (dimethylaminoethyl) ether)
2. Foaming agent (d)
2. Foaming agent (d-1): water Foam stabilizer (e)
Foam stabilizer (e-1): “L-540” manufactured by Toray Dow Corning Co., Ltd.
4). Isocyanate TDI: “Coronate T-80” (tolylene diisocyanate) manufactured by Nippon Polyurethane Industry Co., Ltd.

-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
Elongation: Conforms to JIS K6400, unit is%
Tear strength: Conforms to JIS K6400, unit is kgf / cm
Compression residual strain ratio: Conforms to JIS K6400, unit is%
Humid heat compression residual strain ratio: Conforms to JIS K6400, unit is%

  In Tables 3-5, the urethane foams of Examples 1 to 29 of the present invention have improved foam physical properties, particularly foam hardness, tensile strength, tear strength, and elongation, compared to the urethane foams of Comparative Examples 1 and 2 obtained by the prior art. To do.

<Examples 30 to 44, Comparative Examples 3 to 4>
In accordance with the foaming formulation shown in Tables 6 to 7, the 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 overnight, and various physical properties of the flexible polyurethane foam were measured. The measured values of physical properties are also shown in Tables 6 to 7, 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 foams in Examples 30 to 44 and Comparative Examples 3 to 4 are the same as those shown in Examples and Comparative Examples of polyurethane slab foams, and other items are as follows.
1. Urethane catalyst (c)
Urethane catalyst (c-3): “DABCO-33LV” (33% by weight dipropylene glycol solution of triethylenediamine) manufactured by Air Products Japan Co., Ltd.
2. Foam stabilizer (e)
Foam stabilizer (e-2): “TEGOSTAB B8737” manufactured by EVONIK
3. Isocyanate 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))

4). Polyol (p)
Polymer polyol (p-1): 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
Polyol (p-2): Polyoxyethylene polyoxypropylene polyol polyol having an average number of functional groups of 3.0 obtained by randomly adding PO and EO to glycerin, a hydroxyl value of 24, and a total of EO units = 72% (p- 3): Polyoxypropylene polyol having an average functional group number of 6.0 and a hydroxyl value of 490 obtained by adding PO to sorbitol Polyol (p-4): Glycerin, average functional group number of 3.0, hydroxyl value of 1829

-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
Elongation: Conforms to JIS K6400, unit is%
Tear strength: Conforms to JIS K6400, unit is kgf / cm
Rebound resilience: Conforms to JIS K6400, unit is%
Compression residual strain ratio: Conforms to JIS K6400, unit is%
Humid heat compression residual strain ratio: Conforms to JIS K6400, unit is%

  In Tables 6 to 7, the urethane foams of Examples 30 to 43 of the present invention have improved foam physical properties, particularly tensile strength, tear strength, and elongation, as compared with the urethane foams of Comparative Examples 3 to 4 obtained by the prior art.

<Examples 45-58, Comparative Examples 5-6>
According to the foaming formulations shown in Tables 8 to 9, a rigid polyurethane foam was foamed in a mold under the following foaming conditions to form a foam, and left for a day and night after demolding, and various physical properties of the rigid polyurethane foam were measured. The measured values of physical properties are also shown in Tables 8-9.

(Foaming conditions)
Mold size: 40cm x 40cm x 5cm (height)
Mold temperature: 35 ℃
Mold material: Aluminum Mixing method: High pressure urethane foaming machine (manufactured by Polymer Engineering Co., Ltd.) Mixing polyol premix and isocyanate at 12 MPa

The raw materials of the rigid polyurethane foams in Examples 45 to 58 and Comparative Examples 5 to 6 are the same as those shown in the above Examples, and the other items are as follows.
1. Urethane catalyst Urethane catalyst (c-4): “U-CAT 1000” (amine-based catalyst) manufactured by San Apro Co., Ltd.
2. Blowing agent Blowing agent (d-1): Water blowing agent (d-2): “HFC-245fa” (1,1,1,3,3-pentafluoropropane) manufactured by Central Glass Co., Ltd.
3. Foam stabilizer (e-3): “SF-2936F” manufactured by Toray Dow Corning Co., Ltd.
4). Flame retardant Flame retardant (g-1): “TMCPP” manufactured by Daihachi Chemical Industry Co., Ltd. (Tris (β-chloropropyl phosphate 5. Isocyanate Japan Polyurethane Industry Co., Ltd. “Millionate MR-200”) )
6). Polyol polyol (p-7): Polyoxypropylene polyol having an average functional group number of 8.0 and a hydroxyl value of 490, obtained by adding PO to sucrose

The measurement method for each item is as follows. The obtained results are shown in Tables 8-9.
Density: Conforms to JIS A9511, unit is kg / m ³
Compressive strength: Conforms to JIS A9511, unit is kPa

  In Tables 8-9, the urethane foams of Examples 45-58 of the present invention have improved foam physical properties, particularly compressive strength, as compared with the urethane foams of Comparative Examples 5-6 obtained by conventional techniques.

The polyurethane obtained by using the polyol of the present invention can be used in various applications such as foams, elastomers and coating materials. Examples of the foam include automotive cushion materials, sound-absorbing and sound-insulating materials, and handles, elastomers include cast potting materials, and coating materials include adhesives and paints.
The polyurethane foam and polyurethane elastomer using the polyol of the present invention are generally excellent in resin physical properties (tensile strength, hardness, elongation at break) as compared with the case of using the polyol obtained by the prior art.
Therefore, the polyurethane resin of the present invention can be widely used as an adhesive, a sealing material, a coating material, a heat insulating material, a synthetic wood and the like.
Among the polyurethane foam resins of the present invention, the flexible polyurethane foam is superior in hardness, foam strength, and elongation physical properties as compared with conventional products. Therefore, the foamed polyurethane resin of the present invention, particularly the flexible polyurethane foam, can be widely used for cushion materials, shock absorbers, cushioning materials, sound insulation materials, and the like.

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 9: Adsorption tower 10: Decompression line

Claims (11)

A polyol composition (PL) for producing a polyurethane foam comprising a polyol (A) and a compound (B) having a cyclic structure in the main chain. The polyol for producing a polyurethane foam according to claim 1, wherein the compound (B) is at least one compound (b) selected from the following compounds (b1) to (b3).
Compound (b1): A fluorene compound represented by the following general formula (2).

[In general formula (2), R ² is a cyano group, a halogen atom or an alkyl group, R ³ is an alkylene group, R ⁴ is a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryl group, an aryloxy group, an aralkyloxy group. Represents an acyl group, an alkoxycarbonyl group, a halogen atom, a nitro group, a cyano group or a substituted amino group. A plurality of R ^{2 to} R ⁴ may be the same or different. m represents an integer of 0 or more, k represents an integer of 0 to 4, and n represents an integer of 0 to 4]
Compound (b2): a polyol having a structure represented by the following general formula (3) at both ends, and at least one of the repeating units constituting the structure being a ring structure represented by the following general formula (4) (B2-1) or at both ends each independently has a structure represented by the following general formula (5), and at least one of the repeating units constituting the structure is a ring structure represented by the following general formula (6) A certain polyol (b2-2).

[In General Formula (3), i and j independently represent an integer of 0 to 5]

[In General Formula (4), R ^{5 to} R ¹² are each independently a halogen atom, a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (2 of R ^{5 to} R ¹² . Two or more may be linked to form a ring.), A cyano group, a hydroxyl group, an alkoxyl group, an alkoxycarbonyl group, an acyl group, a formyl group, a carboxyl group (an acid anhydride may be formed from two carboxyl groups) Or a silyl group. ]

[In General Formula (5), i and j independently represent an integer of 0 to 5]

[In General Formula (6), R ^{13 to} R ²⁰ are each independently a halogen atom, a hydrogen atom, or a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (R ¹⁵ and R ¹⁶ , R ¹⁷ and R ¹⁸ may be independently an alkylidene group in each group, or two or more of R ^{13 to} R ²⁰ may be linked to form a ring.), Cyano group, hydroxyl group, alkoxyl group, alkoxycarbonyl A group, an acyl group, a formyl group, a carboxyl group (an acid anhydride may be formed from two carboxyl groups) or a silyl group. ]
Compound (b3): a polyol having a liquid crystalline skeleton in the molecule. The polyol (A) has a number average functional group number of 2 to 8, a hydroxyl value of 20 to 1000 (mgKOH / g), and a polyol composition (PL) for producing polyurethane foam has a hydroxyl value of 20 to 1000 (mgKOH / g). The polyol composition for producing a polyurethane foam according to claim 1 or 2, which is g). The polyol composition for producing polyurethane foam according to any one of claims 1 to 3, comprising 0.1 to 50 parts by weight of the foaming agent (D) with respect to the total weight of the polyol (A) and the compound (B). object. Polyol (A) is an alkylene oxide adduct of an active hydrogen-containing compound (H), and 40% or more of the hydroxyl groups located at the terminals are primary hydroxyl group-containing groups represented by the following general formula (1) It is an oxyalkylene polyol (a), The polyol composition for polyurethane foam manufacture of Claims 1-4.

[In General Formula (1), R ¹ represents a hydrogen atom, an alkyl group, a cycloalkyl group, or a phenyl group. Carbon number of an alkyl group, a cycloalkyl group, or a phenyl group is 1-12. The alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group. ] The polyol composition for producing a polyurethane foam according to any one of claims 1 to 5, wherein the content of the compound (B) is 0.1 to 90% by weight based on the weight of the polyol composition (PL). The polyol composition for producing a polyurethane according to any one of claims 1 to 6, wherein the polyol (A) is a polyol represented by the following general formula (7).

[In the general formula (7), R ²¹ is an s-valent group obtained by removing s active hydrogens from the active hydrogen-containing compound (H); Z is a carbon represented by the following general formula (8) or (9) It is an alkylene group of 2 to 12. The alkylene group may be substituted with a halogen atom or an aryl group. ; A is a C3-C12 alkylene group represented by the following general formula (10) or (11). The alkylene group may be substituted with a halogen atom or an aryl group. When there are a plurality of Z or A, each may be the same or different; s 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 0 to 200 It is an integer. ]

[In General Formulas (8) and (9), R ²² represents a hydrogen atom or an alkyl group, cycloalkyl group or phenyl group having 1 to 10 carbon atoms. The alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group. In formulas (10) and (11), R ²³ represents an alkyl group having 1 to 10 carbon atoms, a cycloalkyl group, or a phenyl group. The alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group. ] The polyurethane foam production according to claim 7, wherein 40% or more of the structure of A located at the terminal in the part of (AO) _{q in} the general formula (7) is a structure represented by the general formula (11). Polyol composition. The polyol composition for producing a polyurethane foam according to any one of claims 1 to 8, wherein 60% or more of the hydroxyl group-containing groups located at the terminals are primary hydroxyl group-containing groups represented by the general formula (1). In the method for producing a polyurethane foam by reacting a polyol component and an isocyanate component, the polyol component (PL) according to any one of claims 1 to 9 is 10 to 100 wt% relative to the weight of the polyol component. % Of polyurethane foam production method. The polyurethane according to claim 10, wherein the polyol component and the isocyanate component are reacted in the presence of the foaming agent (D), and the amount of the foaming agent (D) used is 0.1 to 50% by weight based on the weight of the polyol component. Form manufacturing method.

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