JP2012062412A - Polyol composition and method for production of polyurethane using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyol composition whose tensile characteristic and wet heat compression property do not degrade even when improving the hardness of a soft polyurethane foam.SOLUTION: The polyol composition comprises a polyol (A) and a carbon nanotube (B). A polyol (a) contained in the polyol (A) is an alkylene oxide adduct of an active hydrogen-containing compound (H), and in more details, is polyoxyalkylene polyol in which 40% or more of the hydroxy groups positioned at the terminal of molecule are the groups containing a specific primary hydroxy group, and a hydroxy value x, total unsaturation degree y and the content z of an ethylene oxide unit satisfy the relation of numerical expression (1): y≤28.3×x×(100-z)/100 (wherein, z is the ethylene oxide content of 0-50 wt.%).

Description

  The present invention relates to a polyol composition and a method for producing a polyurethane using the polyol composition. More specifically, the present invention relates to a polyol composition that is suitable as a polyurethane raw material such as polyurethane foam and imparts excellent mechanical properties to polyurethane.

Conventionally, for the purpose of improving the hardness of flexible polyurethane foam, a method using a low molecular weight polyol (so-called crosslinking agent), a method using a polymer polyol, and a method of adding an inorganic filler have been used (for example, Patent Document 1). .
In addition, the applicant of the present application has previously found that mechanical properties such as hardness are improved by using a polyol having a low total unsaturation and a high primary ratio of the terminal hydroxyl group (for example, Patent Document 2). .

JP 2004-210976 A JP 2003-113219 A

However, when the hardness is improved by a method of adding a low molecular weight polyol, a polymer polyol, or an inorganic filler, there is a problem that the tensile properties are remarkably lowered. In addition, the conventional method using a polyol having a high degree of primary hydroxyl group hydroxylation does not sufficiently improve the hardness, and it is necessary to further add a low molecular weight polyol, a polymer polyol, and an inorganic filler, especially for applications requiring high hardness. There is an inevitable decrease in tensile properties.
An object of this invention is to provide the polyol composition which solved these problems.

［一般式（Ｉ）中、Ｒ¹は、水素原子、又は炭素数１〜１２のアルキル基、シクロアルキル基若しくはフェニル基を表す。アルキル基、シクロアルキル基又はフェニル基は、ハロゲン原子又はアリール基で置換されていてもよい。］
ｙ≦２８．３×ｘ^-2×（１００−ｚ）／１００ （１）
［数式（１）中、ｘは単位ｍｇＫＯＨ／ｇで表される水酸基価、ｙは単位ｍｅｑ／ｇで表される総不飽和度を表す。ｚは、（ａ）の重量を基準とするエチレンオキサイド含有量であり、０〜５０重量％である。］
また、本発明のポリウレタンの製造方法は、ポリオール成分とイソシアネート成分とを反応させてポリウレタンを製造する方法において、ポリオール成分として本発明のポリオール組成物をポリオール成分の重量を基準として１０〜１００重量％含有するポリオール成分を用いることを要旨とする。 That is, the gist of the present invention is a polyol composition comprising a polyol (A) and a carbon nanotube (B), wherein (A) comprises the following polyol (a).
Polyol (a): an alkylene oxide adduct of the active hydrogen-containing compound (H), wherein 40% or more of the hydroxyl groups located at the terminals are primary hydroxyl group-containing groups represented by the following general formula (I), A polyoxyalkylene polyol in which the valence x, the total degree of unsaturation y, and the ethylene oxide content z satisfy the relationship of formula (1).

[In General Formula (I), R ¹ represents a hydrogen atom or an alkyl group, cycloalkyl group, or phenyl group having 1 to 12 carbon atoms. The alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group. ]
y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)
[In Formula (1), x represents the hydroxyl value represented by the unit mgKOH / g, and y represents the total degree of unsaturation represented by the unit meq / g. z is the ethylene oxide content based on the weight of (a), and is 0 to 50% by weight. ]
The polyurethane production method of the present invention is a method of producing a polyurethane by reacting a polyol component and an isocyanate component. The polyol composition of the present invention is used as a polyol component in an amount of 10 to 100% by weight based on the weight of the polyol component. The gist is to use the polyol component contained.

The polyol composition of the present invention and the polyurethane obtained using the same have the following effects.
(1) The polyurethane foam produced using the polyol composition of the present invention has good hardness and tensile properties.

6 is a diagram showing a process flow of Production Example 1. FIG.

The polyol composition of the present invention contains a polyol (A) and a carbon nanotube (B).
The polyol (A) contains the polyol (a) as an essential component.
The polyol (a) 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 primary hydroxyl group-containing groups represented by the following general formula (I): It is a polyoxyalkylene polyol in which the hydroxyl value x, the total unsaturation y, and the ethylene oxide content z satisfy the relationship of the following mathematical formula (1).

y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)

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

y is the total unsaturation degree (meq / g) of the polyoxyalkylene polyol, and is determined according to JISK-1557-3.
The range of y is preferably 0 to 0.04, more preferably 0 to 0.02, particularly preferably 0 to 0.01 from the viewpoint of mechanical properties of polyurethane.

  Z is the ethylene oxide content based on the weight of the polyol (a). The range of z is 0 to 50% by weight, preferably 0 to 25% by weight, particularly preferably 0 to 20% by weight. When z exceeds 50% by weight, the physical properties of polyurethane are 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)

  The number average molecular weight (hereinafter abbreviated as Mn) of the polyol (a) is preferably 500 to 20,000, more preferably 1,200 to 20,000, from the viewpoint of mechanical properties of the polyurethane and handling properties (viscosity) of the polyol composition. 15,000, particularly preferably 2,000 to 9,000.

As described above, the relationship among the hydroxyl value x, the total degree of unsaturation y, and the ethylene oxide content z of the polyol (a) satisfies the relationship of the 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 by using this (a) has high reactivity at the time of production, and the mechanical properties of the resin, particularly tensile properties (elongation, tensile strength) are good.

More preferably, (a) satisfies the relationship of Equation (3).
y ≦ 18.9 × x ⁻² × (100−z) / 100 (3)
In (a) satisfying the mathematical formula (3), the amount of unsaturated monool is reduced as compared with the case where the mathematical formula (1) is satisfied. A polyurethane (including a polyurethane foam) produced using such a polyoxyalkylene polyol is used. ) Mechanical properties are further improved.

The polyol (a) is an alkylene oxide adduct of the active hydrogen-containing compound (H).
Examples of the active hydrogen compound (H) include a compound having 2 to 8 or more polyvalent hydroxyl groups, an amino group-containing compound having polyvalent active hydrogen, a polyvalent carboxyl group-containing compound, a polyvalent thiol group-containing compound, And phosphoric acid compounds having active hydrogen; and compounds having two or more active hydrogen-containing functional groups in the molecule; and mixtures of two or more thereof.

Examples of the polyhydric 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 having a polyvalent active hydrogen include amines, polyamines and amino alcohols. 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.

  Polyvalent carboxyl group-containing compounds include: aliphatic polycarboxylic acids such as succinic acid and adipic acid; aromatic polycarboxylic acids such as phthalic acid and trimellitic acid; polycarboxylic acid heavy compounds such as (co) polymers of acrylic acid Combined (functional group number 2-100) etc. are mentioned.

Examples of the polyvalent 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 the phosphoric acid compound having polyvalent active hydrogen include phosphoric acid, phosphorous acid, and phosphonic acid.

Of these active hydrogen-containing compounds (H), from the viewpoint of the mechanical properties of polyurethane, polyhydric hydroxyl group-containing compounds and amino group-containing compounds having polyvalent active hydrogen are preferred, and water, polyhydric alcohols and amines are particularly preferred. It is.
The active hydrogen equivalent of the active hydrogen-containing compound is preferably 20 to 300 from the viewpoint of mechanical properties of the resulting polyurethane.

  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). Abbreviation), 1,3-propyloxide, 1,4-butylene oxide, and the like. Among these, PO and EO are preferable from the viewpoint of mechanical properties of polyurethane. 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.

  AO is preferably composed only of C3 or more 1,2-AO and EO, but in addition to these, AO other than these is contained in a small proportion (for example, 5% by weight or less based on the weight of the total AO). You may go out. In the AO to be used, the content of 1,2-AO of C3 or more is preferably 50% by weight or more, more preferably 70% by weight or more based on the weight of all AOs, from the viewpoint of mechanical properties of the obtained polyurethane. .

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

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

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

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

  Specific examples of Z include ethylene group, propylene group, butylene group, chloropropylene group, phenylethylene group, 1,2-cyclohexylene group and the like, and combinations of two or more thereof. From the viewpoint of productivity of the polyol (a), a propylene group, a butylene group, and an ethylene group are preferable. When taking into consideration ensuring the hydrophobicity of the resulting polyol (a), a propylene group, a butylene group or the like may be used, or an ethylene group and another alkylene group may be used in combination.

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

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

  Specific examples of A include a propylene group, a butylene group, a chloropropylene group, a phenylethylene group, a 1,2-cyclohexylene group, and a combination of two or more thereof. Among these, a propylene group and a butylene group are preferable from the viewpoint of productivity of the polyol (a).

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

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

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

Among those represented by the general formula (II), 40% or more of the structure of A located at the terminal in the part of (AO) _{q in} the general formula (II) is represented by the general formula (VI). The structure is preferable, more preferably 50% or more, and particularly preferably 65% or more. Within this range, it is easy to satisfy the relationship of Equation (1).

The polyol (a) is a primary hydroxyl group-containing group in which 40% or more of the terminal hydroxyl groups are represented by the above general formula (I).
For example, when (a) is represented by the above general formula (II), the hydroxyl group-containing group located at the terminal includes a primary hydroxyl group-containing group represented by the above general formula (I) and r = 0. Two types of secondary hydroxyl group-containing groups represented by the following general formula (VII) can be considered, but (a) is a hydroxyl group located at the terminal regardless of the value of r in the above general formula (II). 40% or more is the primary hydroxyl group-containing group represented by the general formula (I).
In (a), the ratio of the primary hydroxyl group-containing group represented by the general formula (I) to the total hydroxyl groups at the terminals (this is the primary hydroxyl group ratio in the present specification. The same applies hereinafter. Is 40% or more based on the amount of all terminal hydroxyl groups in (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 (I) represents a hydrogen atom or a C1-12 alkyl group, cycloalkyl group or phenyl group, and the alkyl group, cycloalkyl group or phenyl group is substituted with a halogen atom or an aryl group. It may be. R ⁵ in the general formula (VII) represents a C1-12 alkyl group, cycloalkyl group or phenyl group, and 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 ⁵ include those obtained by removing a hydrogen atom from 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 hydroxyl group at the end of the 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 number average molecular weight of the polyol (a) is appropriately selected depending on the use of (a), for example, the required physical properties of a thermosetting resin such as polyurethane to be produced, and is not particularly limited. , 000 is preferred, preferably 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 (VIII) can be produced by a generally known method, for example, ring opening addition of C2-12 AO to the active hydrogen-containing compound (H). It can manufacture by superposing | polymerizing and the catalyst of this superposition | polymerization is not specifically limited.
The polyol (a) is obtained by ring-opening addition polymerization of C3-12 AO to (J) in the presence of the catalyst (C) to obtain an active hydrogen compound (K) represented by the following general formula (IX). be able to. 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 addition-polymerized at the end of (K), (K) is (a), and the hydroxyl value x and total unsaturation y of (a) obtained satisfy the relationship of formula (1). Just do it.

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

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

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

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

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

  In the presence of the catalyst (C), AO is added to the active hydrogen-containing compound (J) to obtain the active hydrogen compound (K), and the number of moles of AO to be added is the active hydrogen-containing compound (J). The amount is preferably 1 to 200 mol, more preferably 1 to 100 mol, based 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 an active hydrogen-containing compound (K) represented by the above general formula (IX) is obtained by adding AO 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 a 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) obtained when the EO is not added and polymerized to the produced active hydrogen-containing compound (K) contains the catalyst (C). Depending on the application, decomposition of the catalyst (C) and Execute removal process.

  As a decomposition method, there is a method of adding water and / or an alcohol compound and, if necessary, a basic substance such as an alkali compound or an amine compound. As the alcohol compound, the aforementioned polyhydric alcohol and / or polyhydric phenol can be used. Moreover, as alcohol compounds, monovalent alcohols such as methanol, ethanol, butanol and octanol, and phenols such as phenol and cresol 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. As the amine compound, one or more selected from the aforementioned amino group-containing compounds having polyvalent active hydrogen can be used. 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. The water or alcohol compound 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 or amine 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.

  Two or more of the polyols (a) used in the present invention may be used in combination. The average number of functional groups per molecule of (a) is preferably 2 to 6, more preferably 2.5 to 4.5, from the viewpoint of the mechanical properties of polyurethane.

The polyol (A) contains the polyol (a) as an essential component, but may contain other polyols (a2). (A2) is a polyol that does not correspond to the polyol (a), and is a known polyol used in the production of polymer polyols (Japanese Patent Laid-Open Nos. 2005-162791, 2004-018543, and 2004-002800). Publications (corresponding to US Patent Application: US2005 / 245724 A1) etc. can be used.
Specific examples of the polyol (a2) include compounds having a structure in which AO is added to the aforementioned active hydrogen-containing compound (H) and mixtures thereof. Among these, AO adducts of polyhydric alcohols are preferred from the viewpoint of mechanical properties of polyurethane.

  Examples of the AO include those described above. Of these AOs, C2-8 are preferred from the viewpoint of the mechanical properties of the resulting polyurethane, more preferably EO, PO, 1,2-, 2,3- and 1,3-butylene oxide, tetrahydrofuran, styrene. Oxides and combinations of two or more of these (block addition and / or random addition), particularly preferably PO or a combination of PO and EO [EO content is 25% by weight or less based on the weight of (A), preferably 1 to 20% by weight].

  Specific examples of the AO adduct include PO adducts and POs of known active hydrogen-containing compounds {JP 2005-162791 A, JP 2004-002800 A (corresponding US patent application: US 2005/245724 A1)}. And other AO (EO is preferred).

  Two or more of the polyols (a2) used in the present invention may be used in combination. The average number of functional groups per molecule, hydroxyl equivalent, hydroxyl value, and Mn in (a2) are the same as those in the polyol (a) described above, and the preferred ranges are also the same.

  The content (% by weight) of the polyol (a) in the polyol (A) is preferably 40 to 100, more preferably 60 to 100, based on the weight of (A), from the viewpoint of the mechanical properties of the resulting polyurethane. Especially preferably, it is 80-100.

  The average number of functional groups per molecule, hydroxyl equivalent, hydroxyl value, and Mn of the polyol (A) are the same as those of the polyol (a) described above, and the preferred ranges are also the same.

The carbon nanotube (B) is made of carbon and has a tube shape with a diameter of the order of nanometers. The carbon nanotube (B) has a structure in which hexagonal networks formed by carbon atoms are connected in a tube shape.
(B) includes a single wall nanotube (hereinafter abbreviated as SWNT) having a single hexagonal tube, and a double-walled nanotube (hereinafter referred to as DWNT) having a double-layered hexagonal tube. (Abbreviation) A multi-wall nanotube (hereinafter abbreviated as MWNT) which is composed of a hexagonal mesh tube having three or more layers.

The aspect ratio (length / diameter ratio) of (B) is preferably from 10 to 30,000, more preferably from 30 to 20,000, from the viewpoint of the tensile properties of the urethane foam and the handleability of the polyol composition.
The diameter of (B) is preferably 0.1 to 50 nm, more preferably 0.1 to 40 nm, from the viewpoint of dispersibility.

  The carbon nanotube (B) is produced by a known method (for example, described in JP-A-6-157016, JP-A-6-280116, JP-A-10-203810, JP-A-11-11917). be able to. In addition, an arc discharge method, a laser evaporation method, a thermal decomposition method, or a plasma discharge method described in “Basics of Carbon Nanotubes” (P23 to P57, Saito, Itoh, Corona Publishing, 1998) Also good.

The carbon nanotube (B) may be modified by a known method.
For example, a method for introducing silicone into the carbon nanotube surface (Japanese Patent Laid-Open No. 08-295694), a method for introducing fluorine into the carbon nanotube surface (Japanese Patent Laid-Open No. 09-141730), and a method for introducing an acrylic group into the carbon nanotube surface. (Japanese Patent Laid-Open No. 2003-246904), a method of introducing a hydroxyl group onto the surface of a carbon nanotube (J. Polym. Sci. Part A, Vol. 46, No. 14, 4857 (2008)). From the viewpoint of the dispersibility of (B) in the polyol composition, a method of introducing a hydroxyl group onto the carbon nanotube surface is preferred.

  The content of the carbon nanotube (B) is preferably 0.2 to 20% by weight, more preferably from the viewpoint of the mechanical properties of the polyurethane and the dispersibility of (B), based on the weight of the polyol (A). Is 0.5 to 15% by weight, particularly preferably 1 to 10%.

  The volume average particle diameter of the carbon nanotube (B) in the polyol (A) is preferably from 0.01 to 30 μm, more preferably from 0.02 to 20 μm, from the viewpoints of handleability of the polyol composition and mechanical properties of the polyurethane. Particularly preferably, the thickness is 0.03 to 10 μm. The volume average particle diameter is measured by a dynamic light scattering measurement method.

The method for producing the polyol composition of the present invention is not particularly limited. For example, a method in which the total amount of carbon nanotubes (B) is added to the polyol (A) at once, or (B) is dividedly added and mixed with a disperser or the like. Can be mentioned. From the viewpoint of the dispersibility of (B), a method of dividing and mixing (B) is preferred.
The mixing temperature is preferably 10 to 150 ° C., more preferably 20 to 120 ° C., and particularly preferably 30 to 100 ° C. from the viewpoint of the dispersibility of (B).

If necessary, a flame retardant may be added to the polyol composition of the present invention. As the flame retardant, various flame retardants (such as those described in JP-A No. 2005-162791, or phosphoric esters, halogenated phosphoric esters, melamine, phosphazene, etc.) can be used. From the viewpoint of handleability of the polyol composition, a flame retardant having a low viscosity (100 mPa · s or less / 25 ° C.) is preferable, and among the halogenated phosphates, tris (chloroethyl) phosphate and tris (chloropropyl) are more preferable. It is phosphate.
The content of the flame retardant in the polyol composition is preferably 10% by weight or less, more preferably, based on the total weight of the polyol (A), from the viewpoint of the flame retardancy of the polyurethane and the mechanical properties of the resulting polyurethane. 0.01 to 5% by weight, particularly preferably 0.05 to 3% by weight.

  The polyol composition of the present invention can be used as a polyol component used for producing polyurethanes such as polyurethane elastomers and polyurethane foams. That is, a polyol component (Po) containing the polyol composition of the present invention and an isocyanate component (Is) containing a polyisocyanate [in the following, a composition comprising (Po) and (Is) may be referred to as a polyurethane-forming composition. . ] Can be reacted by a known method {method described in JP 2004-263192 A (corresponding US patent application: US 2003/4217 A1)} or the like.

As the polyol component (Po) used for producing the polyurethane, in addition to the polyol composition of the present invention, if necessary, a polyol other than the polyol composition of the present invention and a polymer polyol may be used.
As the polyol other than the polyol composition of the present invention, the above-described polyol (A) and the like can be used, and as the polymer polyol, JP-A-2005-162791, JP-A-2004-263192 (corresponding US patent application: US2003). / 4217 A1), and polymer polyols described in JP 2008-274245 A can be used.

  The used amount of the polyol composition of the present invention in the polyol component (Po) is preferably 10 to 100% by weight based on the weight of (Po), from the viewpoint of the mechanical properties of the resulting polyurethane and the viscosity of the polyol component. More preferably, it is 15 to 90% by weight, particularly preferably 20 to 80% by weight, and most preferably 25 to 70% by weight.

As the isocyanate component (Is), known polyisocyanates conventionally used in the production of polyurethane {JP 2005-162791 A, JP 2004-263192 A (corresponding US patent application: US 2003/4217 A1)]. Can be used.
Among these, from the viewpoint of mechanical properties of polyurethane, 2,4- and 2,6-tolylene diisocyanate (TDI), crude TDI (residue when TDI is purified); 4,4′- and 2,4 '-Diphenylmethane diisocyanate (MDI), crude MDI (residue when MDI is purified) is preferred.

  The NCO index [equivalent ratio of NCO group and active hydrogen atom (NCO group / active hydrogen atom) × 100] in the production of polyurethane can be appropriately adjusted from the viewpoint of the mechanical properties of polyurethane, but is preferably 80 to 140. More preferably, it is 85-120, Most preferably, it is 95-115.

  Various catalysts used in the urethanization reaction (described in JP-A-2005-162791 and JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1) in order to accelerate the reaction in the production of polyurethane) Can be used. The amount of the catalyst used is preferably 10% by weight or less, more preferably 0.001 to 5% by weight, based on the total weight of the polyurethane-forming composition.

A foaming agent can be used in the production of the polyurethane foam. For example, water, HFC (hydrofluorocarbon), HCFC (hydrochlorofluorocarbon), methylene chloride, and those described in JP-A-2006-152188 and JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1) Is mentioned.
The amount of foaming agent used can vary depending on the desired density of the polyurethane foam and is not particularly limited, but is preferably 20% by weight or less based on the total weight of the polyurethane-forming composition.
A foam stabilizer can be used in the production of the polyurethane foam. Examples of the foam stabilizer include those described in JP-A No. 2005-162791, JP-A No. 2004-263192 (corresponding US patent application: US 2003/4217 A1), and the like. From the viewpoint, a silicone surfactant (for example, a polysiloxane-polyoxyalkylene copolymer) is preferable.
The amount of the foam stabilizer used is preferably 5% by weight or less, more preferably 0.01 to 2% by weight, based on the total weight of the polyurethane-forming composition.

In the production of polyurethane, a flame retardant can be used if necessary. Examples thereof include melamine, phosphate ester, halogenated phosphate ester, phosphazene, and those described in JP-A-2005-162791, JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1). .
The amount of flame retardant used is preferably 30% by weight or less, more preferably 0.01 to 10% by weight, based on the total weight of the polyurethane-forming composition.

  In the production of polyurethane, if necessary, at least one selected from the group consisting of reaction retarders, colorants, internal mold release agents, anti-aging agents, antioxidants, plasticizers, bactericides, and fillers (including carbon black). Can be used.

Polyurethane can be produced, for example, by the method described in JP-A-2005-162791, JP-A-2004-263192 (corresponding US patent application: US2003 / 4217 A1). One-shot method, semi-prepolymer Method and prepolymer method.
For the production of polyurethane, a conventionally used production apparatus (such as a low-pressure or high-pressure machine) can be used. In the case of the absence of a solvent, an apparatus such as a kneader or an extruder can be used, and when a non-foamed or foamed polyurethane is produced, a closed mold or an open mold can be used.

  In the obtained polyurethane, from the viewpoint of mechanical properties, the volume average particle diameter of the carbon nanotubes contained is preferably 0.005 to 30 μm, more preferably 0.005 to 20 μm, particularly preferably 0.05 to. 10 μm.

  Hereinafter, although an example and a comparative example explain the present invention further, the present invention is not limited to these. Hereinafter, unless otherwise specified, parts are parts by weight.

The composition and symbols of the raw materials used in Examples and Comparative Examples are as follows.
(1) Polyol Polyol (PL-1): A polyol having a hydroxyl value of 56 and an internal EO unit content of 9% by weight, which is block-added to glycerin in the order of PO-EO-PO. Terminal primary ratio = 2 mol%. [Product name "Sanniks GP-3030", manufactured by Sanyo Chemical Industries, Ltd.]
(2) Polymer polyol Polymer polyol (POP-1): A polyol having a hydroxyl value of 56, an EO unit content of 10% by weight, and a terminal primary-modification ratio of 75 mol%, which are block-added to glycerin in the order of PO-EO. Polymer polyol containing 40% by weight of polymer (acrylonitrile / styrene = 30/70% by weight) particles having a volume average particle diameter of 0.6 μm.
(3) Polyisocyanate TDI-80: Trade name “Coronate T-80” [manufactured by Nippon Polyurethane Industry Co., Ltd.] (TDI / MDI = 80/20 wt%)
(4) Catalyst Catalyst-1: Trade name “Neostan U-28” (stannous octylate) [manufactured by Nitto Kasei Co., Ltd.]
Catalyst-2: Trade name “TEDA-L33” (triethylenediamine / dipropylene glycol = 33/67 wt% solution) [manufactured by Tosoh Corporation]
(5) Foam stabilizer Product name “SRX-280A” (polyether siloxane polymer) [manufactured by Toray Dow Corning Silicone Co., Ltd.]
(6) Carbon nanotube SWCNT: Single wall nanotube (diameter 0.8-1.2 nm, length 100-1000 nm) [manufactured by Science Laboratories]
MWCNT: multi-wall nanotube (diameter 20-30 nm, length 0.5-500 μm) (manufactured by Shenzhen Nanotechport)

The measurement and evaluation methods in the examples are as follows.
<Method for Measuring Dispersion Particle Diameter of Carbon Nanotube in Polyol Composition>
The polyol composition was put into a measuring cell, and the dispersed particle size on a volume basis was measured using a particle size distribution measuring device [model number: SALD-7100, manufactured by Shimadzu Corporation].
<Method for evaluating properties of polyurethane foam>
(1) Density (kg / m ³ ): compliant with JIS K6400 (2) 25% ILD (hardness) (kgf / 314 cm ² ): compliant with JIS K6400 (3) Tensile strength (kgf / cm ² ): JIS K6400 Conformity (4) Elongation (%): Conforms to JIS K6400 (5) Humid heat compression residual strain (%): Conforms to JIS K6400

<Method for evaluating the dispersion state of carbon nanotubes in polyurethane foam>
The foam specimen (thickness 1 to 4 mm) was observed using a scanning electron microscope (magnification: 10,000 times). The evaluation criteria are as follows.
A: Observed at 20 locations, there were no aggregates of carbon nanotubes having a dispersed particle size of 30 μm or more.
X: 20 places were observed, and one or more carbon nanotube aggregates having a dispersed particle diameter of 30 μm or more were observed.

Production Example 1 [Production of polyol (a-1)]
As in the embodiment shown in FIG. 1, a stainless steel autoclave {reaction vessel (1)} equipped with a stirrer having a capacity of 2500 ml, a temperature controller and a raw material supply line (5), 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) and (8).
After charging 400 g of glycerin PO adduct (hydroxyl value 280) and 0.09 g of tris (pentafluorophenyl) borane into the reaction tank (1), the reaction tank (1), the reaction tower (2) and the circulation line ( 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 separated from PO and removed out of the system. 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 reached 1920 ml, the PO was stopped, the gas phase circulation was terminated, the mixture was aged at 70 ° C. for 4 hours, 170 g of water was added, and the mixture was heated at 130 to 140 ° C. for 1 hour. Thereafter, water was distilled off at atmospheric 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 to 50 torr while introducing steam at 130 to 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, it was filtered using 1 micron filter paper and then dehydrated under reduced pressure to obtain a liquid glycerin POEO adduct (a-1).
The glycerin PO adduct used as a raw material was synthesized by a known method. 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)]
Instead of using 400 g of glycerin PO adduct (hydroxyl value 280), 240 g of glycerin PO adduct (hydroxyl value 280) is used, instead of “stopping PO addition when the amount of liquid in the autoclave reaches 1920 ml” In addition, the liquid glycerin POEO was synthesized in the same manner as in Production Example 1 except that the PO addition was stopped when the amount of liquid in the autoclave reached 1800 ml and that 200 g of EO was used instead of 80 g of EO. An adduct (a-2) was obtained.

Production Example 3 [Production of polyol (a-3)]
Instead of using 400 g of the glycerin PO adduct (hydroxyl value 280), 200 g of the pentaerythritol PO adduct (hydroxyl value 280) is used. “When the amount of liquid in the autoclave reaches 1920 ml, PO charging is stopped”. Instead, it was synthesized in the same manner as in Production Example 1 except that PO charging was stopped when the amount of liquid in the autoclave reached 1840 ml, and 160 g of EO was used instead of 80 g of EO. Erythritol POEO adduct (a-3) was obtained.
The pentaerythritol PO adduct (hydroxyl value 280) was synthesized by a known method. After adding a predetermined amount of propylene oxide to pentaerythritol 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.

Comparative Production Example 1 [Production of polyol (a′-1)]
[Step 1] After 31 parts of glycerin and 2.1 parts of potassium hydroxide are added to a stainless steel autoclave equipped with a stirrer and a temperature controller, PO687 parts are added dropwise at a reaction temperature of 90 to 110 ° C. over 12 hours. Aged at 100 ° C. for 6 hours. After cooling to 60 ° C., 29 parts of synthetic silicate (Kyoward 600, manufactured by Kyowa Chemical) and 14 parts of water were added and treated at 60 ° C. for 3 hours. After cooling to 25 ° C. and taking out from the autoclave, the mixture was filtered through a 1 μm filter and then dehydrated under reduced pressure to obtain a polyol intermediate (S-1).
[Second step] In a stainless steel autoclave equipped with a stirrer and a temperature controller, 718 parts of (S-1), 0.10 parts of tris (pentafluorophenyl) borane and 232 parts of PO are charged, and the reaction temperature is kept at 65 to 75 ° C. While being controlled in this manner, the solution was dropped over 10 hours and then aged at 70 ° C. for 5 hours. Water was added and propionaldehyde as a by-product was distilled off together with water at 105 to 110 ° C. for 4 hours at normal pressure. Thereafter, while maintaining the temperature at 90 to 100 ° C. and the pressure at 30 to 50 torr, the by-product propionaldehyde was distilled off with water under reduced pressure for 5 hours while continuously introducing water vapor. After stopping the introduction of water vapor, 0.67 part of potassium hydroxide was added, and the temperature was further raised to 130 ° C. for 3 hours, and the pressure was kept at 50 torr or less for dehydration. Subsequently, 50 parts of EO was added dropwise over 3 hours while controlling the reaction temperature to be 125 to 135 ° C., and then aged at 130 ° C. for 2 hours. After cooling to 60 ° C., 40 parts of synthetic silicate (Kyoward 600, manufactured by Kyowa Chemical) and 20 parts of water were added and treated at 60 ° C. for 3 hours. After cooling to 25 ° C. and taking out from the autoclave, it was filtered through a 1 μm filter and then dehydrated under reduced pressure to obtain a liquid polyol (a′-1).

  Table 1 shows the properties of the polyols obtained in Production Examples 1 to 3 and Comparative Production Example 1.

Production Example 4 [Production of carbon nanotube (B-1)]
In a flask equipped with a stirrer and a thermometer, 0.6 part of SWNT was placed in 40 parts of a sulfuric acid / nitric acid mixture (volume ratio 1: 1), stirred at 140 ° C. for 1 hour, and then water (ion-exchanged water, the same applies hereinafter). 500 parts were added and stirred for 30 minutes. Further, the precipitate was separated by filtration and washed 5 times with 500 parts of water. Then, it was spread on a release paper and dried for 120 minutes in a 130 ° C. vacuum dryer to obtain a carbon nanotube (B-1) having an oxidized surface.

Production Example 5 [Production of carbon nanotube (B-2)]
In a flask equipped with a stirrer, thermometer, condenser, and gas inlet tube, 6 parts of 1,4-dioxane, 2 parts of acrylic acid chloride, and 0.02 part of 1,1′-azobis (2-methylbutyronitrile) And after sufficiently substituting with nitrogen gas, stirring for 24 hours at 60 ° C. while venting a small amount of nitrogen, and then dispersing 0.05 parts of carbon nanotubes (B-1) in 100 parts of 1,4-dioxane The solution was added dropwise over 1 hour and further stirred at 60 ° C. for 24 hours. Further, the precipitate was filtered off and washed with 500 parts of tetrahydrofuran three times. Thereafter, the film was spread on a release paper and dried for 120 minutes in a vacuum dryer at 100 ° C., and the surface of the carbon nanotube was modified with polyacrylic acid chloride.
After putting the carbon nanotube modified with polyacrylic acid chloride and 100 parts of 1,4-dioxane on the obtained surface into a flask equipped with a stirrer, thermometer, cooling pipe and gas introduction pipe and applying ultrasonic waves for 1 hour After sufficiently substituting with nitrogen gas, 5.0 parts of ethylene glycol, 0.5 parts of triethylamine and 20 parts of 1,4-dioxane were added dropwise over 1 hour while venting a small amount of nitrogen. Stir for hours. Further, the precipitate was filtered off and washed with 500 parts of tetrahydrofuran three times. Then, it was spread on a release paper and dried for 120 minutes with a vacuum dryer at 100 ° C. to obtain a carbon nanotube (B-2) having a hydroxyl group introduced on the surface.

Production Example 6 [Production of carbon nanotube (B-3)]
A carbon nanotube (B-3) was obtained in the same manner as in Production Example 4 except that SWCNT was changed to MWCNT.

Production Example 7 [Production of carbon nanotube (B-4)]
A carbon nanotube (B-4) was obtained in the same manner as in Production Example 5 except that the carbon nanotube (B-1) was changed to (B-3).

Example 1 [Production of polyol composition (A-1)]
In a flask equipped with a stirrer and a thermometer, 95 parts of polyol (a-1) was added, the temperature was adjusted to 60 ° C., 2.5 parts of carbon nanotube (B-1) was added, and the mixture was stirred for 1 hour. Subsequently, 2.5 parts of (B-1) was further added and stirred for 4 hours to obtain a polyol composition (A-1).

Examples 2 to 10 and Comparative Examples 1 and 2 [Production of polyol compositions (A-2) to (A-10), (A′-1), (A′-2)]
In Example 1, the polyol composition (A-2) to (A-10) was carried out in the same manner as in Example 1 except that the kind and part of the polyol and the kind and part of the carbon nanotube were changed to those shown in Table 2. ), (A′-1) and (A′-2) were obtained. In addition, when charging the carbon nanotubes, the entire amount of the carbon nanotubes was divided into two equal parts as in Example 1.

Example 11 [Production of polyol composition (A-11)]
A flask equipped with a stirrer and a thermometer was charged with 95 parts of polyol (a-1), temperature-controlled at 60 ° C., 2.5 parts of SWCNT were added and stirred for 1 hour, and then an ultrasonic cleaner (model number: UT-205H). Were used for 2 hours. Next, 2.5 parts of SWCNT was further added and stirred for 4 hours, and then an ultrasonic wave was applied for 2 hours to obtain a polyol composition (A-11).

  About the polyol composition obtained in Examples 1-11 and Comparative Examples 1-2, the evaluation result of the volume average particle diameter in a polyol composition was shown in Table 2.

Examples 12 to 24 and Comparative Examples 3 to 4 [Production of polyurethane foam]
Polyol compositions (A-1) to (A-11) obtained in Examples 1 to 11 and comparative polyol compositions (A′-1) to (A′-2) obtained in Comparative Examples 1 and 2 ), And a polyurethane foam was produced by the following foaming formulation at the blending ratio shown in Table 3. The physical properties of these foams were evaluated by the following methods. The results are shown in Table 3.
<Foaming prescription>
[1] The temperature of each of the polyol composition, polyol, polymer polyol and polyisocyanate was adjusted to 25 ± 2 ° C.
[2] A polyol composition, a polyol, a polymer polyol, a foam stabilizer, water, and a catalyst were charged in a 1 L stainless steel beaker, stirred and mixed at 25 ° C. ± 2 ° C., immediately added with a polyisocyanate, and a stirrer [ Homo disperser (manufactured by Tokushu Kika Co., Ltd.)] (stirring conditions: 2,000 rpm × 8 seconds).
[3] After the stirring was stopped, the contents of the beaker mixed in a wooden box (25 ° C. ± 2 ° C.) of 25 × 25 × 10 cm were added and foamed to obtain a polyurethane foam.

From the results shown in Table 3, the polyurethane foam produced using the polyol composition of the present invention has 25% ILD, tensile strength, elongation and wet heat compression residual strain, although the density is equivalent to that of the comparative example. Excellent results were obtained in all items. In particular, the results are very good at 25% ILD and tensile strength.
In general, the physical properties of polyurethane foam indicate that 25% ILD, tensile strength and elongation are better as the numerical value is larger, and that the wet heat compression residual strain is smaller as the numerical value is smaller.

Since the polyol composition of the present invention improves the mechanical properties of polyurethane using these, the polyol composition can be widely used in a wide range of polyurethanes such as foams (soft, rigid, semi-rigid foams), elastomers, RIM molded products and the like. In particular, when used in the production of polyurethane foam, the physical properties of the polyurethane foam can be adjusted with good balance, which is preferable.
The polyurethane obtained from the polyol composition of the present invention is used in a wide variety of applications, and is particularly suitably used as a polyurethane foam for automobile interior parts, indoor furniture for furniture, and the like.

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

Claims (5)

A polyol composition comprising a polyol (A) and a carbon nanotube (B), wherein (A) comprises the following polyol (a).
Polyol (a): an alkylene oxide adduct of the active hydrogen-containing compound (H), wherein 40% or more of the hydroxyl groups located at the terminals are primary hydroxyl group-containing groups represented by the following general formula (I), A polyoxyalkylene polyol in which the valence x, the total degree of unsaturation y, and the ethylene oxide content z satisfy the relationship of formula (1).

[In General Formula (I), R ¹ represents a hydrogen atom or an alkyl group, cycloalkyl group, or phenyl group having 1 to 12 carbon atoms. The alkyl group, cycloalkyl group or phenyl group may be substituted with a halogen atom or an aryl group. ]
y ≦ 28.3 × x ⁻² × (100−z) / 100 (1)
[In Formula (1), x represents the hydroxyl value represented by the unit mgKOH / g, and y represents the total degree of unsaturation represented by the unit meq / g. z is the ethylene oxide content based on the weight of (a), and is 0 to 50% by weight. ] The polyol composition according to claim 1, wherein the polyol (a) is a polyol represented by the following general formula (II).

[In the general formula (II), R ² is an m-valent group obtained by removing m active hydrogens from the active hydrogen-containing compound (H); Z is a carbon represented by the following general formula (III) or (IV) It is an alkylene group or a cycloalkylene group having a number of 2 to 12. The alkylene group or cycloalkylene group may be substituted with a halogen atom or an aryl group. ; A is a C3-C12 alkylene group or cycloalkylene group represented by the following general formula (V) or (VI). The alkylene group or cycloalkylene 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; m is an integer of 2 to 100; p is an integer of 0 to 200, q is an integer of 1 to 200; r is 0 to 200 It is an integer. ]

[In General Formulas (III) and (IV), R ³ 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 the general formulas (V) and (VI), R ⁴ 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 polyol composition according to claim 1 or 2, wherein the volume average particle diameter of the carbon nanotube (B) in the polyol (A) is 0.01 to 30 µm. The polyol composition according to any one of claims 1 to 3, wherein the content of the carbon nanotube (B) is 0.2 to 20% by weight based on the weight of the polyol (A). In a method for producing a polyurethane by reacting a polyol component and an isocyanate component, a polyurethane composition using the polyol composition according to any one of claims 1 to 4 as a polyol component based on the weight of the polyol component. Production method.

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