JPH10195167A - Polyol composition, polyurethane composition, urethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce a polyurethane having excellent conductivity using a polyol composition for producing a non-charged polyurethane which is low in viscosity and easy to handle. SOLUTION: Carbon polyol is dispersed in a polyol, a polystyrene oligomer having a weight average molecular weight of 400 to 5000 is dissolved, and the polyol is a polyoxyalkylene polyol and a specific polyol. Using things,
The composition is reacted with an organic polyisocyanate, if necessary, in the presence of a catalyst, a foam stabilizer, a foaming agent and other auxiliaries to produce a non-chargeable polyurethane.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a polyol composition suitable for producing a non-chargeable polyurethane, and a non-chargeable polyurethane composition and a non-chargeable polyurethane foam obtained by using the same.

[0002]

2. Description of the Related Art Conventionally, in the production of non-charged polyurethane, a method has been known in which a conductive material such as a metal or an electrolyte salt is kneaded into a polyurethane raw material and molded. However, when a metal is used as the conductive compound, there is a problem that the metal precipitates in the polyurethane raw material, and when an electrolyte salt is used, there is a problem that the obtained polyurethane has a large humidity dependency of conductivity. . In order to improve the precipitation and the dependence on humidity, methods using carbon black as a conductive compound have been proposed (for example, JP-A-2-18490, JP-A-2-18490).
-40683).

[0003]

However, in the case of carbon black, the problems of sedimentation and humidity are improved, but the problem that the blending of carbon black increases the viscosity of the polyurethane raw material, the fluidity is lost, and handling is difficult. was there.

[0004]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies with the aim of improving the flowability problem associated with the increase in the viscosity of a polyurethane raw material containing carbon black, and as a result, the specific polyol composition It has been found that not only is this polyol composition in which carbon black is dispersed improved in this flowability problem, but the polyurethane reacted with an organic polyisocyanate using this composition has improved conductivity. Reached. That is, the present invention is the following polyol composition, non-chargeable polyurethane composition and non-chargeable polyurethane foam.

The carbon black (b) is dispersed in the polyol (a) and has a weight average molecular weight of 400
Is a polyol composition for producing a non-chargeable polyurethane, in which (a) the oxyalkylene group has 2 or less carbon atoms.
Or 3 polyoxyalkylene polyol (a1) 80
９９99.5 mass% and the following polyol (a2) 0.5〜
20% by mass of polyol, (a) 1 to 20 parts by mass, (c) 0.3 to 5 parts by mass, and viscosity of 2,000 to 60,000 mPa · s per 100 parts by mass.
s is a polyol composition. Polyol (a2): Polyester polyol (a2
1), polybutadiene polyol (a22), hydrogenated polybutadiene polyol (a23) and carbon number 5 to 30
At least one polyol selected from the group consisting of polyoxyalkylene polyols having an oxyalkylene group (a24)

A non-chargeable polyurethane composition derived from the polyol composition and an organic polyisocyanate (n), wherein carbon black is dispersed in polyurethane.

A non-chargeable polyurethane foam derived from the polyol composition and an organic polyisocyanate (n), wherein carbon black is dispersed in a polyurethane foam layer.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION The polyol (a) is the polyoxyalkylene polyol (a1) and the polyol (a).
2). Among these, as the polyoxyalkylene polyol (a1), alcohols, ammonia,
Examples thereof include polyoxyalkylene polyols obtained by adding an alkylene oxide having 2 and / or 3 carbon atoms to a compound containing an active hydrogen atom such as amines, polyhydric phenols, and polycarboxylic acids.

Among the compounds containing an active hydrogen atom, alcohols include methanol, ethanol, butanol, ethylene glycol, propylene glycol, 1,4-butanediol, 1,6-hexanediol, glycerin, trimethylolpropane, pentaerythritol,
Methyl glycoside, sorbitol, sucrose and the like can be mentioned. Examples of amines include monoamines (dimethylamine, ethylamine, butylamine, etc.), aliphatic polyamines (ethylenediamine, triethylenediamine, diethylenetriamine, etc.), alicyclic polyamines (piperazine,
N-aminoethylpiperazine), aromatic polyamines (phenylenediamine, tolylenediamine, xylylenediamine, diphenylmethanediamine, polyphenylmethanepolyamine, etc.) and alkanolamines (monoethanolamine, diethanolamine, triethanolamine, etc.). Can be Examples of the polyhydric phenols include polyhydric phenols (such as pyrogallol and hydroquinone) and bisphenols (such as bisphenol A). Examples of the polycarboxylic acids include aliphatic polycarboxylic acids (succinic acid, adipic acid, etc.) and aromatic polycarboxylic acids (phthalic acid, terephthalic acid, trimellitic acid, etc.). Two or more of these active hydrogen atom-containing compounds may be used in combination.

As the alkylene oxide having 2 and / or 3 carbon atoms, ethylene oxide (hereinafter abbreviated as EO)
Alternatively, propylene oxide (hereinafter abbreviated as PO) and a combination thereof may be used. The addition method of the alkylene oxide may be a conventional method, and when used in combination, the addition form may be either block addition or random addition.

The polyoxyalkylene polyol (a
Preferred as 1) are compounds obtained by adding PO alone or a combination of PO and EO to alcohols or amines, and particularly preferred are ethylene glycol, propylene glycol, glycerin, trimethylolpropane, and pentane. At least one of erythritol, monoethanolamine, diethanolamine, triethanolamine and ethylenediamine,
It is a compound added alone or in combination with PO and EO. EO when adding PO and EO together
The content is usually 30% by weight or less, preferably 20% by weight or less.

The polyoxyalkylene polyol (a
The average number of functional groups in 1) is usually 2 to 5, preferably 2 to 4.
It is. The active hydrogen equivalent is usually from 200 to 5,000, preferably from 1,000 to 3,000. When the average number of functional groups is less than 2 or the active hydrogen equivalent exceeds 5000, the compression residual strain rate and the wet heat residual strain rate increase when used in polyurethane foam, and the reactivity is low and the curability is low when used in a polyurethane elastomer. Will be insufficient.
On the other hand, the average number of functional groups exceeds 5, or the active hydrogen equivalent is 2
If it is less than 00, when used for a polyurethane foam, the polymer forming the foam is rigid and the polyurethane foam becomes brittle, and when used for a polyurethane elastomer, the elongation becomes small.

The polyol (a2) is a polyester polyol (a21) or a polybutadiene polyol (a2).
2) a group consisting of hydrogenated polybutadiene polyol (a23) and polyoxyalkylene polyol (a24) containing 30 to 100% by mass of an oxyalkylene group having 5 to 30 carbon atoms and having an oxyalkylene group having 2 to 4 carbon atoms. At least one polyol selected from

Examples of the polyester polyol (a21) include condensed polyester polyols, lactone-based polyester polyols and polycarbonate-based polyester polyols described in "Polyurethane Resin Handbook" by Keiji Iwata, pages 108 to 111 of Nikkan Kogyo Shimbun. JP-B-2-55470, JP-B-4-639
No. 12, dimer acid-based polyols, castor oil-based polyols, and the like. The condensed polyester polyol is produced by a dehydration condensation reaction between a dibasic acid such as adipic acid and a glycol such as ethylene glycol, diethylene glycol, butylene glycol, neopentyl glycol, and trimethylolpropane, and triol.
The lactone polyester polyol is obtained by ring-opening polymerization of ε-caprolactam.

As the polybutadiene polyol (a22), for example, those described in the above-mentioned pages 112 to 113,
JP-B 2-55470 and JP-B 4-63912. Polybutadiene polyol is a butadiene having a hydroxyl group at the terminal and a copolymer thereof. Examples of the hydrogenated polybutadiene polyol (a23) include those disclosed in JP-A-2-298574. The hydrogenated polybutadiene polyol is obtained by hydrogenation of the above-mentioned polybutadiene polyol.

The polyol (a24) usually contains 30 to 100% by mass of oxyalkylene group having 5 to 30 carbon atoms and contains oxyalkylene group of 2 to 4 carbon atoms in an amount not exceeding 70% by mass. There may be mentioned polyoxyalkylene polyols, which, for example,
The active hydrogen compound exemplified as the starting material of the polyoxyalkylene polyol (a1) contains 30 to 100% by mass of an α-olefin oxide (5 to 30 carbon atoms) and 0 to 70% by mass of an alkylene oxide having 2 to 4 carbon atoms. Is obtained by addition polymerization. Examples of the alkylene oxide having 2 to 4 carbon atoms include EO, PO, 1,2-, 1,3-, 1,4
-, 2,3-butylene oxide and a combination of two or more thereof. The addition method of the α-olefin oxide and the alkylene oxide having 2 to 4 carbon atoms may be either block and / or random addition.

The average number of functional groups of the polyol (a2) is usually 1 to 4, preferably 2 to 3. Active hydrogen equivalent is
Usually 200 to 5,000, preferably 300 to 3,000
0. Outside this range, it is difficult to achieve both viscosity and conductivity of the composition.

The carbon black (b) is not particularly limited, and examples thereof include those produced by a furnace method, a channel method, a thermal method, and natural products (such as graphite). In order to impart good conductivity to the obtained polyurethane, the particle size of the carbon black (b) and the nitrogen adsorption specific surface area (ASTM D3037) are important, and the particle size is 10 to 60 nm and the nitrogen adsorption specific surface area is It is preferable to use the one of 30 to 1,000 m ² / g.

The weight average molecular weight of the polystyrene oligomer (c) is usually 400 to 5000, preferably 100.
0 to 3000. If the weight average molecular weight is less than 400, bleed out from polyurethane is likely to occur, and
If it exceeds 00, the compatibility with the polyol (a) decreases. Polystyrene oligomer (c) is polyol (a)
It may be polymerized in the inside.

(A1) in (a) is usually 80 to 99.5.
% By mass, preferably 90 to 99.5% by mass;
2) is usually 0.5 to 20% by mass, preferably 0.5 to 1
It is 0 mass%. Also, (a) per 100 parts by mass,
(B) is usually 1 to 20 parts by mass, preferably 1 to 10 parts by mass, and (c) is usually 0.3 to 5 parts by mass, preferably 0.5 to 3 parts by mass. (A1) in (a), (a)
If the amounts of (2) and (b) and (c) with respect to (a) are outside the above ranges, it is difficult to achieve both the viscosity and conductivity of the composition.

When producing the polyurethane composition of the present invention or the polyurethane foam of the present invention, a known polymer polyol may be used together with the polyol composition of the present invention, if necessary, as a polyol component. Known polymer polyols that can be used in combination include the above-mentioned polyols (a1)
Alternatively, in at least one of other polyols, a polymer obtained by polymerizing and stably dispersing a vinyl monomer such as acrylonitrile or styrene in the presence of a radical polymerization initiator may be used.
The content of the polymer in the polymer polyol is usually 10 to 50.
% By weight.

In the present invention, as the organic polyisocyanate (n), a known organic polyisocyanate (n) which is generally used for polyurethane, for example, an aromatic polyisocyanate having 6 to 20 carbon atoms (excluding the number of carbon atoms in the NCO group) Isocyanate [2,4- or 2,6-tolylene diisocyanate (TDI), crude TDI, 2,4 '
-Or 4,4'-diphenylmethane diisocyanate (MDI), crude MDI, polyaryl polyisocyanate (PAPI), etc.]; aliphatic isocyanates having 2 to 18 carbon atoms (hexamethylene diisocyanate, lysine diisocyanate, etc.); To 18 alicyclic polyisocyanates (isophorone diisocyanate, dicyclohexyl diisocyanate, etc.);-modified products of these polyisocyanates (urethane group,
Carbodiimide group, allophanate group, urea group, uretdione group, burette group, uretonimine group, isocyanurate group, oxazolidone group-containing modified product, etc.); and a mixture of two or more thereof. Preferred among these is TDI.

The isocyanate index [NCO group / active hydrogen atom-containing group equivalent ratio × 100] when producing the polyurethane composition of the present invention or the polyurethane foam of the present invention.
Is usually 70 to 140, preferably 85 to 120, particularly 95 to 115. The polyisocyanurate can also be introduced into the polyurethane with an isocyanate index significantly higher than the above range (e.g. 300 to 1000 or more).

When the polyurethane composition of the present invention or the polyurethane foam is produced, if necessary, a known catalyst, a foam stabilizer, a chain extender and / or a cross-linking agent which are usually used in the production of polyurethane may be used. it can. As the catalyst, metal salts of carboxylic acids [sodium acetate, potassium octylate, lead octylate, zinc octylate, cobalt naphthenate, stannased dioctoate, etc.]; Alkali metal or alkaline earth metal alkoxides or phenoxides [Sodium methoxide, sodium phenoxide, etc.];-Tertiary amines [triethylamine, triethylenediamine, N-methylmorpholine, dimethylaminomethylphenol, etc.];-Quaternary ammonium salt [tetraethylammonium hydroxide, etc.];-Imidazoles [ Imidazole, 2-ethyl-4-methylimidazole and the like]; and organometallic compounds containing a metal such as tin and antimony [tetraphenyl tin, tributyl antimony oxide and the like] and the like. Preferred of these are:
A tertiary amine, a metal salt of a carboxylic acid containing tin or lead, an organometallic compound, and a combination of two or more thereof.

Specific examples of the foam stabilizer include: “SZ-1306” and “SZ” manufactured by Nippon Unicar Co., Ltd.
-1142 "," L-5309 "," L-5366 ",
"L-520", "L-540", "L-5420",
"L-580", "SZ-1127", etc .; "SH" manufactured by Dow Corning Silicone Toray Co., Ltd.
-190 "," SH-193 "," SF-8427 ",
And dimethylsiloxane-based foam stabilizers such as "SRX-294A" and "SRX-274C".

As the chain extender and / or the crosslinking agent,
What is usually used for polyurethane is used, and specific examples include ethylene glycol, diethanolamine,
Examples thereof include triethanolamine, glycerin, trimethylolpropane, D-sorbit and the like, or PO and / or EO adducts such as diethanolamine, triethanolamine and diethylenetriamine.

As the foaming agent for producing the polyurethane foam of the present invention, water alone is mainly used, but if necessary, a low boiling point foaming agent such as methylene chloride can be used in combination.

When producing the polyurethane composition of the present invention or the polyurethane foam, a flame retardant, if necessary,
Other additives can be used. As flame retardants, melamines, phosphoric acid esters, halogenated phosphoric acid esters,
Examples include phosphazene derivatives, and other additives include known additives such as a reaction retarder, an internal release agent, an antioxidant, an antioxidant, a plasticizer, a bactericide, and a filler.

The polyurethane composition of the present invention and the method for producing the polyurethane foam may be a conventionally known polyurethane or polyurethane foam forming method, and any one-shot method, prepolymer method or quasi-prepolymer method may be applied. . The polyurethane foam may be manufactured by a known method, such as a slab method, a hot cure method, a cold cure method, an RIM method, molding by an open mold, integral molding with a composite material, an on-site construction method, a spray method, and a casting method. , Injection, coating, impregnation, etc. can be applied. In particular,
Japanese Patent Publication No. 39-24737, Japanese Patent Publication No. 47-15108
JP-A-46-5750, JP-A-55-13341
No. 7, the method for producing the foam described in each publication; JP-A-49-
99597, JP-A-50-23497, JP-A-53.
No. 16,796, JP-A-53-42294, etc. can be used, and the catalysts, surfactants and other auxiliaries, equivalent ratios, addition amounts, and the like to be used are also described. Can be used. The polyurethane foam of the polyurethane composition of the present invention usually has a volume resistivity value of usually 10 ³ to 10 ⁹ Ω · c.
m.

[0030]

The present invention will be described in more detail with reference to the following examples, which, however, are not intended to limit the scope of the present invention. In addition, the numerical values in the “parts” in the production examples and the numerical values in the foaming prescription columns in the examples and the comparative examples indicate parts by mass, respectively.

[Explanation of Symbols of Starting Materials] Polyol (a1): a1-1: PO adduct of glycerin, hydroxyl value = 5
6 Polyester polyol (a21): a21-1: Polyester polyol having a molecular weight of 2,000 by adding ε-caprolactone to a polyether polyol having a molecular weight of 200 and PO added to propylene glycol Polybutadiene polyol (a22): a22-1: manufactured by Idemitsu Petrochemical Polybutadiene polyol “R15HT”, hydroxyl value = 102.7 Polyol (a24): a24-1: Polyoxy having a molecular weight of 3,000 added to glycerin in a molar ratio of PO / α-olefin oxide having 12 to 14 carbon atoms = 1/1 Alkylene polyol a24-2: Polyoxyalkylene polyol having a molecular weight of 3000 in which α-olefin oxide having 12 to 14 carbon atoms is added to glycerin.

Carbon black (b): b-1: Oil furnace method carbon black having a particle diameter of about 25 nm and a nitrogen adsorption specific surface area of about 215 m ² / g Polystyrene oligomer (c): c-1: Polystyrene oligomer, weight average molecular weight 2,000 Organic polyisocyanate (n): T-80: Nippon Polyurethane Industry Co., Ltd. "Coronate T-80" (TDI-80, NCO% = 48.2)
8)

Other auxiliaries: Catalyst-1: "Minico L-10" manufactured by Kokusai Kagaku Co., Ltd.
20 "(a 33% solution of triethylenediamine in dipropylene glycol) Catalyst-2: Stanas Dioctoate" Neostan U-28 "manufactured by Nitto Kasei Foam stabilizer-1:" SZ-114 "manufactured by Nippon Unicar Co., Ltd.
2) Foam stabilizer-2: "L-5366" manufactured by Nippon Unicar Co., Ltd.

Examples 1 to 6 (a1-1) 95 parts, (a21-1) 5 parts, (c-1)
2 parts and 7 parts of (b-1) were mixed with a sand mixer,
Carbon dispersed PPG was prepared and the viscosity (rotor No. 4,
6 rpm). This carbon-dispersed PPG is shown in Table 1.
Was foamed in a 10 × 10 × 3 cm aluminum mold according to the formula shown in Table 1 to obtain a foam molded product. The Form C hardness and the volume resistivity value of this were measured. Table 1 shows the results. Similarly, molded articles of Examples 2 to 6 were obtained. These results are shown in Table 1.
It was shown to.

[0035]

Table 1---------------------------------------------------------- −−−−−−−−−−−−−−−−−−−−−−−−− a−1 95 95 95 95 95 95 a21-1 5 5 5a22-1 5 a24-1 5 a24-2 5 b-1 7 7 7 7 7 7 c-1 2 1 0.5 1 1 1 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Viscosity (mPa ・ s) 22000 34500 41500 33500 34000 27200 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Foaming formulation Carbon dispersion PPG 100 100 100 100 100 100 Catalyst-1 0.6 0.6 0.6 0.6 0.6 0.6 Water 0.3 0.3 0.3 0.3 0.3 0.3 Foamer-1 0.1 0.1 0.1 0.1 0.1 0.1 Foamer-2 0.2 0.2 0.2 0.2 0.2 0.2 Catalyst-2 0.3 0.3 0.3 0.3 0.3 0.3 T-80 10.9 10.9 11.0 11.3 10.9 10.9 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−−− Total density (g / cm ³ ) 0.29 0.30 0.30 0.29 0.29 0.30 C hardness 16 16 17 15 17 16 Volume resistivity (Ωcm) 2.1E06 5.0E05 1.5E05 4.2E05 8.2E05 2.2E05 −−−−−−−−−−−−−−−−−−−−−−−−−−−−−− −−

Comparative Examples 1 to 3 By the same operation as in Examples 1 to 6, molded products of Comparative Examples 1 to 3 were obtained. The results are shown in Table 2.

[0037]

Table 2 Comparative Example 12 3------------------------------------------a1-1 100 70 70 a21-1 30 a22-1 30 b-1 7 7 7 −−−−−−−−−−−−−−−−−−− Viscosity (mPa ・ s) 71000 10500 64600 −−−−− −−−−−−−−−−−−−− Foaming formula Carbon dispersion PPG 100 100 100 Catalyst-1 0.6 0.6 0.6 Water 0.3 0.3 0.3 Foaming agent-1 0.1 0.1 0.1 Foaming agent-2 0.2 0.2 0.2 Catalyst- 2 0.3 0.3 0.3 T-80 11.0 11.0 13.0 −−−−−−−−−−−−−−−−−−−− Total density (g / cm ³ ) 0.30 0.29 0.30 C hardness 15 8 10 Volume resistivity ( Ωcm) 2.5E07 5.2E09 1.9E08 −−−−−−−−−−−−−−−−−−−−−

As is clear from the examples, the polyol composition of the present invention has a lower viscosity than that of a conventional polyether polyol in which carbon black is dispersed, and the obtained polyurethane has a higher conductivity than the conventional polyurethane. Has improved.

[0039]

The polyol composition of the present invention has a low viscosity and is easy to handle. In addition, by using the composition as an essential polyol component, it becomes possible to produce a polyurethane having excellent conductivity and with little deterioration in performance over time. From the above effect, the conductive polyurethane obtained by using the polyol composition of the present invention is a conductive roller, a conductive blade, a conductive flooring material, a conductive coating material, a conductive foam, an antistatic clothing, an electrostatic charge. It is useful as a material for preventing shoes.

Continuation of front page (51) Int.Cl. ⁶ Identification code FI // (C08G 18/48 101: 00) (C08L 71/02 25:06)

Claims (3)

[Claims] A carbon black (b) is dispersed in a polyol (a) and has a weight average molecular weight of 400.
A polystyrene oligomer (c) having a molecular weight of from 5,000 to 5,000.
Or 3 polyoxyalkylene polyol (a1) 80
９９99.5 mass% and the following polyol (a2) 0.5〜
20% by mass of polyol, (a) 1 to 20 parts by mass, (c) 0.3 to 5 parts by mass, and viscosity of 2,000 to 60,000 mPa · s per 100 parts by mass.
s is a polyol composition. Polyol (a2): Polyester polyol (a2
1), polybutadiene polyol (a22), hydrogenated polybutadiene polyol (a23) and carbon number 5 to 30
At least one polyol selected from the group consisting of polyoxyalkylene polyols (a24) having an oxyalkylene group 2. A non-chargeable polyurethane composition, which is derived from the polyol composition according to claim 1 and an organic polyisocyanate (n), and in which carbon black is dispersed in the polyurethane. 3. A non-chargeable polyurethane foam derived from the polyol composition according to claim 1 and an organic polyisocyanate (n), wherein carbon black is dispersed in a polyurethane foam layer.