JPH10195289A - Polyol composition, polyurethane composition and urethane foam - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a polyol composition low in viscosity and good in handleability, and useful for polyurethanes capable of exhibiting an excellent conductivity and conductivity sustainability and used for producing conductive rollers, conductive coatings, etc., by dispersing carbon black in a specific polyol composition. SOLUTION: This polyol composition having a viscosity of 2000-60000mPa.s and useful for using non-antistatic polyurethanes is obtained by dispersing (B) carbon black in (A) a polyol. The polyol composition preferably is obtained by dissolving (C) 0.3-5 pts.wt. of a polystyrene oligomer having a weight-average mol.wt. of 400-50000 in 100 pts.wt. of the component A comprising a polyoxy (2 or 3C) alkylene polyol (e.g. the propylene oxide adduct of an alcohol or amine) and subsequently dispersing 1-20 pts.wt. of the component B in the solution.

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-chargeable polyurethane, there has been known a method in which a conductive compound 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 viscosity of the polyurethane raw material is increased due to the compounding of carbon black, the fluidity is lost, and the 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 The polyol composition in which carbon black is dispersed not only improves the problem of fluidity, but the polyurethane obtained by reacting with the organic polyisocyanate using this composition is found to have improved conductivity. Reached. That is, the present invention provides the following polyol composition, non-chargeable polyurethane composition and non-chargeable polyurethane foam.

A polyol composition for producing a non-chargeable polyurethane comprising carbon black (b) dispersed in polyol (a), wherein polyol (a) has an oxyalkylene group having 2 and / or 3 carbon atoms. It is composed of a polyoxyalkylene polyol, and a polystyrene oligomer (c) having a weight-average molecular weight of 400 to 5,000 is further dissolved in the polyol (a). (B) 1 to 20 parts by mass per 100 parts by mass of (a) , (C) is 0.3 to 5 parts by mass, and the viscosity is 2,000 to 60,000 mPa · s.
A polyol composition, characterized in that:

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) used in the present invention includes compounds having an active hydrogen atom such as alcohols, ammonia, amines, polyhydric phenols, and polycarboxylic acids, each having 2 and / or carbon atoms. And polyoxyalkylene polyols to which an alkylene oxide (3) is added.

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, etc.), 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 compounds may be used in combination.

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

[0011] As the polyol (a), preferred are alcohols or amines, PO alone or P
A compound obtained by adding O and EO in combination, particularly preferably at least one of ethylene glycol, propylene glycol, glycerin, trimethylolpropane, pentaerythritol, monoethanolamine, diethanolamine, triethanolamine and ethylenediamine To PO alone or in combination with PO and EO. When PO and EO are added in combination, the EO content is usually 30% by weight or less, preferably 20% by weight or less.

The average number of functional groups of the polyol (a) is usually 2 to 5, preferably 2 to 4. The active hydrogen equivalent is
Usually 200 to 5000, preferably 1000 to 3000
It is. The average number of functional groups is less than 2 or the active hydrogen equivalent is 5
When it exceeds 000, when it is used for a polyurethane foam, the residual compression ratio and the residual heat / moisture ratio become large, and when it is used for a polyurethane elastomer, the reactivity is low and the curability becomes insufficient. On the other hand, when the average number of functional groups is 5
When the active hydrogen equivalent is more than 200 or less than 200, the polymer forming the foam becomes rigid and the polyurethane foam becomes brittle when used for polyurethane foam, and the elongation becomes small when used for polyurethane elastomer.

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 and the nitrogen adsorption specific surface area (ASTM D3037) of the carbon black (b) are important, and the particle size is 10 to 60 nm and the nitrogen adsorption specific surface area is It is preferable to use one having 30 to 1,000 m ² / g.

The polystyrene oligomer (c) has a weight average molecular weight of usually 400 to 5,000, 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 inside.

(A) (b) is usually 1 per 100 parts by mass.
To 20 parts by mass, preferably 1 to 10 parts by mass,
(C) is usually 0.3 to 5 parts by mass, preferably 0.5 to 3 parts by mass.
Parts by weight. Outside this range, it is difficult to achieve both viscosity and conductivity of the composition.

In producing the polyurethane composition of the present invention or the polyurethane foam, a known polymer polyol may be used in combination with the polyol composition of the present invention, if necessary, as a polyol component. Known polymer polyols that can be used in combination include those obtained by polymerizing and stably dispersing a vinyl monomer such as acrylonitrile or styrene in the presence of a radical polymerization initiator in at least one of the above-mentioned polyols (a) or other polyols. No. 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 one 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, buret group, uretonimine group, isocyanurate group, oxazolidone group-containing modified product); and a mixture of two or more of these. Preferred among these is TDI.

Isocyanate index [Equivalent ratio of NCO group / active hydrogen atom-containing group × 100] when producing the polyurethane composition or polyurethane foam of the present invention.
Is usually 70 to 140, preferably 85 to 120, particularly preferably 95 to 115. Further, the isocyanate index is set to be much higher than the above range (for example, 300 to 1).
000 or more), it is also possible to incorporate polyisocyanurates into the polyurethane.

When producing the polyurethane composition or polyurethane foam of the present invention, if necessary, known catalysts, foam stabilizers, chain extenders and / or cross-linking agents which are usually used for the production of polyurethane can be used. . Examples of the catalyst include:-metal salts of carboxylic acids [sodium acetate, potassium octylate, lead octylate, zinc octylate, cobalt naphthenate, stannas dioctoate, etc.];-alkoxides or phenoxides of alkali metals or alkaline earth metals [Sodium methoxide, sodium phenoxide, etc.];-Tertiary amines [triethylamine, triethylenediamine, N-methylmorpholine, dimethylaminomethylphenol, etc.];-Quaternary ammonium salts [tetraethylammonium hydroxide, etc.];-Imidazoles [ Imidazole, 2-ethyl-4-methylimidazole, etc.]; and organometallic compounds containing metals such as tin and antimony [tetraphenyltin, tributylantimony oxide, etc.]. Preferred of these are:
Tertiary amines, metal salts of carboxylic acids containing tin or lead, organometallic compounds and combinations of two or more of these.

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

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.

In producing the polyurethane composition and the polyurethane foam of the present invention, a flame retardant and other additives can be used if necessary. Melamines as flame retardants,
Phosphate esters, halogenated phosphoric acid esters, phosphazene derivatives and the like can be mentioned. Other additives include a reaction retarder, an internal release agent, an antioxidant, an antioxidant,
Known additives such as a plasticizer, a bactericide, and a filler are included.

The polyurethane composition and the polyurethane foam of the present invention can be produced by a conventionally known polyurethane or polyurethane foam forming method, and any one of a one-shot method, a prepolymer method and a quasi-prepolymer method can be applied. The polyurethane foam production method may be a conventionally known method, a slab method,
Any of a hot cure method, a cold cure method, a RIM method, molding by an open mold, integral molding with a composite material, an on-site construction method, a spray method, a casting method, injection, coating, impregnation, etc. can be applied. In particular,
JP-B-39-24737, JP-B-47-15108
JP-A-46-5750, JP-A-55-13341
No. 7, each method for producing a foam described in JP-A No. 7-49;
No. 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 used, equivalent ratios, addition amounts, and the like are also described. Can be used. The polyurethane foam of the present invention has a volume resistivity of usually 10 ³ to 10 ⁹ Ω · c.
m.

[0025]

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 Raw Materials Used] Polyol (a): a-1: PO adduct of glycerin, hydroxyl value = 56 a-2: PO and EO adduct of glycerin (EO content: 20%), hydroxyl group Value = 56 a-3: PO and EO adduct of triethanolamine (EO content: 20%), hydroxyl value = 56 Carbon black (b): b-1: Particle diameter of about 25 nm, nitrogen adsorption specific surface area of about 2
15 m ² / g oil furnace carbon black polystyrene oligomer (c): c-1: polystyrene oligomer, weight average molecular weight 2000 organic polyisocyanate (n): T-80: “Coronate T-80” manufactured by Nippon Polyurethane Industry Co., Ltd. (TDI-80, NCO% = 48.28)

Other auxiliaries: Catalyst-1: "Minico L-102" manufactured by Active Materials Chemical Co., Ltd.
0 "(33% diethylene glycol solution of triethylenediamine) Catalyst-2:" Neostan U-28 "(stanas dioctoate) manufactured by Nitto Kasei Co., Ltd. Foam stabilizer-1:" SZ-1142 "manufactured by Nippon Unicar Co., Ltd. Foaming agent-2: "L-5366" manufactured by Nippon Unicar Co., Ltd.

Examples 1 to 5 (a-1) 100 parts, (c-1) 3 parts and (b-1)
Seven parts were mixed with a sand mixer to prepare a carbon-dispersed PPG, and the viscosity (rotor No. 4, 6 rpm) was measured. This carbon-dispersed PPG was prepared as 10x
Foaming was performed with a 10 × 3 cm aluminum mold to obtain a foam molded product. The foam C hardness and volume resistivity were measured. Table 1 shows the results. Similarly, molded articles of Examples 2 to 5 were obtained. The results are shown in Table 1.

[0029]

Table 1------------------------------------------------------------Example −−−−−−−−−−−−−−−− a-1 100 100 100 50 50 a-2 50 a-3 50 c-1 3 1 0.5 0.5 0.5 b-1 7 7 7 7 7 −−− −−−−−−−−−−−−−−−−−−−−−−−−−− Viscosity (mPa ・ s) 12400 24000 41000 39800 38000 −−−−−−−−−−−−−−−−− −−−−−−−−−−−−− Foaming formula Carbon dispersed PPG 100 100 100 100 100 Catalyst-1 0.6 0.6 0.6 0.6 0.6 Water 0.3 0.3 0.3 0.3 0.3 Foaming agent-1 0.1 0.1 0.1 0.1 0.1 Foaming agent- 2 0.2 0.2 0.2 0.2 0.2 Catalyst -2 0.3 0.3 0.3 0.3 0.3 T-80 10.8 10.9 11.0 11.0 11.0--------------------------All Density (g / cm ³ ) 0.30 0.30 0.30 0.29 0.28 C hardness 16 15 15 15 15 Volume resistivity (Ωcm) 1.1E07 8.1E06 3.2E06 5.1E05 2.1E05 −−−−−−−−−−−−−− −−−−−−−− -------

Comparative Examples 1 to 3 By the same operation as in Examples 1 to 5, molded products of Comparative Examples 1 to 3 were obtained. Table 2 shows the results.

[0031]

Table 2 Comparative Example 12 3------------------------------------------a1-1 100 100 100 c-1 0 0 30 b-1 7 7 7 −−−−−−−−−−−−−−−−−−−− Viscosity (mPa ・ s) 71000 10000 22000 −−−−−−− −−−−−−−−−−−−− Foaming formula carphone Dispersed 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 10.3 9.2 −−−−−−−−−−−−−−−−−−−−−− Total density (g / cm ³ ) 0.30 0.29 0.29 C hardness 15 14 16 Volume resistivity (Ω ・(cm) 2.5E07 4.7E09 2.7E11 −−−−−−−−−−−−−−−−−−−−−

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.

[0033]

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. Due to the above effects, the conductive polyurethane obtained by using the polyol composition of the present invention is a conductive roller, a conductive blade, a conductive flooring, a conductive paint, a conductive foam, an antistatic clothing, It is useful as a material for prevention shoes.

Claims (3)

[Claims] 1. A polyol composition for producing a non-chargeable polyurethane comprising carbon polyol (a) dispersed in polyol (a), wherein polyol (a) has an oxyalkylene group having 2 and / or 2 carbon atoms. 3, a polystyrene oligomer (c) having a weight average molecular weight of 400 to 5,000 is further dissolved in the polyol (a), and (b) is 1 to 20 per 100 parts by mass of (a). Parts by mass, (c) is from 0.3 to 5 parts by mass, and the viscosity is from 2,000 to 60,000 mPa · s.
A polyol composition, characterized in that: 2. A non-chargeable polyurethane composition derived from the polyol composition according to claim 1 and an organic polyisocyanate (n), wherein 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.