CARBONACEOUS FILLER-CONTAINING POLYOLS DISPERSION

Abstract

A carbonaceous filler-containing polyols dispersion obtained by blending a carbonaceous filler with polyols, wherein the carbonaceous filler has a component content (anhydrous basis weight) with 80% or more fixed carbon, less than 8% volatile content, and less than 4% ash content by industrial analysis, the carbonaceous filler has a phenolic hydroxy group per external specific surface area of 0.005 mmol/m.sup.2 or more, the carbonaceous filler is a carbon based material having an average particle diameter (D50) of 0.1 to 100 μm, and the carbonaceous filler-containing polyols dispersion is characterized by including 1 to 80 parts by weight of the carbonaceous filler with respect to 100 parts by weight of the polyols.

Claims

1. A carbonaceous filler-containing polyols dispersion obtained by blending a carbonaceous filler with polyols, wherein the carbonaceous filler has a component content (anhydrous basis weight) with 80% or more fixed carbon, less than 8% volatile content, and less than 4% ash content, the carbonaceous filler has a phenolic hydroxy group per external specific surface area of 0.005 mmol/m.sup.2 or more, and the carbonaceous filler is a carbon based material having an average particle diameter (D50) of 0.1 to 100 μm.

2. The carbonaceous filler-containing polyols dispersion according to claim 1, wherein the carbonaceous filler has a carboxyl group per external specific surface area of 0.001 mmol/m.sup.2 or less.

3. The carbonaceous filler-containing polyols dispersion according to claim 1, wherein the carbonaceous filler has a true specific gravity of 1.5 or less.

4. The carbonaceous filler-containing polyols dispersion according to claim 1, wherein the carbonaceous filler is dispersed in the polyols without using a dispersant.

5. The carbonaceous filler-containing polyols dispersion according to claim 1, wherein the carbonaceous filler is a carbonaceous material selected from bio carbons.

6. The carbonaceous filler-containing polyols dispersion according to claim 1, wherein the carbonaceous filler is a bio raw material mainly composed of lignin/cellulose/hemicellulose or a carbonaceous material obtained by carbonizing low carbonization lignite at 1000° C. or less.

7. The carbonaceous filler-containing polyols dispersion according to claim 1, wherein the carbonaceous filler is obtained by carrying carbon black on a carbonaceous material.

8. The carbonaceous filler-containing polyols dispersion according to claim 1, wherein 1 to 80 parts by weight of the carbonaceous filler is included with respect to 100 parts by weight of the polyols.

9. A thermosetting resin obtained by reacting the polyols dispersion according to claim 1 as a part or all of raw materials.

10. A phenolic resin, urea resin, melamine resin, modified unsaturated polyester resin, raw material for alkyd resin, or epoxy resin obtained by reacting the polyols dispersion according to claim 1 as a part or all of raw materials.

11. A polyurethane obtained by mixing the polyols dispersion according to claim 1 with one or more types of polyols selected from a group formed of polyester polyol, polyether polyol, polycarbonate polyol, polymer polyol, a modified product or mixture thereof, and reacting with polyisocyanates.

12. A thermosetting resin in which a carbonaceous filler is dispersed, wherein the carbonaceous filler has a component content (anhydrous basis weight) with 80% or more fixed carbon, less than 8% volatile content, and less than 4% ash content, the carbonaceous filler has a phenolic hydroxy group per external specific surface area of 0.005 mmol/m.sup.2 or more, and the carbonaceous filler is a carbon based material having an average particle diameter (D50) of 0.1 to 100 μm.

13. The thermosetting resin according to claim 12, wherein the carbonaceous filler has a carboxyl group per external specific surface area of 0.001 mmol/m.sup.2 or less.

14. The thermosetting resin according to claim 12, wherein the carbonaceous filler has a true specific gravity of 1.5 or less.

15. The thermosetting resin according to claim 12, wherein a dispersant is not included.

16. The thermosetting resin according to claim 12, wherein the carbonaceous filler is a carbonaceous material selected from bio carbons.

17. The thermosetting resin according to claim 12, wherein the carbonaceous filler is a bio raw material mainly composed of lignin/cellulose/hemicellulose or a carbonaceous material obtained by carbonizing low carbonization lignite at 1000° C. or less.

18. The thermosetting resin according to claim 12, wherein the carbonaceous filler carries carbon black on a carbonaceous material selected from bio carbons.

19. The thermosetting resin according to claim 12, wherein the thermosetting resin is phenolic resin, urea resin, melamine resin, modified unsaturated polyester resin, raw material for alkyd resin, or epoxy resin.

20. The thermosetting resin according to claim 12, wherein the thermosetting resin is polyurethane.

Description

EXAMPLE

[0064] Below, the present invention is described in detail with reference to an example.

[0065] For the carbonaceous filler, the carbonaceous material below was used.

Carbonaceous material CC1: Pulverized charcoal product derived from pine wood carbonized at 550° C. (manufactured by CarbonNeat, Sanyo Trading Sales “Neat90”)

[0066] Average particle diameter (D50) 5 μm

[0067] External specific surface area (STSA) 1 m.sup.2/g

[0068] True specific gravity 1.12

[0069] Industrial analysis of fixed carbon 96.1%, volatile content 1.8%, ash content 2.1%, (anhydrous basis weight)

[0070] Ph-type OH group amount per external specific surface area: 0.080 mmol/m.sup.2

[0071] COOH group amount per external specific surface area: measurement limitation or less

Carbonaceous material CC2: Pulverized charcoal product derived from mixed wood carbonized at 600° C.

[0072] Average particle diameter (D50) 5 μm

[0073] External specific surface area (STSA) 0.5 m.sup.2/g

[0074] True specific gravity 1.1

[0075] Industrial analysis of fixed carbon 90.3%, volatile content 2.5%, ash content 7.2% (anhydrous basis weight)

[0076] Ph-type OH group amount per external specific surface area 0.005 mmol/m.sup.2

[0077] COOH group amount per external specific surface area: measurement limitation or less

[0078] For the carbon black, the materials below were used.

Carbon black CB1: grade equivalent of “N220”

[0079] Average particle diameter (D50) 0.02 μm (20 nm)

[0080] True specific gravity 1.8 to 1.9

[0081] Volatile content 1.0%, ash content 0.03%

[0082] Nitrogen adsorption specific surface area (N2SA) 120 m.sup.2/g

[0083] External specific surface area (STSA) 106 m.sup.2/g

[0084] DBP absorption 114 mL/100 g

[0085] Ph-type OH group amount per external specific surface area: 0.00085 mmol/m.sup.2

[0086] COOH group amount per external specific surface area: 0.00028 mmol/m.sup.2

Carbon black CB2: grade equivalent of “N990”

[0087] Average particle diameter (D50) 0.3 μm (300 nm)

[0088] True specific gravity 1.9

[0089] Volatile content 0.5%, ash content 0.1%

[0090] Nitrogen adsorption specific surface area (N2SA) 8 m.sup.2/g

[0091] External specific surface area (STSA) 8 m.sup.2/g

[0092] DBP absorption 40 mL/100g

[0093] Ph-type OH group amount per external specific surface area: 0.00025 mmol/m.sup.2

[0094] COOH group amount per external specific surface area: measurement limitation or less

Synthesis Example 1

[0095] 20 g of carbonaceous material “CC2” and 4 g of carbon black “CB1” were placed in a mortar, and the particles were brought into contact with each other under a pressure of 2 kg for 10 minutes to obtain a carbon black-carrying carbonaceous filler used in Example 9.

Synthesis Example 2

[0096] 40 g of carbonaceous material “CC1” and 8 g of carbon black “CB2” were placed in a mortar, and the particles were brought into contact with each other under a pressure of 2 kg for 10 minutes to obtain a carbon black-carrying carbonaceous filler used in Example 10.

Examples 1 to 10, Comparative Examples 1 to 4

[0097] A carbonaceous filler and carbon black CB1 and CB2 for comparison were used, blended with polyols, and after dispersibility was confirmed, they were blended with polyisocyanates for Examples 5 to 8 to produce polyurethane.

[0098] For polyols and polyisocyanates, the materials below were used.

Polyol B1: Polyether polyol “P-3000” manufactured by ADECA
Polyol B2: Foam urethane resin for casting A liquid polyol manufactured by Nissin Resin
Polyol B3: Urethane resin for casting “Gummy Cast” A liquid polyol manufactured by Nissin Resin
Polyisocyanate C1: Foam urethane resin for casting B liquid diisocyanate manufactured by Nissin Resin
Polyisocyanate C2: Polyurethane resin for casting “Gummy Cast” B liquid modified isocyanate manufactured by Nissin Resin

[0099] According to the formulation shown in Table 1, the polyol and the carbonaceous filler were put in order into a 500 mL polyethylene beaker and stirred with a glass rod for 3 minutes. For Examples 8 to 10, after stirring for 3 minutes, a predetermined amount of polyisocyanates was added, further stirred for 1 minute, and allowed to stand at room temperature.

[0100] The dispersibility of the carbonaceous filler in the polyols was evaluated according to the following criteria.

⊚: It has flowability and is dispersed well.
o: Although there is an increase in viscosity and there is no flowability, it is dispersed.
x: Gel-like and undispersed lumps are generated, and it does not disperse.
xx: It separates and settles from the polyols, and it does not disperse.

[0101] In both Examples 9 and 10, when the carbonaceous filler was dispersed in the polyol liquid, the carbon black did not settle or aggregate in the polyol liquid, and it could be confirmed that the carbon black was carried on the carbonaceous material.

[0102] The polyurethane produced in Examples 5 to 8 were molded and evaluated for appearance according to the criteria below.

[0103] o: Aggregation derived from the carbon black could not be confirmed at all, and the appearance was good.

[0104] Δ: Slight aggregation could be confirmed, but there was no problem in practical use and appearance.

[0105] x: Aggregation of carbon black occurred.

TABLE-US-00001 EX- EX- EX- EX- EX- EX- EX- EX- EX- EX- COMPAR- COMPAR- COMPAR- COMPAR- AM- AM- AM- AM- AM- AM- AM- AM- AM- AM- ATIVE ATIVE ATIVE ATIVE PLE PLE PLE PLE PLE PLE PLE PLE PLE PLE EXAM- EXAM- EXAM- EXAM- 1 2 3 4 5 6 7 8 9 10 PLE 1 PLE 2 PLE 3 PLE 4 CARBONACEOUS  40  60 100  60  60 100  40 MATERIAL CC1 CARBONACEOUS 100  60  20 MATERIAL CC2 CB 1  4  20  10 CB 2  8  20  4 POLYOL B1 100 100 100 100 100 100 100 100 100 POLYOL B2 100 100 100 POLYOL B3 100 100 CARBONACEOUS B1 B2 B3 B4 B5 B6 B7 B8 B9 B10 B11 B12 B13 B14 FILLER DISPERSION POLYISOCYANATE C1 40 40 POLYISOCYANATE C2 40 40 DISPERSIBILITY ⊚ ⊚ ⊚ ⊚ ⊚ ⊚ ◯ ◯ ⊚ ⊚ X X X XX MOLDED PRODUCT — — — — ◯ ◯ ◯ Δ — — — — — — APPEARANCE