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US-12617928-B2 - Carbonaceous filler-containing polyols dispersion

US12617928B2US 12617928 B2US12617928 B2US 12617928B2US-12617928-B2

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 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.

Inventors

  • Takaaki Kanai
  • Hiroyuki Uchino

Assignees

  • SANYO TRADING CO., LTD.

Dates

Publication Date
20260505
Application Date
20230414
Priority Date
20211029

Claims (20)

  1. 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 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 carries carbon black on a carbonaceous material.
  2. 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 2 or less.
  3. 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. 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. 5 . The carbonaceous filler-containing polyols dispersion according to claim 1 , wherein the carbonaceous filler is a carbonaceous material selected from bio carbons.
  6. 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. 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. 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. 9 . A thermosetting resin obtained by reacting the polyols dispersion according to claim 1 as a part or all of raw materials.
  10. 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. 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. 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 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 carries carbon black on a carbonaceous material.
  13. 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 2 or less.
  14. 14 . The thermosetting resin according to claim 12 , wherein the carbonaceous filler has a true specific gravity of 1.5 or less.
  15. 15 . The thermosetting resin according to claim 12 , wherein a dispersant is not included.
  16. 16 . The thermosetting resin according to claim 12 , wherein the carbonaceous filler is a carbonaceous material selected from bio carbons.
  17. 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. 18 . The thermosetting resin according to claim 12 , wherein the carbonaceous material is selected from bio carbons.
  19. 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. 20 . The thermosetting resin according to claim 12 , wherein the thermosetting resin is polyurethane.

Description

The contents of the following Japanese patent application are incorporated herein by reference: NO. 2021-177079 filed in JP on Oct. 29, 2021NO. PCT/JP2022/035840 filed in WO on Sep. 27, 2022 BACKGROUND 1. Technical Field The present invention relates to a polyols dispersion formed by dispersing a carbonaceous filler in polyols that are raw materials for resin or intermediates for resins such as polyurethane or the like without impairing properties such as electrical properties and colorability or the like possessed by the carbonaceous filler, and without using a dispersant. 2. Related Art The polyols in the present invention are polyhydric alcohols that serve as raw materials or intermediates for resins and are used as raw material or intermediates for phenolic resin, urea resin, melamine resin, modified unsaturated polyester resin, alkyd resin, and epoxy resin in addition to polyurethane. Polyurethane is a product of reaction of polyols and polyisocyanates. It has excellent moldability, various forms and a wide range of mechanical properties, so it is used widely, such as for gravure ink, synthetic leather, elastomer, paint, adhesive, coating, cushioning material, or the like. On the other hand, polyurethane also has disadvantages such as being easily broken down by light and heat and being easily charged. In order to make up for these disadvantages, or to add various properties such as conductivity and reinforcement, a procedure of blending a carbonaceous filler has been performed in various uses. A procedure of blending a carbonaceous filler has been performed in various uses for a similar purpose as for the polyurethane for phenolic resin, urea resin, melamine resin, modified unsaturated polyester resin, raw material for alkyd resin, and epoxy resin. However, for example, even if a large amount of carbon black that is a representative carbonaceous filler is blended with polyurethane, since the dispersibility of carbon black and polyols is poor, typically, the upper limit of the blending amount is considered to be about 1%. This is because the carbon black surface has few functional groups that increase affinity with polyols and affinity with the polyols is not good, and particle diameter is small at several tens to several hundreds of nanometers and the carbon black aggregates together in the polyols. Under these circumstances, various proposals have been made to disperse more carbon black that is a representative carbonaceous filler in polyols. A procedure of blending a diene-based copolymer (rubber) or a diene polyol that is well compatible with carbon black has been proposed (for example, Patent Documents 1 and 3). A procedure of adding a dispersant such as a surfactant or the like, a modifying component, or an active component based on a pigment resin dispersion technique to a raw material for polyurethane has also been proposed (for example, Patent Documents 2, 4, 5, 6, and 8). However, when the dispersion or the like is diluted with polyols or mixed with isocyanates, the dispersibility may not be maintained, and the stability in the polyurethane may be impaired. Due to influence of dispersants or the like, there is a risk that expected properties such as weather resistance, conductivity, and reinforcement or the like obtained by fine uniform dispersion may not be sufficiently exhibited by adding carbon black, and there is a concern about clouding of the surface due to bleed out. A procedure for modifying the surface of carbon black has also been proposed (for example, Patent Document 7). However, since it is required to cause a chemical reaction with the surface of the carbon black that is inherently low in reactivity and inactive, the cost is greatly increased, and only a part of the carbon black surface is modified. Therefore, there is still a limit to the amount of carbon black that can be uniformly dispersed in polyol. Note that general carbon black has a specific gravity of 1.5 times or more that of polyols, and it is required to consider the mixing/stirring operation and the storage ability to allow for the difference in specific gravity. PRIOR ART DOCUMENTS Patent Documents Patent Document 1: Japanese Patent Application Publication No. H 1-37407Patent Document 2: Japanese Patent Application Publication No. S 61-23939Patent Document 3: Japanese Patent Application Publication No. H 3-69301Patent Document 4: Japanese Patent No. 3092533Patent Document 5: Japanese Patent No. 4343064Patent Document 6: Japanese Patent No. 4925744Patent Document 7: Japanese Patent No. 5120747Patent Document 8: Japanese Patent No. 6795040 Therefore, the present inventors have performed intensive research on the form of a carbonaceous filler that represents good dispersibility in polyols without chemically changing the surface or using a dispersant or the like that may impair the original properties of the carbonaceous filler, and they have found that that purpose can be achieved by blending a particular carbonaceous