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Definitions

• the present invention relates to a glassy carbon molded product that can be developed for various uses requiring thickness, and a method for producing the glassy carbon molded product.
• glassy carbon which is obtained by carbonizing and firing a curable resin and has a very homogeneous and dense glass-like structure, is widely used.
• amorphous carbon which is obtained by carbonizing and firing a curable resin and has a very homogeneous and dense glass-like structure.
• carbon materials In addition to the characteristics of general carbon materials such as conductivity, chemical stability, heat resistance, and high purity, such carbon materials have excellent features such as impermeability and no shedding of constituent particles. .. Glassy carbon that takes advantage of these features is used in jigs, containers, semiconductor manufacturing equipment members, and the like.
• Patent Document 1 is characterized in that it contains an amorphous carbon component as a skeleton material, contains 0 to 50% of carbon powder in its structure by weight, and has a bulk density of 0.3 to 1.3 g / cm 3.
• the carbonaceous porous body is disclosed.
• amorphous carbon is contained as a skeleton material, the bulk density is 0.3 to 1.0 g / cm 3 , and the proportion of voids on the surface portion thereof is smaller than that of the central portion.
• a polyporous material is disclosed.
• Patent Document 3 is a method of curing a curable resin and firing the obtained cured resin to produce a glassy carbon material, wherein the curable resin is thermoplastic before being cured.
• a method for producing a glassy carbon material, which comprises dissolving a phenol resin, is disclosed.
• thermosetting resin capable of containing 20% by weight or more of water in the state of an initial condensate before curing is carbonized and fired at a temperature of 800 ° C. or higher in an inert atmosphere to obtain a glassy carbon material.
• a method for producing a glassy carbon material in which the thermosetting resin has a predetermined composition and viscosity is disclosed.
• the present invention is as follows: ⁇ Aspect 1> A glassy carbon molded body having a maximum inscribed sphere diameter of 5 mm or more, pores having a diameter of 500 nm or less dispersed in the glassy carbon molded body, and a density of 1. A glassy carbon molded body having a diameter of 1 g / cm 3 or more. ⁇ Aspect 2> The glassy carbon molded product according to Aspect 1, wherein the acoustic impedance is 2 to 6 Millyl.
• a curable resin, a vanishing substance, and a solvent are mixed to be compatible with each other to prepare a precursor composition, and the precursor composition is heat-treated in a non-oxidizing atmosphere. 1.
• the curable resin is carbonized to form the main body of the glassy carbon molded product, and the vanishing substance is eliminated to form the pores of the glassy carbon molded product.
• ⁇ Aspect 9> The method for producing a glassy carbon molded product according to Aspect 7 or 8, wherein the pyrolysis temperature of the vanishing substance is 300 ° C. to 500 ° C.
• ⁇ Aspect 10> The method for producing a glassy carbon molded product according to any one of aspects 7 to 9, wherein the precursor composition further contains a carbonaceous powder.
• ⁇ Aspect 11> The method for producing a glassy carbon molded product according to any one of aspects 7 to 10, wherein the solvent has a boiling point of 150 ° C. or higher.
• the glassy carbon molded body of the present invention has a maximum inscribed sphere diameter of 5 mm or more, has pores having a diameter of 500 nm or less dispersed in the glassy carbon molded body, and has a density of 1.1 g / cm 3
• the above is a glassy carbon molded body.
• a glassy carbon molded product having a large mechanical strength can be obtained due to the presence of pores having a diameter of 500 nm or less and a high density despite the large size.
• the "glassy carbon molded body” means, for example, that the glassy carbon is 50% by volume or more, 60% by volume or more, 70% by volume or more, 80% by volume or more, or 90% by volume of the molded body. It means that it occupies 100% by volume or less, 98% by volume or less, or 95% by volume or less. Further, preferably, the glassy carbon molded body is composed of 90% by volume or more, 95% by volume or more, or 98% by volume or more of glassy carbon and a carbonaceous powder dispersed in the glassy carbon. There is.
• the large diameter of the maximum inscribed sphere of the glassy carbon molded body means that the size of the glassy carbon molded body is large, and the values are 5 mm or more, 7 mm or more, 10 mm or more, 13 mm or more, and 15 mm. It can be 18 mm or more, or 20 mm or more, and can be 100 mm or less, 90 mm or less, 80 mm or less, 70 mm or less, 60 mm or less, 50 mm or less, 40 mm or less, 35 mm or less, 30 mm or less, or 25 mm or less. ..
• the density of the glassy carbon compact may be 1.1 g / cm 3 or more, or 1.2 g / cm 3 or more, and 1.8 g / cm 3 or less, 1.7 g / cm 3 or less, 1.6 g. It may be / cm 3 or less, 1.5 g / cm 3 or less, 1.4 g / cm 3 or less, or 1.3 g / cm 3 or less. This density may be the density measured according to JIS Z 8807.
• the glassy carbon molded product of the present invention may be in the form of a carbon block, a carbon plate, or the like.
• the above-mentioned maximum inscribed sphere diameter is the thickness of the thickest portion of the carbon plate.
• the acoustic impedance of the glassy carbon molded product of the present invention is preferably 2 or more, or 3 or more, from the viewpoint of increasing the mechanical strength of the glassy carbon molded body. Further, it can be 6 mile or less, 5 mile or less, or 4 mile or less.
• the above sound velocity may be, for example, a sound velocity measured in accordance with JIS Z 2353-2003.
• the above acoustic impedance can be adjusted by adjusting the type and content of the carbonaceous powder and the type and content of the vanishing substance, for example, in the method for producing a glassy carbon molded product described below.
• the diameter of the pores of the glassy carbon molded product of the present invention is more than 0 nm, 1 nm or more, 3 nm or more, 5 nm or more, 8 nm or more, 10 nm or more, 15 nm or more, 20 nm or more, 30 nm or more, 40 nm or more, 50 nm or more, 60 nm or more. 70 nm or more, 80 nm or more, or 90 nm or more is preferable from the viewpoint of facilitating degassing of the thermally decomposed gas generated in the carbonization process and facilitating production, and 500 nm or less, 450 nm or less, 400 nm or less, 350 nm.
• the diameter of the pores may be an average diameter measured by, for example, an image analysis method using a scanning electron microscope (SEM), an X-ray CT method, a gas adsorption method, or the like.
• the bending strength of the glassy carbon molded product having the above structure according to JIS K 7074 can be 50 MPa or more, 60 MPa or more, 70 MPa or more, 80 MPa or more, 90 MPa or more, 100 MPa or more, or 110 MPa or more.
• the bending strength can be 250 MPa or less, 240 MPa or less, 230 MPa or less, 220 MPa or less, 210 MPa or less, 200 MPa or less, 190 MPa or less, 180 MPa or less, 160 MPa or less, 150 MPa or less, 140 MPa or less, or 130 MPa or less.
• the flexural strength is measured in accordance with JIS K 7074. Specifically, a load (three-point bending) is applied to one point of the test piece whose both ends are simply supported, and the test piece is bent at a predetermined test speed, and the load at breakage or the maximum load obtained is used.
• L means the distance between fulcrums (mm)
• b means the width of the test piece (mm)
• h means the thickness of the test piece (mm)
• Pb means the load at breakage or the maximum load (N). It should be noted here that the test piece can be cut into arbitrary sizes for measurement.
• the bending elastic modulus of the glassy carbon molded product having the above configuration according to JIS K7074 is 10 GPa or more, 11 GPa or more, 12 GPa or more, 13 GPa or more, 14 GPa or more, 15 GPa or more, 16 GPa or more, or 17 GPa or more. it can. Further, the flexural modulus can be 35 GPa or less, 33 GPa or less, 30 GPa or less, 29 GPa or less, or 28 GPa or less.
• the flexural modulus is measured in accordance with JIS K 7074. Specifically, a load (three-point bending) is applied to one point of a test piece whose both ends are simply supported, the test piece is bent at a predetermined test speed, a load-deflection curve is recorded, and a load-deflection curve is recorded. It refers to the flexural modulus Eb (MPa) obtained by the following formula using the initial gradient of the straight line portion of.
• E b (1/4) x (L 3 / bh 3 ) x (P / ⁇ )
• L is the distance between fulcrums (mm)
• b is the width of the test piece (mm)
• h is the thickness of the test piece (mm)
• P / ⁇ is the slope of the straight part of the load-deflection curve (N /). It means mm). It should be noted here that the test piece can be cut into arbitrary sizes for measurement.
• the glassy carbon molded product of the present invention may further contain a carbonaceous powder dispersed in the glassy carbon.
• Glassy carbon can be obtained, for example, by carbonizing a precursor composition containing a curable resin, a vanishing substance, and a solvent. In detail, a method for producing a glassy carbon molded product will be described.
• the carbonaceous chondrite may be carbon particles dispersed in glassy carbon.
• carbon particles examples include amorphous carbon powder, graphene, carbon nanotubes, graphite, carbon black and the like. These may be used alone or in combination.
• the shape of the carbon particles is not particularly limited, and may be, for example, a flat shape, an array shape, a spherical shape, or the like.
• the average particle size of carbon particles shall be 10 nm or more, 20 nm or more, 30 nm or more, 50 nm or more, 70 nm or more, 100 nm or more, 200 nm or more, 300 nm or more, 500 nm or more, 700 nm or more, 1 ⁇ m or more, 2 ⁇ m or more, or 3 ⁇ m or more. It can also be 20 ⁇ m or less, 18 ⁇ m or less, 15 ⁇ m or less, 13 ⁇ m or less, 10 ⁇ m or less, or 7 ⁇ m or less.
• the average particle diameter means the median diameter (D50) calculated by the volume standard in the laser diffraction method.
• the average particle size of the carbon particles is 10 nm or more, dispersion can be facilitated and thickening can be suppressed, and as a result, filling into the mold and defoaming treatment can be facilitated. Further, when the average particle size of the carbon particles is 20 ⁇ m or less, the precipitation of the carbon particles can be suppressed, and as a result, the dispersion can be facilitated.
• the content of carbonaceous powder in the glassy carbon molded body is 50% by weight or less, 45% by weight or less, 40% by weight or less, 35% by weight or less, and 30% by weight based on the total weight of the glassy carbon molded body.
• it can be 25% by weight or less, 20% by weight or less, or 15% by weight or less, and can be 5% by weight or more, 7% by weight or more, or 10% by weight or more.
• the content of the carbonaceous powder is 50% by weight or less, the glassy carbon molded product can be molded more easily. Further, when the content of the carbonaceous powder is 5% by weight or more, good mechanical properties of the glassy carbon molded product can be ensured.
• the method of the present invention for producing a glassy carbon molded article includes: A curable resin, a vanishing substance, and a solvent are mixed to be compatible with each other to prepare a precursor composition, and the precursor composition is heat-treated in a non-oxidizing atmosphere to obtain a curable resin. To carbonize to form the main body of the glassy carbon molded product and to eliminate the vanishing substance to form the pores of the glassy carbon molded product.
• the present inventors have found that a glassy carbon molded body having a maximum inscribed sphere diameter of 5 mm or more can be produced by the above method. Specifically, due to the compatibility of the curable resin, the vanishing substance and the solvent, the path through which gas can escape from the inside of the carbon precursor at the stage of carbonization is biased to the entire carbon precursor. As a result, the stress associated with the accumulation of gas can be satisfactorily suppressed, so that the above-mentioned glassy carbon molded product can be produced without causing cracks.
• the density of the glassy carbon molded product produced as described above can be 1.1 g / cm 3 or more, or 1.2 g / cm 3 or more, and 1.8 g / cm 3 or less, 1.7 g. It can be / cm 3 or less, 1.6 g / cm 3 or less, 1.5 g / cm 3 or less, 1.4 g / cm 3 or less, or 1.3 g / cm 3 or less.
• the method of the present invention may further include molding the precursor composition by putting the precursor composition into a mold and curing it.
• the precursor composition is prepared by mixing a curable resin, a vanishing substance, and a solvent to make them compatible with each other.
• Mixing can be performed by a known stirring means such as a disper.
• Carbonaceous chondrite may be further added to the precursor composition.
• the carbonaceous chondrite may be added together with the curable resin, the vanishing substance, and the solvent, or may be added after mixing these.
• the molding of the precursor composition can be carried out by putting the precursor composition into a mold and curing it.
• the precursor composition is heat-treated in a non-oxidizing atmosphere to carbonize the curable resin to form the main body of the glassy carbon molded body, and to eliminate the vanishing substance.
• the purpose is to form the pores of the glassy carbon molded body.
• the heat treatment is, for example, 800 ° C. or higher, 850 ° C. or higher, or 900 ° C. or higher, and 3000 ° C. or lower, 2800 ° C. or lower, 2500 ° C. or lower, 2200 ° C. or lower, 2000 ° C. or lower, 1800 ° C. or lower, 1600 ° C. or lower, 1500 ° C.
• the temperature can be raised to 1400 ° C. or lower, 1300 ° C. or lower, 1200 ° C. or lower, 1150 ° C. or lower, 1100 ° C. or lower, 1050 ° C. or lower, or 1000 ° C. or lower.
• a curable resin is generally a resin that is three-dimensionally crosslinked and cured.
• the curable resin of the present invention uses a curable resin that can be carbonized without thermal decomposition when heated to 1000 ° C. in a non-oxidizing atmosphere and has a carbonization yield of 40% or more. Is preferable.
• curable resin examples include one or two curable precursors such as furan resin, phenol resin, epoxy resin, furan-phenolic resin, phenol-modified furan cocondensate, melamine resin, urea resin, and furan-urea resin. More than seeds can be used.
• an organic sulfonic acid-based curing agent such as paratoluenesulfonic acid can be used as the curing agent. ..
• Dissolvable substances are substances that can be eliminated by thermal decomposition at a given thermal decomposition temperature, especially organic substances.
• This thermal decomposition temperature can be obtained by TG measurement under a nitrogen atmosphere at a heating rate of 10 ° C./min. Specifically, at the weight loss rate W (%) at each measurement temperature T, the peak temperature of dW / dT when the dW / dT at each temperature is obtained and plotted can be set as the thermal decomposition temperature of the substance. it can.
• the thermal decomposition temperature of the vanishing substance is preferably a temperature lower than the temperature at which the above-mentioned curable resin is carbonized, and is, for example, 500 ° C. or lower, 480 ° C. or lower, 450 ° C. or lower, or 420 ° C. or lower. preferable.
• the thermal decomposition temperature is the above temperature, it is possible to satisfactorily construct a path for removing the gas made of the low molecular weight substance generated in the carbonization temperature range of the curable resin.
• the thermal decomposition temperature is preferably 300 ° C. or higher, 320 ° C. or higher, 350 ° C. or higher, or 380 ° C. or higher.
• the thermal decomposition temperature of 300 ° C. or higher suppresses the rapid shrinkage of the precursor composition due to the formation of a large amount of low molecular weight material at the initial temperature of carbonization, and as a result, the above path is closed. It can be suppressed.
• polyvinyl butyral PVB
• polyvinylpyrrolidone polyethylene glycol and the like
• polyethylene glycol polyethylene glycol
• the molecular weight of the vanishing substance is 400 or more, 600 or more, 800 or more, 1000 or more, 3000 or more, 5000 or more, 8000 or more, 10000 or more, 12000 or more, 14000 or more. , Or 17,000 or more, and 100,000 or less, 90,000 or less, 80,000 or less, 70,000 or less, 60,000 or less, 50,000 or less, 45,000 or less, 40,000 or less, 35,000 or less, 30,000 or less, or 25,000 or less. It is preferable from the viewpoint of keeping it within the above range.
• the weighted average of the molecular weights weighted by the content of each component may be within the above range.
• the content of the vanishing substance may be more than 0% by weight, 1% by weight or more, 2% by weight or more, 3% by weight or more, or 4% by weight or more based on the weight of the solid content of the precursor composition.
• the glass is preferably 10% by weight or less, 9% by weight or less, 8% by weight or less, 7% by weight or less, 6% by weight or less, or 5% by weight or less. It is preferable from the viewpoint of improving the mechanical strength of the carbon compact.
• the "weight of the solid content of the precursor composition” means the total weight of the curable resin and the vanishing substance.
• the solvent of the present invention is a solvent that can be compatible with a curable resin and a vanishing substance.
• compatible means an undissolved substance when the precursor composition is observed with an optical microscope at a magnification of 100 times or more before curing and before the addition of carbonaceous chondrite. It means a state that cannot be confirmed.
• the boiling point of the solvent is 150 ° C. or higher from the viewpoint of maintaining the compatible state with the vanishing substance for a long time and, as a result, forming a good path.
• This boiling point may be 150 ° C. or higher, 160 ° C. or higher, 170 ° C. or higher, 180 ° C. or higher, 190 ° C. or higher, or 200 ° C. or higher, and may be 300 ° C. or lower, 280 ° C. or lower, or 250 ° C. or lower. ..
• solvent for example, alcohol such as benzyl alcohol, N-methyl-2-pyrrolidone (NMP), dimethyl sulfoxide (DMSO), 1,3-dimethyl-2-imidazolidinone (DMI), N, N-dimethylformamide ( Aproton polar solvents such as DMF), N, N-dimethylacetamide (DMAC), glycol solvents such as propylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol having a molecular weight of 600 or less, 3-methoxy-3-methyl Examples thereof include glycol ethers such as -1-butanol (Solvent). These may be used alone or in admixture of two or more.
• the combination of the curable resin / thermosetting organic substance / solvent that satisfies the above solubility parameter conditions for example, the following combinations can be adopted: Furan resin / polyethylene glycol / benzyl alcohol + tetraethylene glycol, furan resin / polyethylene glycol / benzyl alcohol + triethylene glycol, furan resin / polyethylene glycol / benzyl alcohol + diethylene glycol, furan resin / polyvinylpyrrolidone / benzyl alcohol + tetraethylene glycol, Phenol resin / polyethylene glycol + PVB / tetraethylene glycol + benzyl alcohol, furan resin / polyethylene glycol / NMP. These are examples, and can be adopted as long as they have a uniform combination of compatible states.
• Example 1 120 parts by weight of furan resin (VF303, Hitachi Kasei Co., Ltd.) as a curable resin, 14 parts by weight of polyethylene glycol (PEG) (pyrolysis temperature 426 ° C.) having a molecular weight of 11000 as a vanishing substance, and benzyl alcohol as a solvent.
• PEG polyethylene glycol
• BA (boiling point 205 ° C.) 26 parts by weight and tetraethylene glycol (TEG) (boiling point 328 ° C.) 40 parts by weight were blended and stirred well with a disper or the like to obtain a uniform solution.
• the content of the vanishing substance was 10% by weight based on the weight of the solid content of the precursor composition.
• PTS paratoluenesulfonic acid
• the obtained glassy carbon molded product has a pore diameter of about 50 nm, a flexural strength of 80 MPa, a flexural modulus of 19 GPa, and an acoustic impedance of 4.5 Milly measured by an image analysis method using an SEM. Met.
• Example 2 As a curable resin, 126 parts by weight of furan resin (VF303, Hitachi Kasei Co., Ltd.), 10 parts by weight of polyethylene glycol (pyrolytic temperature 426 ° C.,) having a molecular weight of 20000 as a pyrolytic organic substance, and Solfit (boiling point) as a solvent. 20 parts by weight (174 ° C.) and 30 parts by weight of triethylene glycol (TrEG) (boiling point 287 ° C.) were blended and stirred well with a disper or the like to obtain a uniform solution. The content of the vanishing substance was 7% by weight based on the weight of the solid content of the precursor composition.
• the obtained glassy carbon molded product has a pore diameter of about 50 nm, a flexural strength of 96 MPa, a flexural modulus of 17.5 GPa, and an acoustic impedance of 4.4 Mrayl measured by an image analysis method using an SEM. It was a molded body.
• Example 3 80 parts by weight of furan resin (VF303, Hitachi Kasei Co., Ltd.) as a curable resin, 2 parts by weight of polyethylene glycol (pyrolysis temperature 426 ° C.) having a molecular weight of 20000 as a thermally decomposable organic substance, and polyethylene glycol having a molecular weight of 600 (pyrolysis temperature 390). 2 parts by weight (° C.), 10 parts by weight of benzyl alcohol (boiling point 205 ° C.) and 10 parts by weight of diethylene glycol (DEG) (boiling point 244 ° C.) as a solvent were mixed and stirred well with a disper or the like to obtain a uniform solution.
• furan resin VF303, Hitachi Kasei Co., Ltd.
• polyethylene glycol pyrolysis temperature 426 ° C.
• polyethylene glycol polyethylene glycol having a molecular weight of 20000 as a thermally decomposable organic substance
• amorphous carbon powder (average particle size 10 ⁇ m) was added to the obtained solution, and this was uniformly dispersed by a bead mill, a dispenser or the like. 3 parts by weight of p-toluenesulfonic acid as a curing agent was added to the obtained dispersion, and the mixture was further stirred and homogenized and defoamed under reduced pressure to obtain a precursor composition.
• This precursor composition was filled into a mold having a diameter of 100 mm and a thickness of 30 mm and cured. The cured precursor composition was removed from the mold and heat-treated to a temperature of 1000 ° C. in a nitrogen gas atmosphere to obtain a glassy carbon molded body having a diameter of 80 mm and a thickness of 25 mm.
• the obtained glassy carbon molded body had a pore diameter of about 50 nm, a flexural strength of 115 MPa, a flexural modulus of 24 GPa, and an acoustic impedance of 5.3 Milly measured by an image analysis method using an SEM.
• Comparative Example 1 >> 120 parts by weight of furan resin (VF303, Hitachi Kasei Co., Ltd.) as a curable resin, 26 parts by weight of benzyl alcohol (boiling point 205 ° C.) and 40 parts by weight of tetraethylene glycol (boiling point 328 ° C.) as a solvent are blended and used with a disper or the like. Stir well to obtain a uniform solution.
• furan resin VF303, Hitachi Kasei Co., Ltd.
• a precursor composition 1 part by weight of paratoluenesulfonic acid as a curing agent was added, and the mixture was further stirred and homogenized and defoamed under reduced pressure to obtain a precursor composition.
• This precursor composition was filled into a mold having a diameter of 100 mm and a thickness of 30 mm and cured.
• the cured precursor composition was removed from the mold and heat-treated to a temperature of 1400 ° C. in a nitrogen gas atmosphere, large cracks and fine cracks were formed inside, and a glassy carbon molded product could not be obtained. Therefore, the pore diameter, flexural strength, flexural modulus, and acoustic impedance could not be measured.
• Comparative Example 2 >> 70 parts by weight of furan resin (VF303, Hitachi Kasei Co., Ltd.) as a curable resin, 20 parts by weight of polymethylmethacrylate (PMMA) (particle size 5 ⁇ m, pyrolysis temperature 400 ° C.) as a thermally decomposable organic substance, and as a carbonaceous powder 10 parts by weight of graphite (scaly graphite, Nippon Graphite Co., Ltd., average particle size 5 ⁇ m) was added and uniformly dispersed by a bead mill, a dispenser or the like.
• furan resin VF303, Hitachi Kasei Co., Ltd.
• PMMA polymethylmethacrylate
• graphite carbonaceous powder
• a precursor composition 1 part by weight of p-toluenesulfonic acid as a curing agent was added, and the mixture was further stirred and homogenized and defoamed under reduced pressure to obtain a precursor composition.
• This precursor composition was filled into a mold having a diameter of 100 mm and a thickness of 30 mm and cured.
• the cured precursor composition was removed from the mold and heat-treated to a temperature of 1000 ° C. in a nitrogen gas atmosphere, the carbides were cracked and a glassy carbon molded product could not be obtained. Therefore, the flexural strength, flexural modulus, and acoustic impedance could not be measured.
• Comparative Example 3 >> 126 parts by weight of furan resin (VF303, Hitachi Kasei Co., Ltd.) as a curable resin, 20 parts by weight of Solfit (boiling point 174 ° C) and 30 parts by weight of triethylene glycol (boiling point 287 ° C) as a solvent are blended and used with a disper or the like. Stir well to obtain a uniform solution.
• furan resin VF303, Hitachi Kasei Co., Ltd.
• Table 1 shows the configurations and evaluation results of Examples and Comparative Examples.
• solution state when the precursor composition before curing and before the addition of carbonaceous chondrite is observed with an optical microscope at a magnification of 100 times or more, an undissolved substance cannot be confirmed. Is described as “compatible”, and if not, it is described as “incompatible”.
• Comparative Examples 1 and 3 using the precursor composition containing no vanishing substance and Comparative Example 2 using the precursor composition containing no solvent glass having a thickness of 20 mm or more was used. The shaped carbon molded product could not be produced.

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