JPS6238382B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a composition containing an inorganic material powder. More specifically, together with inorganic material powder,
It has good flow properties and is reactive, and by itself,
Or ceramics containing a new granular or powdered phenol formaldehyde resin that exhibits excellent moldability and carbonization yield when mixed with various inorganic material powders, and exhibits various excellent properties such as excellent mechanical properties. The present invention relates to a composition having excellent moldability and suitable for producing inorganic molded bodies such as. Conventionally, novolac resins and resol resins are known as typical phenol formaldehyde resins. Novolac resins usually have a molar ratio of phenol to formaldehyde of, for example, 1.
in the presence of an acid catalyst such as oxalic acid (usually
0.2-2%) by reacting phenol with formalin. The novolac resin obtained by such a method is mainly composed of trimers to pentamers of phenols bonded mainly through methylene groups, contains almost no free methylol groups, and therefore cannot self-react by itself. It has no crosslinking properties and is thermoplastic. Therefore, the novolac resin is reacted under heat with a crosslinking agent which is itself a formaldehyde generator and also an organic base (catalyst) generator, such as hexamethylenetetramine (hexamine), or with a solid acid catalyst and paraformaldehyde, etc. A cured resin can be obtained by mixing with the resin and subjecting it to a heating reaction. Novolak resin is easy to handle in powder form, but when heating and curing a molded product containing a large amount of inorganic material powder, the curing reaction progresses from the surface of the molded product to the inside, and often the inside is not fully cured. Gives no cured product. For this reason, when such a cured product is heated to a higher temperature and subjected to firing, gas is generated internally, causing cracks and gas blisters in the molded product, and as the firing progresses, these cracks and gas blisters occur. This is even more noticeable, and it is extremely difficult to produce inorganic molded bodies of satisfactory quality. Further, resol resins are usually supplied as a solution, and therefore, it is very difficult to remove the solvent and make a molded product by itself because the gelation reaction rapidly progresses during the removal of the solvent and foaming occurs. Therefore, it is common practice to use a filler material to remove the solvent and then mold the material. Therefore, when inorganic material powder is used, solvent removal is relatively easy. However, when such molded products are heated and subjected to curing or firing, the gelation reaction still progresses rapidly, resulting in gas blisters and cracks as in the case of the novolac resins mentioned above, which deteriorates strength and hardness. It is extremely difficult to produce inorganic molded bodies of satisfactory quality. In addition, in relatively recent years, novolak resins have been heated at high temperatures to obtain products with a fairly high degree of condensation, and this has been purified to separate and remove low condensates, resulting in phenol groups containing 7 to 10 methylene groups. A relatively high condensate bonded by groups is obtained, and this is heated and melt-spun to form a novolak resin fiber, which is immersed in a mixed aqueous solution of hydrochloric acid and formaldehyde, and then heated gradually from room temperature for a long period of time. A method of producing cured novolak resin fibers was proposed by proceeding the curing reaction from the outside of the fibers (Japanese Patent Publication No. 1983-1999).
No. 11284). However, cutting or pulverizing the cured novolac fiber produced as described above is not only expensive, but also cannot be made into a granular or powdered material with good flow characteristics as a molding material. It is difficult to produce a molded body with uniform dispersion. In addition, in recent years, a hydrophilic polymer compound is added to a condensate obtained by reacting phenols and formaldehyde in the presence of at least a nitrogen-containing compound, and the reaction is performed to produce granular or powdered resin. Although a method has been announced (Special Publication 1973-
42077), the non-gelled resin obtained by this method contains a large amount of free phenol, approximately 5-6% (Examples 1 to 4), and the gelled product (Example 5) is an extremely hard non-gelled product. In addition to being a reactive resin, the resin also contains a nitrogen-containing compound and a hydrophilic polymer compound used as a catalyst. Therefore, there is a drawback that cracks and gas blisters occur in the inorganic molded product obtained by curing or firing the molded product obtained using this as a filler. Furthermore, a method is known in which a prepolymer obtained by reacting phenol and formaldehyde in a basic aqueous solution is mixed with a protective colloid and coagulated into inert solid beads under acidic conditions (Japanese Patent Publication No. 51
-13491), which corresponds to the so-called cured resol resin product, has no reactivity, and also contains salts, acids, and other protective colloids, so it can also be used as a filler for molded products. The disadvantage is that cracks and gas blisters occur in the inorganic molded product obtained by curing or firing. As mentioned above, attempts have been made to use phenol-formaldehyde resin as a filler in molded products. First of all, it is difficult to obtain it, and it also has the problem that it contains substances that have an undesirable effect on the molded product during curing or firing. The present inventors have previously provided a new granular or powdery phenol formaldehyde resin that does not have the above-mentioned drawbacks and a method for producing the same. Therefore, an object of the present invention is to provide a composition containing a novel granular or powdered resin and an inorganic material powder. Another object of the present invention is to provide a composition with good moldability, which contains a small proportion of a granular or powdered resin with good flow properties together with a large proportion of inorganic material powder. There is a particular thing. Still another object of the present invention is to use a granular or powdered resin that is reactive alone or with other resins, so that cracks and gas blisters are reduced by hardening or sintering, and internal It is an object of the present invention to provide a composition capable of producing a homogeneous inorganic molded article with almost no unevenness in quality from the outside. Still another object of the present invention is to provide a composition that provides an inorganic molded article exhibiting mechanical properties such as excellent impact properties or excellent electrical properties. Still another object of the present invention is to provide a composition that provides an inorganic molded article having excellent mechanical properties or exhibiting excellent heat resistance, abrasion resistance, sliding properties, or chemical resistance. be. Further objects and advantages of the present invention will become apparent from the following description. According to the present invention, (a) a granular or powdery resin comprising a condensate of phenols and formaldehyde having the following properties (A) and (B); The condensate (1) is substantially composed of carbon, hydrogen and oxygen atoms, (2) contains methylene groups, methylol groups and trifunctional residues of phenols as the main bonding units, (3) The trifunctional residue is phenolic 2,
It is bonded to a methylene group at one position at the 4 and 6 positions, and a methylol group and/or a methylene group at at least one other position, and (4) has an absorption peak of 1600 cm ^-1 (absorption peak attributed to benzene). Absorption intensity D ₁₆₀₀ , 990 ~ 1015 cm ^-1
The maximum absorption intensity in the range (absorption peak attributed to methylol group) is D990 _~1015 ,
When the absorption intensity of 890 m ^-1 (absorption peak of isolated hydrogen atom of benzene nucleus) is expressed as D ₈₉₀ , D _{990 ~ 1015} / D ₁₆₀₀ = 0.2 ~ 9.0 D ₈₉₀ / D ₁₆₀₀ = 0.09 ~ 1.0. , and (B) the granular or powdered resin has a particle size of 1 to 150
(b) an inorganic material powder containing micron spherical primary particles and secondary aggregates; It is constituted by a composition characterized in that it contains 0.2% by weight or more and less than 11% by weight based on the total amount of powder material (b). The granular or powdered phenolic formaldehyde resin used in the present invention may contain phenol or a phenol containing at least 50% by weight, especially at least 70% by weight of phenol, e.g.
-cresol, m-cresol, p-cresol, bis-phenol A, o-, m- or p-
It includes a condensate of formaldehyde and a mixture with one or more of known phenol derivatives such as _C2 - _C4 alkylphenol, p-phenylphenol, xylenol, and resorcinol. The granular or powdered phenol formaldehyde resin used in the present invention is as described above.
It has the characteristics of (A) and (B). In specifying (A) and (B) above, specifying that the particle size of the spherical primary particles and secondary aggregates thereof in (B) is 0.1 to 150 microns, D _{990 to 1015} / D ₁₆₀₀ = in (A) The specification of 0.2 to 9.0 D ₈₉₀ /D ₁₆₀₀ = 0.09 to 1.0 is based on the measurement method described below. The first characteristic of the above granular or powdered phenol formaldehyde resin is that it is extremely difficult to crush a conventionally known cured product of novolac resin or cured product of resol resin, but it can be Completely different from the known pulverized cured novolac resin fibers, the above (B)
Contains spherical primary particles and secondary aggregates thereof, with a particle size of 0.1 to 150 microns, preferably 0.1 to 100 microns, as specified in . The above granular or powdered phenol formaldehyde resin usually has at least 30%, preferably at least 50%, of spherical primary particles and secondary aggregates thereof with a particle size of 0.1 to 150 microns, more preferably 0.1 to 100 microns. Become. This indication of 30% or 50% refers to the entire particle (including secondary aggregates) in one field of view of an optical microscope at a magnification of 100 to 1000 times, as defined in the particle size measurement method below.
This means 30% or 50% of the number of Particularly preferred is one in which 70 to substantially 100% of the granular or powdered phenol-formaldehyde resin consists of spherical primary particles and secondary aggregates thereof having a particle size of 0.1 to 150 microns. Particularly preferred is at least 30%, especially at least 50%, especially at least 50% of the number of particles in the field of the optical micrograph according to the above definition (as the average value of 5 fields).
70 to substantially 100% consist of spherical primary particles and secondary aggregates thereof ranging from 0.1 to 100 microns, more preferably from 0.1 to 50 microns. As mentioned above, the above granular or powdered phenol formaldehyde resin is formed mainly of the above spherical primary particles and microparticles of secondary aggregates thereof, so it is extremely small and the whole is extremely small. at least 50% by weight, preferably 70% by weight, particularly preferably at least 80% by weight of the total
Pass through the sieve of 100 Tyler meshes. Such an indication that the granular or powdered phenol-formaldehyde resin used in the present invention is passed through the sieve may be indicated by gently kneading the granular or powdered resin by hand or brushing. A force that does not forcibly destroy the particles (including secondary aggregates) is applied, such as lightly pressing or smoothing the particles on the sieve with a sieve, or tapping them with your hand. This does not exclude anything. Furthermore, as specified in (A) above, the granular or powdered phenol-formaldehyde resin used in the present invention has the following properties in the infrared absorption spectrum: D _{990 - 1015} / D ₁₆₀₀ = 0.2 - 9.0 D ₈₉₀ / D ₁₆₀₀ = 0.09 ~1.0. Further, the granular or powdered phenol formaldehyde resin used in the present invention preferably has a D _{990 to 1015} /D ₁₆₀₀ of 0.3 to 7.0, particularly 0.4 to 5.0.
Furthermore, it has a characteristic that D ₈₉₀ /D ₁₆₀₀ is 0.1 to 0.9, particularly 0.12 to 0.8. In the infrared absorption spectrum, the peak at D ₁₆₀₀ indicates absorption attributed to the benzene nucleus, and the peak at D _{990 to 10}
The _peak D 890 shows an absorption attributed to the methylol group, and the peak D ₈₉₀ shows an absorption attributed to the isolated hydrogen atom of the benzene nucleus.
Formaldehyde resins are already widely known. The granular or powdered phenol-formaldehyde resin used in the present invention has D _{990 to 1015} / D ₁₆₀₀ =
The characteristic value of 0.2 to 9.0 means that the granular or powdered phenol formaldehyde resin used in the present invention contains at least a certain amount of methylol groups, and the methylol group content varies considerably. It shows that you can get it. Especially D _990~10
The phenol formaldehyde resin preferably used in the present invention, where ₁₅ = 0.3 to 7.0, especially 0.4 to 5.0, contains a moderate concentration of methylol groups and is more stable. Further, in the infrared absorption spectrum of the granular or powdered phenol formaldehyde resin used in the present invention, D ₈₉₀ /D ₁₆₀₀ = 0.09 to 1.0, and a more suitable resin has D ₈₉₀ /D ₁₆₀₀ = 0.1 to 0.9, especially 0.12.
The fact that the granular or powdered phenol used in the present invention exhibits a characteristic of ~0.8
Formaldehyde resins exhibit the fact that the reactive sites (ortho and para positions) of their phenolic skeletons are moderately blocked by methylene bonds or methylol groups. Cured products of conventionally known resol resins are generally D
_990-1015 /D ₁₆₀₀ and/or D ₈₉₀ /D ₁₆₀₀ are lower than the lower limit of the above characteristic values of the phenol-formaldehyde resin used in the present invention, and the novolac resin cured with hexamine also has D The characteristic value of ₈₉₀ /D ₁₆₀₀ is the characteristic value of the phenol formaldehyde resin used in the present invention.
This value is generally lower than the lower limit of 0.09. According to elemental analysis, the granular or powdered phenol formaldehyde resin used in the present invention consists essentially of carbon, hydrogen, and oxygen, and has the following composition: C: 70 to 80% by weight, H: 5 to 7% by weight, and O. :17 to 21% by weight (total 100% by weight). The above granular or powdered phenol-formaldehyde resin also has a free phenol content as measured by liquid chromatography.
500 ppm or less, and preferred products have a free phenol content of 400 ppm or less, especially 300 ppm or less. The granular or powdered resin obtained by the method disclosed in Japanese Patent Publication No. 53-42077 contains an extremely large amount of free phenol, from 0.3 to about 6% by weight, whereas the granular or powdered resin used in the present invention The free phenol content of the phenol-formaldehyde resin is thus extremely low, and therefore its handling is extremely easy and safe. The granular or powdered phenol formaldehyde resin used in the present invention may be in either a state in which the curing reaction has not progressed sufficiently or in which the curing reaction has progressed relatively, according to the manufacturing method described later. You can also do it. As a result, the granular or powdered phenol used in the present invention
When formaldehyde resin is thermally pressurized at a temperature of 100°C for 5 minutes according to the thermal fusion measurement method described later, (a) at least a portion of it fuses into a lump or a plate. It includes both those that form a solid body and (b) those that take a granular or powder form without being substantially melted or fused. When 10 g of the granular or powdered phenol formaldehyde resin in (a) above is heated under reflux in 500 ml of substantially anhydrous methanol, the following formula S=W ₀ -W ₁ /W ₀ ×100 is obtained. where W ₀ is the weight (g) of the resin used, W ₁ is the weight (g) of the resin remaining after heating and refluxing, and S is the methanol solubility (% by weight) of the resin. indicates 20% by weight or more. Furthermore, the granular or powdered phenol-formaldehyde resin used in the present invention is manufactured by a manufacturing method that does not substantially contain nitrogen-containing basic compounds or hydrophilic polymer compounds in the reaction system, as is clear from the manufacturing method described below. Since it is manufactured, it usually does not substantially contain nitrogen-containing basic compounds or hydrophilic polymer compounds. Such nitrogen-containing basic compounds and hydrophilic polymer compounds often cause cracks and gas blisters in the final molded product during curing or firing. The granular or powdered phenol formaldehyde resin used in the present invention has (a) the following composition, and a hydrochloric acid (HCl) concentration of 5 to 28% by weight, preferably 10 to 25% by weight, especially 15 to 22% by weight. ), formaldehyde (HCHO) concentration is 3-25
% by weight (preferably 5-20% by weight, especially 7-15% by weight)
weight%), and the total concentration of hydrochloric acid and formaldehyde is 15 to 40
% by weight (preferably 20-35% by weight, especially 25-32% by weight)
%) in a hydrochloric acid-formaldehyde bath, (b) the following formula, bath ratio=weight of the above hydrochloric acid-formaldehyde bath/weight of phenols, is at least 8 or more (preferably 10 or more, especially 10 or more). (c) contacting the phenols with the hydrochloric acid-formaldehyde bath; It can be produced by forming a clear solution (before production) and thereafter forming at least a pink granular or powdery solid. As for the composition of the hydrochloric acid-formaldehyde bath in (1) above, in addition to the three conditions (a), (b), and (c) above,
Furthermore, as condition (d), it is preferable that the molar ratio of formaldehyde in the bath to phenols in contact with the bath be at least 2 or more, particularly 2.5 or more, especially 3 or more. Above condition d)
The upper limit of the molar ratio of is not particularly limited, but is 20 or less,
In particular, 15 or less is preferable. The above molar ratio is particularly from 4 to
15, particularly preferably 8 to 10. The feature of the above production method is that a bath of a hydrochloric acid-formaldehyde aqueous solution having a considerably high concentration of hydrochloric acid (HCl) and containing an excess of formaldehyde relative to phenols is used at a bath ratio of 8 or more, preferably 10 The purpose is to bring it into contact with phenols at such a large ratio. As mentioned above, such phenol-formaldehyde reaction conditions are fundamentally different from the reaction conditions for the production of hitherto known novolac resins and resol resins. Before adding phenols to the hydrochloric acid-formaldehyde bath to generate white turbidity, the bath is stirred so that the added phenols and the bath form as homogeneous a transparent solution as possible, and the turbidity is prevented. It is preferable not to apply mechanical shearing force, such as stirring, to the bath (reaction liquid) during the period from the time of generation until the pale pink solid is formed. The phenol to be added may be the phenol itself, or may be a phenol diluted with formalin, an aqueous hydrochloric acid solution, water, or the like. Furthermore, the temperature of the hydrochloric acid-formaldehyde bath when adding phenols (or their diluted solutions) is 90°C.
Temperatures below 0.degree. C., especially below 70.degree. C. are preferred. If the temperature of the bath is higher than 40℃, especially higher than 50℃,
Since the reaction rate between phenols and formaldehyde is high, it is preferable to add the phenols to the bath as a diluted solution, especially diluted with the formalin solution. Also in this case, since the reaction rate is high, it is preferable to bring the phenols, especially their diluted solutions, into contact with the bath in the form of a trickle or preferably fine droplets. When the bath temperature is 40°C or higher, especially 50°C or higher, when phenols or diluted solutions thereof are brought into contact with this bath, the higher the bath temperature, the faster the reaction rate between the phenols and formaldehyde. After the contact, white turbidity occurs within a short period of time or instantaneously, and a pink granular or powdery solid is rapidly formed. Keep the temperature of the hydrochloric acid-formaldehyde bath below 40℃.
Preferably, the temperature is maintained at 5° to 35°C, especially 10° to 30°C, and phenols or the diluted solution thereof, preferably diluted with water, are added to this bath, and after the formation of cloudiness, the temperature is lower than about 50°C, preferably. For granular or powdered solids that have completed the desired reaction at a temperature of 45°C or lower, the curing reaction has not progressed sufficiently, so they generally do not exhibit thermal adhesive properties in the 100°C thermal adhesion test described below. Become. On the other hand, the temperature of the hydrochloric acid-formaldehyde bath was set to 40
℃ or below, preferably 15° to 35°C, substantially the entire amount of the phenol or its diluted solution to be added to this bath is added under stirring to form a clear solution, and then cloudy without stirring. is produced, and then a light pink granular or powdery solid is produced without raising the temperature, and this solid is heated to 50%
If the desired reaction is completed by heating to a temperature higher than 70°C, preferably 70°C to 95°C, the curing reaction will proceed more, so the heat fusion properties at 100°C will be reduced or substantially reduced. Or, it becomes one that exhibits heat fusibility at a higher temperature, for example, 200°C, or one that has substantially no heat fusibility even at such a high temperature. As the phenol used in the above method, phenol is most suitable, but as long as it contains at least 50% by weight of phenol, especially at least 70% by weight, o-cresol, m-cresol, p-cresol, etc.
It may be a mixture with one or more of known phenol derivatives such as cresol, bis-phenol A, o-, m- or p- _C2 - _C4 alkylphenol, p-phenylphenol, xylenol, resorcinol, etc. . The granular or powdery phenol-formaldehyde resin solids produced in the bath as described above and on which the desired reaction has been completed are separated from the hydrochloric acid-formaldehyde bath, washed with water, and preferably adhered. A desired product can be obtained by neutralizing hydrochloric acid with an alkaline aqueous solution such as ammonia water or methanolic ammonia water and washing with water. In this case, it is preferable to use aqueous ammonia for neutralization because the solid material obtained by maintaining the temperature at 50° C. or lower until the reaction is completed generally has a high solubility in methanol. The composition containing the inorganic material powder of the present invention is
It contains the above granular or powdered phenol formaldehyde resin and inorganic material powder. As mentioned above, the granular or powdered phenol-formaldehyde resin used in the present invention contains very fine particles such as spherical primary particles with a particle size of 0.1 to 150 microns and secondary aggregates thereof, and therefore contains inorganic particles. Good miscibility with powder material. The composition of the present invention contains the granular or powdered phenol formaldehyde resin in an amount of 0.2% by weight or more based on the total amount of the inorganic material powder and the granular or powdered phenol formaldehyde resin11.
It is contained in an amount of less than 0.2% by weight, preferably from 0.2 to 8% by weight, particularly preferably from 0.4 to 5% by weight. The composition of the present invention thus contains a relatively small proportion of granular or powdered phenol-formaldehyde resin, but since the fine resin has excellent miscibility with the inorganic material powder, it can be provided as an intimate mixture. can do. For granular or powdered phenol/formaldehyde resin, temperature is 100℃ according to heat fusion measurement method.
The above-mentioned phenol (a) which is at least partially fused when kept at a temperature of 5 minutes.
Formaldehyde resins or any of the above-mentioned phenol-formaldehyde resins (b) which do not substantially melt or fuse according to the thermal fusion measurement method can be used. The granular or powdered phenol-formaldehyde resin of the present invention is preferably a heat-fusion type resin of the above (a) or a heat-fusion type resin of the above (a) and a heat-non-fusion type of the above (b). A mixture with mold resin is used. When the composition of the present invention containing a heat-fusion type resin (a) is made into a molded article, the resin melts upon heating and becomes a binder for the inorganic material powder. constitutes a preferred composition of the invention. The inorganic material powder in the composition of the present invention is
It is a material in the form of a powder that is generally made of a compound called an inorganic substance, such as a powder of an inorganic compound that can be a raw material for ceramics, or a metal that has a smaller ionization tendency than magnesium. These inorganic materials may be used alone or in combination of two or more, and the metal may be a mixture or an alloy. Examples of inorganic compounds that can be raw materials for ceramics include metal oxides, compositions containing metal oxides as a main component, metal hydroxides, metal sulfides, metal carbides, metal nitrides, inorganic acid salts of metals, and metals. Examples include inorganic complex salts or double salts of. The metals in such inorganic compounds include elements in periods 2 to 7 of groups, elements in periods 3 to 7 of groups, and elements 4 to 7 of groups of the periodic table.
It should be interpreted in the broadest sense to mean the elements of period 7, the elements of period 4 to 6 of group a, and the elements of group a. Examples of metal oxides include beryllium oxide,
boron oxide, magnesium oxide, barium oxide,
Alumina, silica, silica/alumina (including various zeolites), zinc oxide, titanium oxide, zirconium oxide, indium oxide, antimony oxide,
Examples include molybdenum oxide. Examples of compositions containing metal oxides as main components include clay, kaolin, pyrophyllite, montmorillonite (bentonite), clayey mica, talc, red iron oxide, feldspars, pottery stone, pumice,
Volcanic ash, shirasu balloon, volcanic rock, sillimanite, mullite, zircon, rutile, anatase,
brookite, hematite, beryl, asbestos, glass,
cement, etc. Examples of the metal hydroxide include aluminum hydroxide, calcium hydroxide, copper hydroxide carbonate (traditional stone), magnesium silicate hydroxide, iron hydroxide, barium hydroxide, magnesium hydroxide, and the like. Examples of metal sulfides include zinc sulfide (senaenite or wurtzite), antimony sulfide (chianite), cadmium sulfide, silver sulfide, cobalt sulfide,
Examples include iron sulfide, copper sulfide, barium sulfide, and the like. Examples of metal carbides include silicon carbide, zirconium carbide, tungsten carbide, titanium carbide, iron carbide, vanadium carbide, hafnium carbide,
Examples include boron carbide. Examples of metal nitrides include silicon nitride, calcium nitride, zirconium nitride, titanium nitride,
Niobium nitride, vanadium nitride, nitrogen boron, etc. can be mentioned. Examples of inorganic acid salts, inorganic complex salts, or double salts of metals include aluminum sulfate, potassium- or sodium-alum, cadmium sulfate, calcium sulfate (anhydrous, hemihydrate, dihydrate), strontium sulfate, and aluminum sulfate. Salts containing silver sulfate such as nitrate, lead sulfate, barium sulfate, and magnesium sulfate; for example, sodium chloride, silver chloride, potassium chloride, cobalt chloride, iron chloride, copper chloride, platinum chloride, barium chloride, aluminum fluoride, calcium fluoride , halides such as silver fluoride, silver bromide, silver iodide, copper iodide; zinc phosphate, aluminum phosphate,
Calcium phosphate, cerium phosphate, iron phosphate,
Examples include salts containing a phosphate group such as magnesium phosphate and barium phosphate; or carbonates such as calcium carbonate, chromium carbonate, cobalt carbonate, magnesium carbonate, magnesium calcium carbonate (dolomite), barium carbonate, and strontium carbonate. In addition, metals with a smaller ionization tendency than magnesium include, for example, Cu, Ag, Au, Zn,
B, Al, Si, Ti, Zr, Hf, Sn, W, Mn, Fe,
Examples include Co, Ni, Rn, Rh, Pd, Os, Ir, and Pt. These inorganic material powders used in the present invention usually have a size that can pass through a Tyler 20-mesh flow, preferably a size that can pass through a Tyler 32-mesh flow, and more preferably a size that can pass through a Tyler 100-mesh flow. It is. The composition of the present invention can be prepared by physically mixing a predetermined amount of the granular or powdery phenol formaldehyde resin and a predetermined amount of the inorganic material powder. At this time, the resin and the inorganic material powder may be dry mixed as they are using, for example, a V-type blender, or the resin and the inorganic material powder may be mixed in the presence of an auxiliary material. The composition of the present invention will be described below by dividing it into embodiments for convenience of explanation. Generally, the composition of the present invention cannot be used for its final use as it is; it must be molded into a form suitable for its final use and, if necessary, hardened or fired. converted into a product. Therefore, the composition of the present invention includes various embodiments depending on the mixing operation of the granular or powdered resin and the inorganic material powder, the molding operation, and optionally the curing or baking operation. The composition of the present invention is generally produced by mixing predetermined amounts of granular or powdered resin and inorganic material powder. The granular or powdered resin used in the present invention is composed of extremely fine powder consisting of spherical primary particles with a particle size of 0.1 to 150 microns, so it can be dispersed relatively uniformly even though the amount used is small. Give the composition. If only the mixing operation is considered, the homogeneously mixed composition of the present invention can be produced by dry (or wet) mixing. However, in consideration of molding operations other than the mixing operation, the composition of the present invention can preferably be provided in a state in which the mixing operation is performed in the presence of an auxiliary agent and therefore includes the auxiliary agent. In some cases, it may be preferable to provide the product in such a state. A first aspect of the composition of the present invention is a composition that contains a granular or powdered resin that exhibits heat-fusibility when heated, and contains substantially no binder components other than the resin. Such a composition can be prepared by, for example, filling a predetermined amount of the composition into a mold of a certain shape and heating it to a temperature higher than the temperature at which the resin melts, for example 60°C or higher, under a pressure of 50 to 1000 kg/cm ² . By doing so, the resin acts as a binder and is converted into a self-supporting molded article having a certain shape. If the curing reaction of the resin has already progressed sufficiently, the molded product obtained can be left as is.
In addition, if the curing reaction of the resin has not yet progressed sufficiently, the resin is cured and then provided as a cured product. Further, the molded body or the cured body can be further subjected to firing to provide a fired product. The composition of the first aspect of the invention suitable for providing a cured product is characterized in that the inorganic material is, for example, a metal oxide, a metal oxide-based mineral, a metal hydroxide, a metal sulfide or a metal. The composition of the first aspect of the present invention, which is suitable for providing baked products, is a composition in which the inorganic material is, for example, a metal oxide, a mineral containing a metal oxide as a main component, a metal carbide, It is a composition that is a metal nitride or a metal. A second aspect of the composition of the present invention is a composition that contains a granular or powdered resin that does not exhibit heat-fusibility when heated, and does not substantially contain a component that becomes a binder. Such compositions are usually difficult to convert into self-supporting shaped bodies by heat alone, since the resin does not exhibit heat-sealability upon heating. However, the composition of the present invention has a particle size of 0.1 to
It consists of extremely fine granular or powdered resin consisting of primary particles of 150 microns and inorganic material powder, so if this is compressed under extremely high pressure, it can be converted into a self-supporting molded body with a certain shape. be able to. That is, a certain amount of the composition is filled into a mold of a certain shape, for example, from several hundred kilograms to several hundred kilograms.
Applying a pressure of 10ton/cm ² and heating if necessary,
By applying a load, it can be converted into a self-supporting molded body having a certain shape. The obtained molded body is fired if necessary, and is usually provided as a fired product. As suitable compositions of the second aspect of the present invention, the same compositions as those exemplified for the compositions of the first aspect can be exemplified. The third aspect of the composition of the present invention is that the granular or powdered resin may or may not exhibit thermal fusibility when heated;
Even if the resin exhibits heat-fusibility, the composition contains an auxiliary component that serves as a binder in addition to the resin. Since such a composition contains an auxiliary component that serves as a binder, it can generally be converted into a self-supporting molded article having a certain shape without special heating or pressurization. As such an auxiliary component serving as a binder, for example, water is preferably used. Since the specific gravity of the granular or powdered resin used in the present invention is generally smaller than the specific gravity of the inorganic material powder used,
It is undesirable to use too much water so that separation of the resin and the powder easily occurs.
The appropriate amount of water to be used depends on the type and amount of the powder used and the amount of the resin used, but it is desirable to use water in an amount such that the composition exhibits a self-supporting slurry state. . One guide to determining the amount of such water is to calculate the actual volume of solid materials used (the amount of each solid used (g)) and the density of each solid (g/g).
The volume (cc) can be less than three times the sum of the values divided by (cc). In addition to water, auxiliary components that serve as binders include asphalt, synthetic lacquer, stearic acid, pine oil, naphtha, pine tar, glycerin, ethyl cellulose, abietic acid resin, polyvinyl butyral, and starch. Various bonding materials well known in the ceramics art can be used. These binders can generally be used in a proportion of up to 5 parts by weight per 100 parts by weight of the solid material used. When producing a cured molded article from the composition of the present invention, for example, when a refractory raw material such as ceramics or brick or a powder such as cement is used as the inorganic material powder, the curing reaction progresses. It is understood that since water is an essential ingredient for this, it is necessary to use water as an auxiliary ingredient. When manufacturing a fired molded body from the composition of the present invention, a sintering aid required for manufacturing the fired body, such as boron used for manufacturing a silicon carbide sintered body, etc., may be used. is desirable.
Compositions of the invention can contain such sintering aids. These sintering aids are well known in the art. In addition, when producing a fired molded porous body from the composition of the present invention, a porosity-forming agent that is easily thermally decomposed during firing may be used, such as carbohydrates, carbohydrate derivatives, or natural products containing carbohydrates as a main component, such as cellulose ( rayon), starch, sugar, derivatives of carbohydrates such as carboxymethyl cellulose, hydroxyethyl cellulose, acetyl cellulose, or natural products whose main component is carbohydrates such as wood flour, linters, coconut husk, rice husk, grain flour; thermoplastics It is preferable to contain a resin such as polyamide, polyvinyl acetate, vinyl chloride, vinylidene chloride or polyacrylonitrile resin, or a heat-infusible resin such as polyvinyl alcohol or polyvinyl formal. Compositions of the invention can contain such porosity agents. Because the composition of the present invention contains a granular or powdered phenol formaldehyde resin that is reactive with itself or with other resins and has very small particles and a large surface area, it is difficult to combine it with inorganic material powder. Because they are uniformly dispersed among each other and act as a thermosetting binder when heated or as a carbon source during firing, they provide a hardened product that is substantially uniformly hardened to the inside, and also prevent cracks and gas blisters. It is rare that a baked product with The inorganic molded body obtained from the composition of the present invention is
It has mechanical properties such as excellent impact resistance or excellent electrical properties, and also exhibits excellent heat resistance, abrasion resistance, sliding properties, or chemical resistance. The cured product and fired product obtained from the composition of the present invention can be used, for example, in parts for vehicles, aircraft, ships, etc., such as brakes, plugs, gears, and bearings; parts for electrical and energy equipment, such as radio wave absorbers, capacitors, and electrical resistors. , battery insulators, heating elements, sensor protection tubes, heat insulating materials; monolithic refractories such as blast furnaces,
Wall materials for various furnaces such as converters, fire prevention paints, fire prevention pads; Medical materials such as dental materials, aggregates; Mechanical parts such as various tools, sliding members (e.g. bearings, thread guides, seals, etc.), friction materials (e.g. abrasives, polishing powder, brakes, etc.), corrosion-resistant materials; civil engineering construction materials such as bridges, tetrapots, sleepers, roadbeds, piles, ALC (autoclaved lightweight concrete),
It can be used for fireproof, heat insulating, heat retaining and heat absorbing materials, boats, partition walls; industrial materials such as electrodes, fire bricks, tap trough materials, etc. The present invention will be described in more detail below with reference to Examples. 1. Method for measuring 0.1-150μ particles Sample approximately 0.1g of each sample. Such sampling is performed five times from different locations for one sample. One portion of each sample, weighing approximately 0.1 g, is placed on a microscope slide glass. To facilitate observation of the sample placed on a slide glass, spread it out so that the particles do not overlap as much as possible. Microscopic observation shows that granular or powdery substances and/or their secondary aggregates are observed in the visual field under an optical microscope.
Do this for about 50 locations. It is usually desirable to observe at a magnification of 10 ² to ^{10 3} times. The sizes of all particles present in the field of view under the light microscope are read and recorded by a measurer in the field of view under the light microscope. The content (%) of particles with a size of 0.1 to 150μ is determined by the following formula. Content rate (%) of 0.1 to 150μ particles = N ₁ /N ₀ × 100 N ₀ : Total number of particles whose dimensions have been read under the microscope N ₁ : Of particles with dimensions of 0.1 to 150 μ out of N ₀ Number: The content of particles of 0.1 to 150μ is expressed as the average value of the results of five samples for one sample. 2. Amount passing through a 100-meter mesh sieve After thoroughly kneading the dried sample with your hands if necessary, accurately weigh out approximately 10 g of it, and shake it through a 100-meter mesh sieve (the size of the sieve) in small portions over 5 minutes. ;200mmφ, shaking conditions;200RPM)
After adding the sample, shake for another 10 minutes. The amount of passage through a 100 tiler mesh is calculated using the following formula. Amount passing through the 100 Tyler mesh sieve (wt%) = ω ₀ - _{ω 1} / ω ₀ × 100 ω ₀ : Input amount (g) ω ₁ : Amount remaining on the sieve without passing through the 100 Tyler mesh sieve (g ) 3 Measurement of infrared absorption spectrum and determination of absorption intensity (see Figure 1 of the attached drawings) Measurement sample prepared by the usual KBr tablet method using an infrared spectrophotometer (Model 225) manufactured by Hitachi, Ltd. The infrared absorption spectrum was measured. The absorption intensity at a specific wavelength was determined as follows. In the measured infrared absorption spectrum diagram, draw a baseline at the peak whose absorption intensity is to be determined. If the transmittance at the apex of the peak is represented by t _p and the transmittance at the baseline at that wavelength is represented by t _b , then the absorption intensity D at that particular wavelength is given by the following formula. D=logt _b /t _p Therefore, for example, the ratio between the absorption intensity of the peak at 890 cm ^-1 and the absorption intensity of the peak at 1600 cm ^-1 is the ratio of the respective absorption intensities calculated using the above formula (D ₈₉₀ /
D ₁₀₀₀ ). 4 Heat fusion properties at 100°C Approximately 5 g of sample passed through 100 tyler mesh was
A heat press machine (manufactured by Shinto Metal Industry Co., Ltd., single-acting compression molding machine) was prepared by inserting the material between two 0.2 mm thick stainless steel plates and preheated it to 100℃.
Pressed for 5 minutes at an initial pressure of 50 kg. After releasing the press, the hot-pressed sample was taken out from between the two stainless steel plates. If the sample taken out is clearly fixed to form a flat plate due to melting or fusion, it is determined that the sample has fusible properties, and if there is almost no difference between before and after hot pressing, the sample is judged to be It was judged to be infusible. 5. Methanol solubility Accurately weigh approximately 10 g of the sample (the accurately weighed weight is defined as W ₀ ), and dissolve it in approximately 500 ml of substantially anhydrous methanol.
Heat under reflux for 30 minutes. Filter through a glass filter (No. 3), wash the filter residue sample on the filter with about 100 ml of methanol, and then filter the filter residue sample at 40℃ for 5 minutes.
It was dried for an hour (the exact weighed weight is W ₁ ). Methanol solubility (S ₁ %) was determined using the following formula. Methanol solubility (S ₁ % by weight) = W ₀ − W ₁ /W ₀ ×10
0 6 Determination of free phenol content Approximately 10 g of a sample passed through a 100-meter mesh was accurately weighed, and 30 g of free phenol was added to 190 g of substantially anhydrous methanol.
Heat under reflux for a minute. The liquid passed through a glass filter (No. 3) was subjected to high-performance liquid chromatography (6000A manufactured by Waters, USA).
The phenol content in the applied solution was determined, and the free phenol content in the sample was determined from a separately prepared calibration curve. The operating conditions for high performance liquid chromatography are as follows. Equipment: 6000A manufactured by Waters Co., USA Column carrier: μ-Bondapak C ₁₈ Column: 1/4 inch diameter x 1 foot length Column temperature: Room temperature Eluent: Methanol/water (3/7, volume ratio) Flow Speed: 0.5ml/min Detector: UV (254nm), Range0.01
(1 mV) The phenol content in the liquid was determined from a previously prepared calibration curve (relationship between phenol content and peak height based on phenol). 7 OH base value Measure according to the hydroxyl value measurement method (Cosmetic Raw Materials Standard Commentary, 1st edition, Yakuji Nipposha, 1975, General Test Method 377). 8. Bulk density: It tapers off at the 100ml mark.
Pour the sample that has passed through the 100 ml mesh into a 100 ml graduated cylinder from 2 cm above the rim of the graduated cylinder. The bulk density is determined by the following formula. Bulk density (g/ml) = W (g)/100 (ml) W: Weight per 100 ml (g) 9 Hardness of fired product Measured using a Vickers microhardness tester at a load of 500 kg. 10 Bending strength and compressive strength Measured according to JIS-K-6911-1979. 11 Measurement of thermal conductivity Measured according to JIS-A-1412-1968. 12 Electrical specific resistance Measured by voltage drop method according to JIS-R-7202. 13 Apparent density Calculated from the volume determined by measuring the dimensions of the molded product with calipers and the weight of the molded product. Reference Example 1 (1) Put 1500 g of each mixed aqueous solution at 25°C consisting of various compositions of hydrochloric acid and formaldehyde (listed in Table 1) into 2 separable flasks, and
98% by weight of phenol (the remaining 2% by weight is water) and
A mixed aqueous solution (25°C) containing 80 wt% phenol and 5 wt% formaldehyde prepared using 37 wt% formalin and water was prepared.
62.5g was added. After adding and stirring for 20 seconds 60
It was left standing for a minute. While standing for 60 minutes, some of the contents in each separable flask remained transparent (Run No. 1 in Table 1).
and 20), some changed from transparent to cloudy (Run No. 3, 9 and 18 in Table 1), and some changed from transparent to cloudy and then turned pale pink (Run No. 3, 9 and 18 in Table 1). Run No.2, 4-8, 10-17
and 19). When observed under a microscope, this pink colored material already contained spherical objects, aggregates of spherical objects, and a small amount of powdery material. The contents of each separable flask were then heated to 80°C for an additional 60 minutes with occasional stirring;
The reaction product was obtained by holding at a temperature of ~82°C for 15 minutes. The reaction product thus obtained was washed with hot water at 40-45°C and mixed with 0.5% by weight ammonia and 50% by weight.
The sample was treated in a mixed aqueous solution of methanol at 60°C for 30 minutes, washed again with warm water at 40-45°C, and then dried at 80°C for 2 hours. Table 2 shows the properties of the reaction products obtained from the mixed aqueous solutions of hydrochloric acid and formaldehyde of various compositions thus obtained. (2) On the other hand, the following experiment was conducted for comparison. 1
Distilled phenol in a separable flask.
Add 282g, 369g of 37% by weight formalin, and 150g of 26% by weight aqueous ammonia, raise the temperature from room temperature to 70℃ in 60 minutes while stirring, and then
Stir and heat for 90 minutes at a temperature of 70-72°C. Next, the mixture was allowed to cool, and dehydration was carried out by azeotropic distillation under a reduced pressure of 40 mmHg while adding 300 g of methanol little by little. 700 g of methanol was added as a solvent, and a yellow-brown transparent resol resin solution was taken out. When a portion of the thus obtained resol resin was desolvated under reduced pressure, it foamed violently and turned into a gel. This gelled product is further heated at a temperature of 160℃ under nitrogen gas.
After heat curing for 60 minutes, the resulting cured foam was crushed to obtain a small amount of powder that passed through a 100-meter mesh sieve. In this case, the thermosetting resol resin is extremely hard, and it is extremely difficult to obtain a powder of 100 mesh passes even using various types of crushers, ball mills, or vibrating mills for fluorescent X-rays.
The thus obtained thermosetting resol resin powder was mixed with 0.5% by weight of ammonia under the same conditions as described above.
It was treated with a mixed aqueous solution consisting of 50% by weight methanol, washed with warm water and then dried. The properties of the sample thus obtained are listed in Table 2 as Run No. 21. Next, put 390 g of phenol, 370 g of 37% by weight formalin, 1.5 g of oxalic acid, and 390 g of water into a separable flask, and while stirring.
Raise the temperature to 90℃ in 60 minutes, and at a temperature of 90-92℃
Stir and heat for 60 minutes. Then 35% by weight hydrochloric acid
1.0 g was added, and the mixture was further stirred and heated at a temperature of 90 to 92°C for 60 minutes. Next, 500 g of water was added and cooled, the water was removed using a siphon, and the mixture was heated under a reduced pressure of 30 mmHg and heated at a temperature of 100° C. for 3 hours.The temperature was further increased and the mixture was heated under reduced pressure at a temperature of 180° C. for 3 hours.
The resulting novolak resin was obtained as a tan solid upon cooling. This one has a softening temperature of 78
~80°C, and the free phenol content determined by liquid chromatography was 0.76% by weight. The above novolac resin was ground and mixed with 15% by weight of hexamethylenetetramine, the mixture was heat cured in nitrogen gas at a temperature of 160°C for 120 minutes, then ground in a ball mill and passed through a sieve of 100 Tyler mesh. I forced it. The powder thus obtained was treated with a mixed aqueous solution of 0.5% by weight ammonia and 50% by weight methanol under the same conditions as described above, washed with warm water and then dried. The properties of the sample thus obtained are listed in Table 2 as Run No. 22. Furthermore, the above novolac resin was made with a hole diameter of 0.25mmφ.
Melt spinning was carried out at a temperature of 136-138°C using a spinneret with 120 holes. Obtained average fineness
A 2.1 denier spun yarn was immersed in a mixed aqueous solution containing 1.8% by weight of hydrochloric acid and 18% by weight of formaldehyde at a temperature of 20 to 21°C for 60 minutes, and then immersed at 97°C.
It took 5 hours to raise the temperature to 97-98℃.
The temperature was kept at ℃ for 10 hours. The thus obtained cured novolak fibers were washed with warm water under the same conditions as described above, treated with a mixed aqueous solution consisting of 0.5% by weight ammonia and 50% by weight methanol, washed with warm water, and then dried. This material was ground in a ball mill. The properties of the material that passed through the 100-meter mesh sieve are listed in Table 2 as Run No. 23. (3) Table 1 shows the hydrochloric acid and formaldehyde used, the total concentration of hydrochloric acid and formaldehyde, and the molar ratio of formaldehyde to phenol. In addition, Table 2 shows 1-50μ, 1-100μ, and 1-1μ by microscopic observation of the obtained samples.
The content of 150 μ particles, the amount of sieve passing (100 mesh passes) when the obtained sample is passed through a 100-meter mesh sieve, and the infrared absorption spectroscopy of the obtained sample from 990 to 1015 cm ^-1 and 890 cm
The absorption wavelength intensity ratio (IR intensity ratio) of ^-1 to 1600 cm ^-1 is shown.

【table】

【table】

【table】

[Table] In the experiments of Run Nos. 1, 2, 3, 6, 17, and 20 in Table 1, many sticky resins and hard large lumps or plate-like materials were formed at the bottom of the separable flask. Also, in the experiments of Run Nos. 1, 2 and 20, less than 49 g of solids were obtained from the 50 g of phenol used. 1-50μ, 1-100μ and 1-
The values for the content (%) of 150 μ particles and 100 mesh pass (% by weight) are values for granular or powdery materials relative to the total solids including adhesive resin, lumps, and plate-like materials. However, in these experiments, 1 to 50 μ, 1 to 100 μ, and 1 were found only in granular or powdered solids.
The content (%) of ~150 μ particles and 100 mesh pass (% by weight) were the values shown in Table 2, respectively, enclosed by a box. From the above experimental facts including the results listed in Table 2, Run Nos. 1, 2, 3, 6, 17 and 20 cannot be recommended as manufacturing methods. However, even if these manufacturing methods are used, as far as the granules or powders produced are concerned, these granules or powders have characteristics that are fully included in the granules or powders of the present invention. . Reference Example 2 A mixed aqueous solution consisting of 20% by weight of hydrochloric acid and 11% by weight of formaldehyde was added to each of 5 reaction vessels at a bath ratio of 10.24 to 10.24 as shown in Table 3.
I put in 11.65Kg. In each flask, 1.8Kg, 1.5Kg, 0.9Kg, 0.7Kg, 0.4Kg and
Added 0.25Kg. The bath ratios in this case are 7.3, 8.5, and
They were 13.5, 17.0, 28.9 and 45.6. In either case, when stirring was continued after adding the phenol mixed aqueous solution, the mixture suddenly became cloudy in 40 to 120 seconds.
As soon as the mixture became cloudy, stirring was stopped and the mixture was allowed to stand still.
As the internal temperature gradually rose, the contents gradually changed color to pale pink, and 30 minutes after the contents became cloudy, a slurry-like or resin-like substance was observed to be formed in each case.
Next, each content was heated to 75° C. over 2 hours while stirring, and then stirred and heated at a temperature of 75 to 76° C. for 30 minutes. In this case, in the system with a bath ratio of 7.3, a large amount of cured resin material adhered to the stirring rod, making stirring extremely difficult. In both cases, the color of the contents changed from pale pink to pink and then red as the temperature rose. Next, the contents were washed with water, treated in a mixed aqueous solution of 0.1% by weight ammonia and 55% by weight methanol at a temperature of 50°C for 60 minutes, and further washed with warm water at 80°C for 60 minutes. The resulting granules, powders, or lumps were lightly massaged by hand and dried at a temperature of 100° C. for 2 hours. The moisture content after drying is
It was 0.2% by weight or less. The contents are Samples 31, 32, 33, 34, 35, and 36 in descending order of reaction bath ratio. Table 3 shows the maximum temperature reached in the reaction system from the start of the reaction until 30 minutes after it becomes cloudy, the yield of the reaction product, the presence or absence of spherical primary particles as determined by microscopic observation, and the proportion of 100 tyers in the reaction product. The content of the mesh-passed material, the heat-fusibility of the reaction product at 100°C, the elemental analysis value of the reaction product, and the OH group value of the reaction product are shown.

[Table] In Table 3, the OH group value of the product of Run No. 22 fluctuated so much that it could not be measured. In Table 3, in the experiment of Run No. 31, plate-like materials and lumps amounted to about 70% of the total solids formed at the bottom of the flask. Granules or powders accounted for only about 30% of the total solids produced, but about 95% of them passed through a 100 mesh sieve. Note that the presence or absence of spherical primary particles in Run No. 31 is small because the proportion of granular or powdery materials in the solid matter is as small as about 30%. Therefore, although the method of Run No. 31 is not recommended as a manufacturing method, the produced granules or powders are included in the granules or powders of the present invention. Please note that Run No.
Almost all of the granular or powdered materials No. 31 to 36 had a particle size of 1 to 100 microns. Reference example 3 Each of the five separable flasks with 18
1000 g of a mixed aqueous solution containing 9% by weight of hydrochloric acid and 9% by weight of formaldehyde at 25° C. was added. Room temperature is 15
It was warm at ℃. While stirring each of these, a diluted solution prepared by diluting 40 g of phenol with 5 g of water,
I put it into each at once. In both cases, stirring was stopped and stopped 50 seconds after adding the diluted solution, but
62 to 65 seconds after the stirring was stopped, a milky white product was observed which suddenly became cloudy, and the milky white product gradually turned pink. The temperature of each liquid gradually rose from 25℃, and reached 35-36℃ within 16-17 minutes after adding the diluent.
reached its peak and then fell again. After adding the diluent, 0.5 hours (Run No. 41), 1 hour (Run No. 42), 2
After being left at room temperature for 6 hours (Run No. 43), 6 hours (Run No. 44), 24 hours (Run No. 45), and 72 hours (Run No. 46), the contents were washed with water and placed in 1% by weight ammonia water for 15 hours. After treatment at a temperature of ~17°C for 6 hours, it was washed with water, dehydrated, and dried at a temperature of 40°C for 6 hours. Table 4 shows the 100 Tyler mesh sieve passing rate, IR intensity ratio, methanol dissolution amount, and free phenol content of the obtained dried sample. Furthermore, Run No.
All samples from Run No. 41 to Run No. 46 were fused at a temperature of 60°C in the thermal fusion test. FIG. 1 of the attached drawings shows an infrared absorption spectrum diagram of the sample of Run No. 44. FIG. 1 also illustrates how to determine t _p and t _b required when determining the absorption intensity D from an infrared absorption spectrum diagram. A baseline is drawn at a certain peak, and t _p and t _b at that wavelength are determined as illustrated.

[Table] Reference Example 4 Put 800 kg of a mixed aqueous solution at 18°C consisting of 18.5% by weight hydrochloric acid and 8.5% by weight formaldehyde into a 1000° reaction container equipped with a stirring bar, and add 800 kg of a mixed aqueous solution at 20°C while stirring the mixed aqueous solution. 36.4 kg of a wt% phenol aqueous solution was charged. After adding the entire amount of the phenol aqueous solution and stirring for 60 seconds, stirring was stopped and the mixture was left standing for 2 hours. In the reaction vessel, rapid cloudiness was observed 85 seconds after the entire amount of the phenol aqueous solution was added, and the color gradually changed to pale pink, and the internal temperature gradually decreased to 34.5.
It rose to ℃ and then fell again. Next, while stirring the mixed aqueous solution system of the reaction products again, open the valve attached to the bottom of the reaction vessel to take out the contents, and use a Nomex nonwoven fabric to remove the contents.
The reaction product and the mixed aqueous solution consisting of hydrochloric acid and formaldehyde were separated. The reaction product thus obtained was washed with water, dehydrated, immersed in a 0.5% by weight ammonia aqueous solution at 18°C for a day and night, and then washed again with water and dehydrated to obtain 44.6 kg of a reaction product with a water content of 15% by weight. 2.0 kg of the reaction product obtained by the above method was dried at a temperature of 40°C for 3 hours to obtain 1.7 kg of sample (Run No.
47). Table 5 shows the content of 0.1-50μ and 0.1-100μ particles as determined by microscopic observation of the dried sample thus obtained;
The amount passed through a 100-meter mesh sieve (100 mesh passes), the absorption wavelength intensity ratio (IR intensity ratio) of 990 to 1015 cm ^-1 and 890 cm ^-1 to 1600 cm ^-1 and methanol solubility by infrared absorption spectroscopy. Indicated.

[Table] Example 1 The granular or powdered resin obtained in Run No. 35 was added to commercially available clay (Niseido, water content 34% by weight) alone (Run No. 50) and to 134 parts by weight of the above clay. 0.3 parts by weight (Run No. 51) and 1 part by weight (Run No.
52), 3 parts by weight (Run No. 53), 6 parts by weight (Run No.
54), 10 parts by weight (Run No. 55) and 20 parts by weight (Run No. 56) were thoroughly kneaded by hand.
These clay alone and kneaded materials have dimensions of width 15
Using wooden shapes of 10 mm in thickness and 100 mm in length, 5 molded products were molded for each. Next, these molded products were dried at room temperature for 2 days, then ground to a shape with dimensions of 13 mm width, 6 mm thickness, and 80 mm length, and then dried in a dryer at 50 ° C for 8 hours to prepare for firing. It was used as a precursor. These precursors were placed in the center of an alumina-silica furnace tube, and it took 8 hours to raise the temperature from room temperature to 1600°C while flowing nitrogen gas at a rate of 5 ml/cm ² per minute across the cross section of the furnace. The temperature was raised to 1600° C. for 3 hours, and then slowly cooled to take out the fired test piece. Table 6 shows the blending amount of the product of Run No. 35, as well as the appearance, length retention (relative to the precursor) and bending strength of the fired test piece.

【table】

[Table] Example 2 75 parts by weight of fused alumina, 15 parts by weight of silicon carbide,
One in which 7 parts by weight of water is mixed with 100 parts by weight of a mixture consisting of 2 parts by weight of natural graphite and 8 parts by weight of metallic silicon (Run No. 57), and 7 parts by weight in 100 parts by weight of the above mixture. A mixture of water and 5 parts by weight of the reaction product of Run No. 12 (previously passed through a 200 mesh sieve) (Run No. 58)
prepared. Each of these compounds was molded into a mold under a pressure of 5 tons/ ^cm2 , and the dimensions were 5 mm in width and 5 to 5 mm in thickness.
6 mm and 50 mm long specimens for each formulation.
Created 15 pieces. These specimens were then calcined in a coke oven filled with coke powder at a temperature of 800° C. for 5 hours. Table 7 shows the compressive strength and crack occurrence rate determined for the two types of test pieces obtained by the above method. The compressive strength is the average value obtained for the samples cut from 5 of each test piece, and the crack occurrence rate is the crack occurrence rate when 10 of each test piece is heated in a Bunsen burner and then placed in water. It is expressed as the number of test pieces generated.

[Table] Example 3 As a binder for 100 parts by weight of diatomaceous earth
The product of Run No. 47 (Run No. 59), the uncured novolak resin obtained in Run No. 22 was mixed with hexamethylenethramine.
A mixture containing 15% by weight (Run No. 60), a mixture containing 7 parts by weight of each of 6-nylon powder (Run No. 61) and metal aluminum powder (Run No. 62) were prepared. These compounds are heated using a hot press machine.
Molded at a temperature of 250℃ under a pressure of 200-500Kg/ ^cm2 , each compound has dimensions of 100mm width and length.
Five molded plates each having a diameter of 100 mm and a thickness of 8 to 10 mm were made. Table 8 shows the type of binder and the bulk specific gravity, compressive strength, and thermal conductivity of the obtained molded plate. Table 8 also shows each molded plate at 650°C in a nitrogen gas atmosphere.
The compressive strength and thermal conductivity of the molded plate after heat treatment at a temperature of 5 minutes are also shown.

[Table] The heat-treated product of Run No. 61 was brittle and deformed, and its compressive strength and thermal conductivity could not be measured as shown in Table 8. Example 4 For the formulations shown in Table A below, the resol solution obtained in Run No. 21, the novolac resin obtained in Run No. 22 (compounded with 15% by weight of hexamethylenetetramine), and the product of Run No. 46 were respectively added. It was blended in an amount of 10 parts by weight in terms of resin solid content. The resulting mixture was uniformly filled into a mold and compression molded at a temperature of 155° C. and a pressure of 400 kg/cm ² for 30 minutes. After removing the frame, hold it at 170℃ for 24 hours to complete curing, and the dimensions are outer diameter 510mm, thickness 205mm, and hole diameter.
Manufactured a 305mm grinding wheel.

【table】

[Table] Table 9 shows the type of phenolic resin used and the obtained grinding wheel at a grinding wheel circumferential speed of 4800 m/min and a pressing pressure of 500 m/min.
The performance of the grindstone was shown when it was tested under the condition of Kg.

[Table] Example 5 A commercially available special grade product passed through a 300 mesh sieve.
An equal amount of methyl alcohol was added to a dry mixture of 30, 50, and 20 parts by weight of Cr, Al ₂ O ₃ , and Al(OH) _{3 ,} respectively, and the mixture was wet-pulverized and mixed using a vibrating mill. During the wet mixing, 0.25 parts by weight of wax (Run No. 66) or 0.25 parts by weight of the product of Run No. 36 that had been passed through a 300 mesh sieve (Run No. 67) was added to 100 parts by weight of the above dry mixture. were added to each. The resulting mixture was then dried under reduced pressure and further
Heat treated at a temperature of 100°C for 24 hours. Next, each mixture was molded under a pressure of 3 tons/cm ² and the dimensions were 5.
A test piece measuring mm x 3 mm x 50 mm was prepared. Each test piece thus obtained was heated from room temperature to 1650°C while continuously supplying hydrogen passed through hot water heated to 80°C.
It took 24 hours to raise the temperature to a temperature of °C, maintained at the same temperature for 6 hours, and then allowed to cool to obtain a fired test piece. Table 10 shows the types of additives used in the two types of molded products obtained by the above method, as well as the apparent density, bending strength, and electrical resistivity at 700°C and 1000°C of the fired test pieces.

[Table] In Table 10, the electrical resistivity at 700℃ and 1000℃ is determined by attaching lead wires (platinum wires) to both ends of the test piece and placing it in the center of an alumina-silica furnace under a nitrogen atmosphere. The temperature of the furnace was maintained at 700°C or 1000°C. Except for these measurement conditions, the measurement was carried out in accordance with a normal electrical resistivity measurement method. Example 6 A mixture was prepared consisting of 134 parts by weight of the same clay used in Example 1 and 100 parts by weight of silica powder passed through a 100 mesh sieve. Molded articles were obtained in the same manner as in Example 1 using this mixture itself (Run No. 68) and the mixture to which 15 parts by weight of the product of Run No. 45 was added (Run No. 69). Each molded article was air-dried for 2 days and then dried at a temperature of 50° C. for 24 hours. Next, each test piece obtained was placed in a furnace and heated for 20
The temperature of the furnace was raised from room temperature to 1600℃ over 6 hours while blowing a mixed gas consisting of hydrogen chloride at 80% by volume and nitrogen at 80% by volume, and the temperature was maintained at the same temperature for 6 hours, then the blowing gas was turned on. A fired test piece was obtained by cooling while continuing to blow air by switching to nitrogen gas only. Table 11 shows the color tone, hardness, and compressive strength of the obtained fired test pieces.

【table】 [Brief explanation of the drawing]

FIG. 1 of the accompanying drawings is an infrared absorption spectrum diagram of an example of a granular or powdery phenol formaldehyde resin used in the present invention. 1st
The figure also illustrates a method for determining the absorption intensity at a specific wavelength of the peak.

Claims (1)

[Scope of Claims] 1 (a) A granular or powdery resin comprising a condensate of phenols and formaldehyde having the following properties (A) and (B), (A) The condensate is: (1) Substantially (2) Contains trifunctional residues of methylene groups, methylol groups, and phenols as main bonding units; (3) The trifunctional The residue is phenolic 2,
It is bonded to a methylene group at one position at the 4 and 6 positions, and a methylol group and/or a methylene group at at least one other position, and (4) has an absorption peak of 1600 cm ^-1 (absorption peak attributed to benzene). Absorption intensity D ₁₆₀₀ , 990 ~ 1015 cm ^-1
The maximum absorption intensity in the range (absorption peak attributed to methylol group) is D990 _~1015 ,
When the absorption intensity of 890 m ^-1 (absorption peak of isolated hydrogen atom of benzene nucleus) is expressed as D ₈₉₀ , D _{990 ~ 1015} / D ₁₆₀₀ = 0.2 ~ 9.0 D ₈₉₀ / D ₁₆₀₀ = 0.09 ~ 1.0. , and (B) the granular or powdered resin has a particle size of 0.1 to 150
(b) an inorganic material powder containing micron spherical primary particles and secondary aggregates; A composition comprising: 0.2% by weight or more and less than 11% by weight, based on the total amount of powder material (b). 2. The composition according to claim 1, wherein at least 30% of the granular or powdery resin (a) is comprised of spherical primary particles with a particle size of 0.1 to 150 microns and secondary aggregates thereof. 3. The composition according to claim 1 or 2, wherein the granular or powdered resin (a) has a _D990-1015 / _D1600 of 0.3-7.0 in an infrared absorption spectrum determined by the KBr tablet method. 4. The composition according to any one of claims 1 to 3, wherein the granular or powdered resin (a) has a D ₈₉₀ /D ₁₆₀₀ of 0.1 to 0.9 in an infrared absorption spectrum determined by a KBr tablet method. 5. The composition according to any one of claims 1 to 4, wherein at least 50% by weight of the granular or powdered resin (a) has a size that allows it to pass through a 100-meter mesh sieve. 6 Claims 1 to 5, wherein the granular or powdered resin (a) has a free phenol content of 500 ppm or less as measured by liquid chromatography.
The composition according to any of paragraphs. 7. The granular or powdered resin (a) essentially consists of carbon, hydrogen and oxygen as determined by elemental analysis, and has the following composition: C: 70-80% by weight, H: 5-7% by weight and O: 17-21%. % by weight (total 100% by weight). 8. A patent claim in which the granular or powdered resin (a) is at least partially fused when held at a temperature of 100°C for 5 minutes according to the thermal fusion measurement method described in the main text. The composition according to any one of items 1 to 7. 9. 10g of the granular or powdered resin (a) is
When heated under reflux in 500 ml of substantially anhydrous methanol, the following formula S = W ₀ - W ₁ /W ₀ ×100 where W ₀ is the weight (g) of the granular or powdered resin used; W ₁ is the weight (g) of the granular or powdered resin remaining after heating and refluxing, S is the methanol solubility (wt%) of the granular or powdered resin, and the methanol solubility represented by is 20% by weight or more. , The composition according to any one of claims 1 to 8. 10 The granular or powdered resin (a) does not substantially melt or fuse when held at a temperature of 100°C for 5 minutes according to the thermal fusion measurement method described in the main text. The composition according to any one of Item 7. 11. The composition according to claim 1, wherein the inorganic material (b) is an inorganic material that can be used as a raw material for ceramics. 12. The composition according to claim 1, wherein the inorganic material (b) is a metal having a smaller ionization tendency than magnesium, or a mixture or alloy of such metals. 13 The above inorganic material (b) is a metal oxide, a composition containing a metal oxide as a main component, a metal hydroxide, a metal sulfide, a metal carbide, a metal nitride, an inorganic acid salt of a metal, an inorganic complex salt of a metal, or 12. The composition according to claim 1 or 11, which is a double salt. 14 (a) A granular or powdery resin consisting of a condensate of phenols and formaldehyde, having the properties of (A) and (B) below, (A) The condensate is: (1) Substantially carbon, hydrogen and It is composed of oxygen atoms, (2) it contains a methylene group, a methylol group, and a trifunctional residue of phenols as the main bonding unit, and (3) the trifunctional residue is a trifunctional residue of a phenol. 2,
It is bonded to a methylene group at one position at the 4 and 6 positions, and a methylol group and/or a methylene group at at least one other position, and (4) has an absorption peak of 1600 cm ^-1 (absorption peak attributed to benzene). Absorption intensity D ₁₆₀₀ , 990 ~ 1015 cm ^-1
The maximum absorption intensity in the range (absorption peak attributed to methylol group) is D990 _~1015 ,
When the absorption intensity of 890 m ^-1 (absorption peak of isolated hydrogen atom of benzene nucleus) is expressed as D ₈₉₀ , D _{990 ~ 1015} / D ₁₆₀₀ = 0.2 ~ 9.0 D ₈₉₀ / D ₁₆₀₀ = 0.09 ~ 1.0. , and (B) the granular or powdered resin has a particle size of 0.1 to 150
(b) an inorganic material powder containing micron spherical primary particles and secondary aggregates, and (c) an auxiliary material serving as a binder for the inorganic material powder, and the granular or powdered resin (i. ) in an amount of 0.2% by weight or more and less than 11% by weight based on the total amount of the granular or powdered resin (a) and the inorganic material powder (b), and the auxiliary material (c) , based on the above-mentioned total amount on the same basis, in an amount of 5% by weight or less.