JPS58199771A - Composition containing inorganic material powder - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention applies to compositions containing inorganic material powders. More specifically, it is a novel granular or powder that has good flow characteristics and reactivity, and exhibits excellent moldability and carbonization yield by itself or when mixed with various inorganic material powders. Nitrogen-containing phenol alde kF
The present invention relates to a composition having excellent moldability, which is suitable for making an inorganic molded body such as ceramics, which contains wood and exhibits various excellent properties such as excellent mechanical properties.

Conventionally, Norac resin and resol resin have been known as representative phenolic aldehyde trees. Norac resins are usually prepared in the presence of an acid catalyst such as Scherer's acid (usually a! to 3) under conditions of excess phenol such that the molar ratio of phenol to formaldehyde is, for example, 1 to alpha to a9. It is produced by reacting phenol and formalin. The Norac resin obtained by such a method has phenol bonded mainly through methylene groups, contains no main metal, contains almost no free methylol groups, and therefore has no self-crosslinking property by itself. It has thermoplastic properties.

Therefore, the Nogalac resin is reacted under heat with a crosslinking agent such as hexamethylenetetrine, which itself generates formalde and also contains an organic base (catalyst) generator, or For example, solid acid catalyst and 2
A cured resin can be obtained by mixing with formaldehyde or the like and subjecting the mixture to a heating reaction.

Nogilac resin is in powder form and easy to handle, 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 the inside is often not fully cured. Give an uncured cured product. In addition, when such a cured product is heated to a higher temperature (K) and subjected to firing, gas is generated inside the molded product, causing cracks and gas blisters in the molded product, and as firing progresses, these cracks and gas blisters occur. becomes even more pronounced, and it is extremely difficult to produce an inorganic molded body of satisfactory quality.

Additionally, resol resins are usually supplied as solutions, and therefore,
It is very difficult to remove the solvent and make it into a molded product by itself, since the reaction to form a resin rapidly progresses during the removal of the solvent, resulting in foaming.

It is common practice to round the material and mold it by removing the solvent using a filling material.

Therefore, when inorganic material powder is used, the solvent can be removed relatively easily. However, when such a molded product is heated and subjected to curing or firing, K still undergoes a rapid reaction to form a resin, so Kf blisters and cracks occur as in the case of the Girac resin (above). It is very difficult to produce an inorganic molded body of satisfactory quality in terms of strong f or hardness.

Well, in relatively recent years, no? Lac tree @ is heated at high temperature to obtain a product with a fairly large degree of condensation, and this is purified to separate and remove low condensates, resulting in a product in which 7 to 10 phenol groups are bonded with methylene groups and a relatively high degree of condensation is obtained. A high condensate is obtained, heated and melt spun to form a Nogirak tree @ quasi-fiber, which is immersed in a mixed aqueous solution of hydrochloric acid and formaldehyde, and gradually warmed from room temperature for a long period of time. A method for producing hardened ivy woven fibers by proceeding the hardening reaction from the outside of the fibers was proposed (Special Publication No. 4g-11284 of 1983).
.

However, the cured novolac fiber #I't produced as described above is not only expensive but also difficult to use as a molding material in the form of granules or powder with good flow characteristics. W because I can't do it! It is difficult to produce a molded body in which the IN/1 fibers are uniformly dispersed.

In addition, in recent years, a hydrophilic polymer compound is added to a condensate obtained by annealing phenols and formaldehyde in the presence of at least a nitrogen-containing compound, and the reaction produces granular or powdery mt- A production method has been published (Japanese Patent Publication No. 531-42077), but the non-rulylated m fat obtained by this method contains a large amount of free phenol, about 5 to 69 G (Examples 1 to 4 of the same). , the compound thereof (Example b) not only becomes an extremely hard non-reactive resin, but also contains a reproducible polymer compound. The ninth problem is that the inorganic molded product obtained by hardening or firing the molded product obtained using this as a filler causes cracks and gas blisters.

Furthermore, it can be obtained by reacting phenol with formaldehy Pt in a basic aqueous solution! A method is also known in which 4-limer is mixed with a purulent colloid and coagulated into inert solid beads under acidic conditions (Japanese Patent Publication No. 13491/1983), but this corresponds to a so-called cured resol resin and is reactive. does not have
Furthermore, since it contains salts, acids, and other protective colloids, it also has the disadvantage of causing cracks and gas blisters in the inorganic molded product obtained by curing or firing the molded product obtained using these as fillers.

:,,11. As mentioned above, attempts have been made to use phenol/aldehyde resin as a filler in molded products, but when viewed as a filler in molded products, it is difficult to use phenol/aldehyde resin in a shape or shape suitable for use as a filler. First of all, it is difficult to obtain it as a product, 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 nitrogen-containing phenol aldehyde 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 powdery nitrogen-containing resin and a contactless material powder.

Another object of the present invention is to provide a composition having good moldability, which contains a small proportion of a granular or powdery nitrogen-containing resin having good flow properties together with a large proportion of an inorganic material powder. It is possible to provide the following.

Still another object of the present invention is that by using granular or powdered nitrogen-containing tree Nt, which is reactive with itself or with other resins, cracks and gas blisters are reduced by hardening or firing, and the internal and external connections are reduced. To provide a composition capable of giving a homogeneous inorganic molded article with almost no unevenness in quality.
oru.

Still another object of the present invention is to provide a composition which provides an inorganic molded body having excellent mechanical properties such as impact properties or exhibiting 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, sliding properties, or chemical resistance.

I of the present invention! Other objects and advantages will become apparent from the description below.

According to the present invention, the objects and advantages of the invention are as follows: (1) A granular or powdered resin comprising a phenol, a nitrogen-containing compound having at least one active hydrogen, and a condensate with an aldehyde,・++ (A) The granular or powdered resin has a particle size (
Contains spherical-order particles of kl~1oot chron and secondary aggregates thereof, and 0. In the infrared absorption spectrum of the resin by the KB de-tablet method, 1450-1! The maximum absorption intensity in the range of Go-1.・~1. .・, and 960-1020bei-1
The maximum absorption intensity in the range of 1. . 〜1.1゜, If it is expressed as D-60, 111111/D1416〜III@:a
A granular or powdery nitrogen-containing phenol/aldehyde containing granular or powdery nitrogen-containing phenol/aldehyde having a value of 1 to 0, and containing the above nitrogen-containing phenol/aldehyde tree @, the nitrogen-containing phenol/aldehyde This is achieved by a composition characterized in that it contains an amount less than 11% by weight based on the total amount of aldehyde resin and the inorganic material powder.

Such granular or powdered nitrogen-containing phenolic aldehyde resins used in the present invention may be composed of phenol or phenol containing at least 50% by weight of phenol, especially at least 70% by weight of phenol, such as O-cresol, groove-cresol, p-cresol, etc. Cresol, bis-phenol A, o-
lm- or 'l-Cso~C4 alkylphenol, --
Incubation with one or more of the known phenol derivatives such as Hue phenol, xylenol, and resorcinol.
and a nitrogen-containing compound having at least two active hydrogens and a condensate with an aldehyde.

The granular or powdery nitrogen-containing resin in the composition of the present invention has the characteristics of (A) and (B) above. In specifying (A) and (B) above, the particle size of the spherical-order particles and their secondary aggregates of (A) is a
Identification that it is l~100# cron, (B) f)
D@@@, 1lH11/D I416~III@
The specifications of == a l ~10 are all based on the measurement method described below.

The first feature of the granular or powdered nitrogen-containing resin is that it is extremely difficult to crush the conventionally known hardened products of nogalac resin or cured resol resin, but This is completely different from the conventionally known cured M rack resin fiber #11t-pulverized fiber, etc.
) K As specified, most of them are spherical-order particles and their secondary aggregates, and the particle size is α1 to 100 microns, preferably α1 to 50 microns.

The granular or powdered nitrogen-containing resin usually contains at least 30% of the nitrogen-containing resin, preferably at least SO- with a particle size al=100.
(Consists of spherical particles of Chron, more preferably αl to SOS Chron, and secondary aggregates thereof. The expression 30- or #1so- means that the magnification is 100 to Whole particles (including secondary aggregates) in one field of light microscopy at 1000x
The number 30 - also means FiSO arrogance. In a particularly preferred book, 70 to substantially 100% of the granular or powdered nitrogen-containing resin has a spherical shape with a particle size of Al-100#Kron.
It consists of secondary particles and their secondary aggregates.

%, the number of particles in the field of view of an optical micrograph according to the above definition (as the average value of 5 fields) is at least 30-1, especially at least
0- is (kl-set/a-n, more preferably tentative 1-3
It consists of spherical-order particles in the range of 0 to 4 and their secondary agglomerates.

As mentioned above, the granular or powdery nitrogen-containing resin is
Since it is formed mainly of the fine particles of the above-mentioned spherical-order particles and their secondary aggregates, it is extremely small, and the total weight of tsO is at least 10% by weight, preferably 10% by weight. Preferably at least 80% by weight of the total IHO
Pass through Wt of Tyler mesh. This indication that the sea bream passes through L eel means that in the operation of sieving the granular or powdered sea bream product using the core part, which is used in the Kito Meijing, the granular or powdered sea bream product is lightly rubbed by hand or brushed. Do not forcibly destroy the particles (including secondary agglomerates) by lightly pressing or smoothing the grain weight on the sieve with a similar object, or by tapping lightly with your hand. There is nothing that precludes the participation of others.

The above granular or powdery nitrogen-containing resin may further include 1<8
>, in the infrared absorption spectrum, D@@@-JIIIO/D1416~11...""
~"Preferably, further Dno, ss@o/Dsase-,, tmee =
0・l! ! -10.

In addition, preferable granular or powdery nitrogen-containing resins used in the present invention are D@@11-11116/D141 11@@ ""
a” '~α' Preferably, further K D1 place @ fist~-3@・/DI41・~II・・3 (
)・Having the characteristic t- of 2-0, particularly preferred is DI"@~5111@/D141@--11
@@ = a 2 - a 4 preferably D, further D la * -, t l @ 6 / D tase -,
ass* = α! It has a characteristic of 1-15.

Further, the granular or powdery nitrogen-containing resin used in the present invention further has an infrared absorption spectrum of 1
The greatest absorption strength in the range 580-1650 cm-' [
tDsss. ~,・, When expressed as [phase], DHa@
~1@II/ D141@ ~ll@@ ” ' ”
~” (preferably α-5~zO1, particularly preferably LO~
1.5) It has **t- in the infrared absorption spectrum.

Generally, it is difficult to determine the attributes of various functional groups of a substance having a one-three-dimensional crosslinked structure using an infrared absorption spectrum. That is, this is because the peak in an infrared absorption spectrum diagram often shifts significantly.

However, the absorption of phenol aldehyde resin and the absorption of 1]~1020axr-'' is the peak attributed to the methylol group, Tofi, 1280~11NIOam-'
It was determined that the absorption of 145 (1=I5loePII-"f) is the peak associated with the aromatic double bond K11l, and the 145 (1=I5loePII-"f) absorption is the 2-linked peak associated with the 41@ carbon bond.

i9, 1580-16! ! el of absorption of 0cI11-'
Although it is difficult to clarify clearly, using the intensity of this absorption, the above ratio D1□, ~no/D +ave ~110. The value of
Rounding, which shows a value clearly distinguishable from its specific gravity in a nitrogen-free phenol-formaldehy 2-based resin, can similarly be iimized as a characteristic absorption to specify the present O*at.

Infrared absorption spectrum (
The ratio of the above-mentioned absorption intensities in the vector, for example, 1
．． ~．・、. The range of /DI41&-III@crystal to 20 indicates that the nitrogen-containing resin used in the present invention contains a moderate amount of methyl groups, and the content of methylol groups is also within a certain degree. It can be understood as representing a characteristic value associated with such a structure that can be adjusted within a range.

The granular or powdered nitrogen-containing resin used in the present invention usually has a free phenol content of 5 oopps or less as measured by liquid chromatography, and more suitable products have a free phenol content of 5 oopvm or less, especially 1100 pp or less. be. Said special meeting 1977-1! (17
The granular, conditioned, powdered resin obtained by the method disclosed in the above publication contains an extremely large amount of free phenol, α3 to about 6% by weight, whereas the granular or powdered nitrogen-containing resin used in the present invention The free phenol content of is extremely low. This fact indicates that this kind of granular or powdery tree W#I
This is an important advantage in use for K.

The granular or powdered nitrogen-containing resin used in the present invention contains at least 1 weight of 4--preferably! ~3. It is also clear that it contains a significant amount of nitrogen.

The granular or powdered nitrogen-containing resin used in the present invention can be in either a state in which the curing reaction has not progressed sufficiently or in which the curing reaction has progressed to a certain extent according to the manufacturing method described later. . As a result, the granular or powdery nitrogen-containing powder used in the present invention was thermally heated at a temperature of 100° C. for S minutes according to the heating deposition measurement method described in the afterpressure. It includes both ←) those in which at least a portion thereof is fused to form a lump or plate-like body, and -) those that are not substantially melted or fused and take the form of granules or powder.

The solubility of the resin in (a), which has relatively high fusibility, in methanol is measured according to the test method described later! Included are resins exhibiting a methanol solubility of 0 weight or more, further 30 weight iI or more, and as many as 40 weight or more.

In addition, the granular or powdered nitrogen-containing resin used in the present invention is usually hydrophilic because it is produced by a production method that does not substantially contain a hydrophilic polymer compound in the reaction system, as is clear from the production method described below. Contains virtually no synthetic 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 above-mentioned granular or powdery nitrogen-containing resin used in the present invention has the following composition (a): hydrochloric acid (HCI) concentration of 3 to 8S weight - 1 p), formaldehyde (HCHO) 11 [to 3! i weight - and the concentration of aldehydes other than formalde and
・Weight -1 and Kuha), total concentration of hydrochloric acid and formaldehyde is 10 to 40
+2) Phenols and a nitrogen-containing compound having at least three active hydrogens are added to a salt chemistry-almaldehyde bath having a weight of −1 and a nitrogen-containing compound having the following formula (1), when the bath ratio expressed by the weight of the compound is less. It can be manufactured by contacting with KM so that it is 18 or more.

As for the composition of the hydrochloric acid-formaldehyde bath in (1) above, in addition to the three conditions (a), (b), and (b) above, the condition (2) is at least 2 or more, especially Kz 1 or more, especially 8 or more. It is preferable to set K so that The upper limit of the molar ratio in condition 2) above is not particularly limited, but! It is preferable to set K such that K is equal to or less than O. The upper limit of the molar ratio in the above case 2) is not particularly limited, but! O or less, especially IIs or less is suitable. The above molar ratio is preferably 4 to 1 i, particularly preferably 8 to 10. The characteristics of the above production method are that the concentration of hydrochloric acid (MCI) is relatively high, and it contains an excess of formaldehyde relative to the phenols and nitrogen-containing compounds.
Nine baths of formaldehyde aqueous solution are brought into contact with seven enols and a nitrogen-containing compound at a bath ratio of Hatake or higher, preferably 10 or higher.

That is, to explain further, the above method is carried out under the conditions that the respective concentrations of hydrochloric acid and formaldehyde are 3 weight or more and the bath ratio is 8 or more, so that the total amount of phenols and nitrogen-containing compounds is The weight ratio of hydrochloric acid and formaldehyde to the weight is at least! 4
The weight becomes -.

In addition, since the above method is carried out with the total fa of hydrochloric acid and formaldehyde being 10 weight or more, the total weight of hydrochloric acid and formaldehyde relative to the total weight of phenols and nitrogen-containing compounds is 80 weight or more. . Such reaction conditions, as previously mentioned, are fundamentally different from those for producing lac and resol resins.

When bringing the phenol and the nitrogen-containing compound into contact with the hydrochloric acid-formaldehyde bath, the bath ratio represented by the above formula (1) is preferably 10 or more, particularly: 11S to 40.

The phenol and the nitrogen-containing compound are brought into contact with the hydrochloric acid-formaldehyde bath so that after the phenol comes into contact with the bath, a white cloud is formed, and then a granular or powdery solid is formed. The contact between the hydrochloric acid-formaldehyde bath and the enols and the nitrogen-containing compound can be carried out by adding the phenols and the nitrogen-containing compound together into the hydrochloric acid-formaldehyde bath, or by adding the nitrogen-containing compound and then adding the phenol. It is preferred to first form a clear solution, then to form a cloudy cloud, and then to form a granular or powdery solid.

At this time, before adding phenols to the bath to create a cloudy state, the bath is stirred so that the added phenols and nitrogen-containing compounds form a transparent solution as uniform as possible. Depending on the ratio of phenols and nitrogen-containing compounds and the reaction conditions, the bath (reaction liquid) may be subjected to mechanical shearing force, such as stirring, during the period from the time when white turbidity occurs until solid matter is formed. It is preferable to avoid this.

The phenol to be added may be a phenol-like phenol, but it may also be a phenol prepared by diluting it with formalin, an aqueous hydrochloric acid solution, water, or the like.

9. When adding phenols or phenols and nitrogen-containing compounds (or diluted solutions thereof) 1, the temperature of the hydrochloric acid-formaldehyde bath or the temperature V of the hydrochloric acid-formaldehyde bath in which the nitrogen-containing compound has been dissolved in advance is , a temperature of 90°C or lower, particularly 70°C or lower is preferred. The temperature of the bath is 4
If the temperature is higher than 0°C, especially 50°C or higher, the reaction rate of phenols and nitrogen-containing compounds with formaldehyde becomes high, so phenols or phenols and nitrogen-containing compounds are particularly heated in the formalin solution. It is preferred to add it to the bath as a diluted solution.

In this case, since the reaction rate is high, the phenols, or the phenols and the nitrogen-containing compound, are added to the bath in the form of a trickle of a diluted solution thereof or as small as possible droplets and brought into contact with each other. is preferable.

When the bath temperature is higher than 40℃, especially higher than KIO℃,
When phenols, phenols and nitrogen-containing compounds, or diluted solutions thereof are brought into contact with this bath, the higher the bath temperature, the higher the reaction rate f between the phenols and nitrogen-containing compounds, A whitish cloud appears within a short period of time within a few minutes after smoking, and granular or powdery solids are rapidly formed.

Hydrochloric acid-formaldehyde bath 9 temperature f below 40℃, preferably 5@~35℃, % IL < tito ~ 30'CK
Add the phenols and the nitrogen-containing compound as they are or the diluted solution thereof, preferably a water-diluted solution of the phenol and the nitrogen-containing compound, to this bath. The desired reaction is completed at a temperature of 4 s°C or less, and in the case of granular or powdery solids, the curing reaction has not progressed sufficiently, so generally described in 10) below.
It shows heat fusion properties in the °C heat fusion test.

On the other hand, the temperature of the hydrochloric acid-formaldehyde bath is below 40°C, preferably tL<its°~3! ! CK, the phenols and nitrogen-containing compounds to be added to this bath are added as they are or substantially the entire amount of the diluted solution thereof is added under stirring to form a clear solution, and then the cloudiness is removed by running a wheel without stirring. Then, a light pink granular or powdery solid is produced without raising the temperature, and the solid is heated to a temperature higher than SO0C, preferably at a temperature of 1fK at -95'C.
If the desired reaction is completed by heating, the curing reaction will occur)
As the process progresses, the thermal adhesion at 100° C. decreases or virtually disappears, or at higher temperatures, e.g. The material exhibits heat fusion properties at OO'CK, or it has substantially no heat fusion properties at such high temperatures.

In any of the above cases, the nitrogen-containing compound may be added to the Narukome hydrochloric acid-formaldehyde bath, and then only the phenol compound may be added.

The phenols used in the above method include O-cresol, m-cresol, p-cresol, as long as the phenol contains phenol of strength and strength, at least SO type weight, especially at least feet, for which phenol is most suitable. Bis-phenol AX o-1 may be a mixture with one or more of the known phenol derivatives such as tip-C-C4 alkylphenol, p-phenylphenol, cresol, and resorcinol.

The nitrogen-containing compound used in the above method is a compound having at least 42 active hydrogens in the molecule, preferably a 72-group having active hydrogens, an amide group, a thioamide group, a urein group, and a thiouraine group in the molecule. A compound having at least one group selected from the group consisting of:

Such nitrogen-containing compounds include, for example, urea, thiourea, methylol-conductor of urea or thiourea, aniline, meladenane, daanidine, guanamine, dicyandiamide, fatty acid oxide, polyamide, toluidino, cyanuric acid, or their functions. Specific derivatives can be mentioned. These can be used alone or in combination of two or more.

The granular or powdered solid nitrogen-containing phenol aldehyde resin produced in the bath as described above and having completed the desired reaction is separated from the hydrochloric acid-formaldehyde bath, washed with water, and preferably washed with water. Hydrochloric acid is neutralized with an alkaline aqueous solution, such as aqueous ammonia or methanolic aqueous ammonia. By washing with water, the desired product can be obtained. In this case, as a matter of course, if the tree has a relatively high methanol solubility, it is preferable to neutralize it with an aqueous alkaline solution.

The composition containing the inorganic material powder of the present invention contains the above-mentioned granular or powdered nitrogen-containing phenol/aldehyde resin and the inorganic material powder.

The granular or powdered nitrogen-containing phenol/aldehyde tree used in the present invention has a particle diameter of a1 to
Since it contains very fine particles such as spherical particles of 100 (Kron) and secondary aggregates thereof, it has good miscibility with inorganic material powder.

The composition of the present invention contains the granular or powdered nitrogen-containing phenol/aldehyde resin in an amount less than 11% by weight based on the total amount of the inorganic material powder and the granular or powdered nitrogen-containing phenol/aldehyde resin. amount, preferably aS~8
It is contained in an amount of -1 by weight, particularly preferably from a4 to 5 by weight.

Although the composition of the present invention contains a relatively small proportion of the powdered nitrogen-containing phenol aldehyde resin, the fine resin has excellent miscibility with the inorganic material powder, so it can be tightly mixed with the inorganic material powder. Can be provided as a mixture.

As the granular or powdered nitrogen-containing phenol/aldehyde resin, the above-mentioned phenol/aldehyde resin (α) is one that is at least partially fused when held at a temperature of 100°C for 5 minutes according to the thermal fusion measurement method. Any aldehyde resin or phenol-aldehyde resin described in (6) above that does not substantially melt or fuse according to the thermal fusion measurement method can be used. The granular or powdered nitrogen-containing phenol aldehyde resin of the present invention is preferably the heat-fusion type resin of (a) above or the above ((1)
A warm mixture of the heat-fusion type resin of ) and the heat-non-fusion type resin of (6) above is used. The composition of the present invention containing a heat-fusion type resin is a preferred composition of the present invention in this respect because when it is molded into a molded product, the resin melts by heating and becomes a binder for the inorganic material powder. constitute things.

The inorganic material powder in the composition of the present invention is a powdered material consisting of a compound generally called an inorganic substance. An example of such a material is Aigamo, which has a smaller ionization tendency than Gnesium.

These inorganic materials may be used alone or in combination, and may also be a mixture of gold alloys.

Inorganic compounds that can be used as raw materials for ceramics include, for example, metal oxides, compositions containing metal oxides as main components,
Gold peach hydroxide, metal sulfide, total brown carbide, gold @ nitride,
Inorganic acid salts of metals, inorganic complex salts or double salts of metals, etc. f:
I can give it to you.

The metals in such inorganic compounds are metals in the periodic table.
Elements in the 2nd to 7th periods of group Ⅰ, elements in the 3rd to 7th periods of group y, elements in periods 4 to 7 of groups 1 to Ⅰ, elements 4 to 6 of group Ⅰa It should be interpreted in the broadest sense to refer to periodic elements and Group 1 elements.

Examples of metal oxides include barium oxide, boron oxide, magnesium oxide, barium oxide, alumina, silica, silica/alumina (including various zeolites), zinc oxide, titanium oxide, zirconium oxide, indium oxide,
Examples include antimony oxide and molybdenum oxide.

Examples of compositions mainly composed of kinolinite include clay, kaolin, pyrophyllite, montmorillonite (bentonite), clayey mica, talc, red iron, feldspars, pottery stone, pumice, Volcanic ash, shirasu balloon, volcanic rock, sillimanite, mullite, zircon, lutal, anatase, brookite, hematite, beryl, asbestos,
Glass, cement, etc. can be mentioned.

Examples of metal hydroxides include aluminum hydroxide,
Examples include calcium hydroxide, hydroxide ash steel (peacock stone), magnesium hydroxide silicate, iron hydroxide, barium hydroxide, magnesium hydroxide, and the like.

Gold IJ sulfides include, for example, zinc sulfide (cenanite or wurtzite), antimony sulfide (chianite), cadmium sulfide, sulfur; silver, cobalt sulfide, iron sulfide, steel sulfide;
Examples include barium sulfide.

Examples of the metal carbide include silicon carbide, tungsten carbide/brunium carbide, carbide/gesten carbide, titanium carbide, iron carbide, vanadium carbide, hafnium carbide, and boron carbide.

Gold I! Examples of the nitride include silicon nitride, calcium nitride, V-lupnium fluoride, titanium nitride, electrified niobium,
Vanadium nitride, nitrogen boron, etc. can be mentioned.

Examples of gold inorganic acid salts, inorganic complex salts or double salts include aluminum sulfate, potassium or sodium i
Iopane, cadmium sulfate, calcium sulfate (anhydrous,
hemihydrate, dihydrate), strontium sulfate, dow salt,
Salts containing sulfate groups such as lead sulfate, barium sulfate, magnesium sulfate (e.g. chloride), silver chloride, potassium chloride, cobalt chloride, iron chloride, steel chloride, platinum chloride, barium chloride, aluminum fluoride, fluoride calcium,
Halodanides such as silver fluoride, silver bromide, iodide steel, iodide steel; lead phosphate, aluminum phosphate, calcium phosphate, cerium phosphate, iron phosphate, magnesium phosphate, barium phosphate or carbonates such as calcium carbonate, chromium carbonate, cobalt carbonate, magnesium carbonate, magnesium carbonate (dolomite), barium carbonate, and strontium carbonate.

In addition, examples of materials that have a smaller ionization tendency than magnesium include CsSAC55A and Zn.

B, ALX SiX TiX Zr, HfS Sn, W
, Mn.

Fe, Co, N1XRsXRh, Pd, Os, It, P
g.

etc. can be mentioned.

These inorganic material powders used in the present invention are typically sized to pass through a Tylar 20 mesh filter, preferably large enough to pass through a Tyler 32 mesh filter, preferably passed through a Tyler 10 mesh filter. It's the size.

The composition of the present invention can be prepared by physically mixing a predetermined amount of the granular or powdered nitrogen-containing phenol aldehyde resin and a predetermined amount of the inorganic material powder in a tube.
can do. At that time, the resin and the inorganic material powder may be dry mixed as they are using, for example, a Y-type pre/der, or the resin and the inorganic material powder may be mixed in the presence of an auxiliary material. Good too.

Hereinafter, the composition of the present invention will be described in terms of embodiments for the purpose of explanation.

Generally, the composition of the present invention cannot be used as it is for instant-setting purposes, but is molded into a round shape suitable for the final use, and is hardened or fired if necessary. converted into suitable products. Therefore,
The composition of the present invention includes various forms depending on the mixing process of the granular or powdery nitrogen-containing resin and the inorganic material powder, the molding operation, and optionally the curing or firing operation.

The composition of the present invention is generally produced by mixing a predetermined amount of granular or powdered nitrogen-containing resin and inorganic material powder. The granular or powdered nitrogen-containing device @ used in the present invention is composed of extremely fine powder consisting of spherical particles with a particle size (11 to 100 microns), so even though the amount used is small, it is relatively gives a uniformly dispersed composition.If only the mixing operation is considered,
Homogeneously mixed compositions of the invention can be produced by dry or wet mixing.

However, considering the molding operation other than the mixing operation μ, the composition of the present invention is preferably performed in the presence of an auxiliary agent, and therefore may be provided as a composition containing the auxiliary agent. However, it is preferable to provide it as such.

The first component of the composition of the present invention is a component that contains a granular or powdery nitrogen-containing resin that exhibits heat-fusibility when heated, and that the components other than the side 1 become substantially perfoil-1. The composition does not contain. Such a composition is prepared by filling a predetermined appetizer into a mold of a certain shape, for example, 5G-10.
The resin melts under a pressure of
f By heating to a temperature of 6 G'C or higher, for example, c1
As a result of the tree acting as a binder, it is converted into a self-supporting molded body having a certain shape. If the curing reaction of the resulting resin has already proceeded under sufficient pressure, ``ζ: As is, or if the curing reaction of the resin has not yet proceeded under sufficient pressure. After being cured, it is provided as a cured product.Furthermore, 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 mineral based on a metal oxide, a hydroxide, a metal sulfide. The first track-like composition of the present invention is a composition that is a metal and is suitable for providing a carefully fired product. , a composition that is a goldfish or a metal.

A second aspect of the composition of the present invention is a composition that contains a granular or powdery nitrogen-containing resin that does not show heat-fusibility when heated, and does not substantially contain a component that becomes a binder. It is usually difficult to convert such a composition into a self-supporting molded article having a certain shape only by heat, since the resin does not exhibit heat-fusibility when heated.

However, the composition of the present invention has a particle size αl~100j
It is made up of very fine granular or powdered nitrogen-containing resin made of primary particles of Chron and inorganic material powder.
If this is compressed under very high pressure, it can be converted into a self-supporting molded body having a certain shape. That is, a certain amount t of the composition is filled, for example, into a mold of a certain shape,
For example, it is possible to transform the molded product into a molded product having a certain shape, which improves self-reliance while being subjected to a pressure of several hundred to several tens of tons/-, optionally with heating.

The obtained molded body is fired if necessary, and is usually provided as a fired product. Preferred examples of the second composition of the present invention include the same compositions as those exemplified for the first birch composition.

A third aspect of the composition of the present invention is that the granular or powdered nitrogen-containing resin may be one that exhibits heat-fusibility when heated or a resin that does not exhibit heat-fusibility when heated; In addition to the resin, it is made of an acid containing an auxiliary component that serves as a binder.

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. The specific gravity of the granular or powdered nitrogen-containing resin used in the present invention is generally smaller than the specific gravity of the inorganic material powder used. It is not desirable to use too much water.

The appropriate amount of water to be used depends on the type of cough powder used and the tK of the resin used, but it is desirable to use water in an amount that will give the composition a self-supporting slurry state. As a guideline, the amount of such water is determined by dividing the actual volume of solid materials used (amount of each solid <1) by the density of the solids [(f/CC) (al , )) can be set to a volume smaller than three times (l).

In addition to water, auxiliary ingredients for pine paste include asphalt, synthetic lac, stearic acid, pine oil, naphtha, pine tar, glycerin, ethyl cellulose, abietic acid salt, polyvinyl butyral,
Any binder material well known in the ceramics art, such as starch, can be used. These binders can be used generally in a proportion of 5 parts by weight or less per 1'Go weight part of the solid material used.

II. Producing Cured Dermal Acid Forms from Compositions of the Invention
K N 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, water is an essential component for the progress of the hardening reaction, so water may be used as an auxiliary component. It is understood that it will be necessary to use

When producing a sintered body from the composition of the present invention, sintering aids required for producing the sintered body, such as boron, etc., used for producing a silicon carbide sintered body are added. There are so many things I can use.

Compositions of the invention can contain such sintering aids. These sintering aids are well known in the art.

In addition, when producing the entire molded porous body fired from the composition of the present invention, porosity-forming agents that are easily thermally decomposed during firing, such as
Carbohydrates, carbohydrate derivatives, or natural products mainly composed of carbohydrates, such as cellulose (rayon), starch, sugar, etc. Derivatives of vertical hydrates such as oxymethyl cellulose, hydroxyethyl cellulose, and acetyl cellulose, or natural products whose main component is carbohydrates such as wood flour, linters, coconut husk, rice husk, and grain flour; thermoplastic resins such as 4-reaid, 4 ribinyl acetate,
It is preferable to contain vinyl chloride, vinylidene chloride, polyacrylonitrile resin, or heat-infusible resin such as polyvinyl alcohol or polyvinyl formal. Compositions of the invention can contain such porosity agents. Since the composition of the present invention contains a granular or powdered nitrogen-containing phenolic aldehyde resin that has anti-core properties by itself or with other resins and has very small particles and a large surface area, it is possible to use an inorganic material. A rounded product which is uniformly mixed with the powder and is heated to act as a thermosetting binder or as a carbon source during firing, and is substantially uniformly hardened to the inside. Furthermore, it is rare that baked products with cracks or gas blisters are produced.

The inorganic molded article obtained from the composition of the present invention has excellent mechanical properties such as excellent impact resistance or excellent electrical properties, and also has excellent heat resistance, drag resistance, sliding properties, and chemical resistance. Show your gender.

The cured product and the cured product obtained from the composition of the present invention can be used, for example, in parts for vehicles, aircraft, ships, etc., such as brakes, bladders, gears, and bearings; parts for electrical and energy equipment, such as radio wave absorbers, capacitors, and electrical resistors. , battery insulators, heating elements, sensor storage tubes, insulation materials; monolithic fireproof! 1
1! For example, wall materials for various furnaces such as blast furnaces and converters, fire prevention paints, fire prevention materials; medical materials such as ashes, aggregates;
Mechanical parts such as: (Various tools, sliding parts (e.g., bearings, thread guides, seals, etc.), rubbing materials (e.g., abrasives, polishing powder, brakes, etc.), corrosion-resistant materials: Civil engineering** Materials such as bridges, tetrapods, sleepers, roadbeds, piles, ALC (astoala)
vad liyklwatght eO%seat
), fire-resistant, heat-insulating, heat-retaining, moisture-absorbing materials, ? -g, partition a
m: If the wood is grown for the woodwork, it can be used for electrodes, refractory bricks, tapping equipment, etc.

The present invention will be described in more detail below with reference to examples.

Method for measuring L alNIooμ particles Sample approximately αIF from one sample. Such sampling is performed five times for one sample starting from +1j1pfr.

Place one portion of each sample of about 6 α1t on a microscope slide glass. The sample placed on the slide glass has a diameter of 9 mm for easy observation.
Spread the particles so that they do not overlap as much as possible.

The mold observation is performed on a cylindrical portion in which about 10 to 50 particles or powders and/or secondary aggregates thereof are present in the field of view under an optical microscope.

Record.

The content (-) of α1-”100μ particles is determined by the following formula.

No: The total number of particles N, whose size was read in the lower field of the microscope: Of the particles with a size of α1-100μ, the average value of the results of five samples in one sample is 0.1 -10011 particles content.

1 150 Tyler mesh 3-111 passing amount After lightly kneading the dry sample with #1 hand as necessary, accurately weigh about 1Of, and shake it through a 150 Tyler mesh sieve for 2 minutes. The sample was placed in a machine (small size: WOO-φ, negative value for photographing: !OORPM), and was shaken for an additional KIO minute after the sample was placed.

The passing amount of 150 tiles per mesh is calculated using the following formula.

ω,: Amount of input (f) ω,: Leaves remaining on the sieve without passing through the tSO Tyler mesh sieve (f) λ Measurement of infrared absorption spectrum and determination of absorption intensity (see Figure 1 of the attached drawings) Infrared spectrophotometer (225 type) manufactured by Hitachi, Ltd.
The infrared absorption spectrum was measured for a sample prepared using the usual KB decoction method.

The absorption intensity at a specific wavelength was determined by the following equation. In the determined infrared absorption spectrum (in the Quttle diagram, draw a baseline at the peak to be determined for the absorption intensity [1). Express the transmittance of one peak as t'tp, and calculate the transmittance of the baseline at that wavelength. When expressed as t and b, the absorption intensity at that specific wavelength is given by the following formula.

h Therefore, for example, the ratio of the absorption intensity of the peak between 960 and 10102a'' and the absorption intensity of the peak between 1450 and 1500'' can be calculated using the above formula, and the ratio of the respective absorption intensities (D9....
,. ,. /D, 4@@~, 1°. ) is given as

...! 4 Thermal adhesion at 10G'cK J Sample passing through 50 tiles and mesh approx. ! ft-1 sheet of alpha 2 grain stainless steel plate was inserted into the machine (@Shinto Metal Industry Co., Ltd., single-acting compression molding machine) for S minutes at an initial pressure of SO.
- Pressed. After releasing the press, nine samples were taken out by hot pressing between two stainless steel plates. A book in which a failed sample clearly adheres to a flat plate by melting or sacrificial adhesion is judged to have sacrificial adhesion, and there is almost no difference between before and after heat pressing. The sample was determined to be infusible if it did not.

5. A methanol-soluble sample of about 50% (for consideration, its precise weighing type Iil is designated as Wo) is heat treated under electric current for 30 minutes in about 5QQaj of substantially anhydrous methanol. Filter with a glass filter (A3), and further filter the remaining sample on the filter by about Zo
om of methanol, then filter residue sample t
It was dried at a temperature of -40℃ for 5 hours (the precision weighing type 1k was
). Methanol solubility (St *) using the following formula
I asked for

Maki Determination of Free Phenol Content Approximately 10 fli of a sample passing through a 160-meter mesh is accurately weighed and heated under reflux in a substantially anhydrous methanol solution for 30 minutes. The furnace liquid filtered through a glass filter (AB) was subjected to high-performance liquid chromatography (U.S. Waters Corporation @oooA) K. The phenol content in Ffi was quantified, and the phenol content in Ffi was determined from the II*1 line created for 550 pieces. Free phenol content was determined.

The operating conditions for the Ryorin liquid chromatograph are as follows.

*: 5oooA Column manufactured by Waters, USA Column: p-Bondapak C, @Column: Extremely inch x 1 foot Column temperature: Room temperature Eluent: Methanol/water (S/7% volume ratio) flow
Speed = asIII #/min Detector; (7F (54ss), Ravh (Ia
aol (1 mF) The phenol content in the P solution was determined from nine calibration curves (relationship between phenol content and phenol-based welt height) prepared in advance.

7. 100- which is a cut-off trap at the bulk density 100- indicator
into the graduated cylinder, above the edge of the graduated cylinder! Pour the sample that has passed through the 10G tyre mesh from the container and wait. The bulk density is determined by the following formula.

Weight (f) of f: 10 (1-1) a Hardness of fired product Measured using a Vickers microhardness tester at a load of 500 Kf.

9. Bending strength and compressive strength Measured according to JIS-6911-1979.

10. Measurement of thermal conductivity Jl: 5-A-1412-1968.

lt, 1 [Vaporization resistance Measured by voltage drop method according to JIS-R-'1202.

17- Apparent density The dimensions of the molded product were determined from the volume and weight of the molded product, which were determined by measuring with a caliper.

Reference Example 1 In a seno-arm rubble flask with mouth + t and t, 25 ml of various compositions of hydrochloric acid and formaldehyde (listed in Table 1) were placed.
Add 1.500 f of the mixed aqueous solution at ℃, and then add 98
% by weight of phenol (remaining 2 wt. - urea and 3 wt.% in water)
Prepared using 7 weight of formalin and water, 20
A mixed aqueous solution (at 25°C) containing 20% by weight of phenol, 80% by weight of urea and 6% by weight of formaldehyde.
125f of each were added. After adding and stirring for 15 seconds, the mixture was incubated for 60 minutes. During the 60 minutes of electrostatic charging, the contents in each cell/label flask remained partially transparent (Ru%AI and 20% in Table 1).
), some liquids change from transparent to cloudy and remain cloudy (Ru%A3.9 and 18 in Table 1), and some
i1 Clear condition: cloudy and gave a white precipitate (7?5sAi114-8.10-17 and 19 in Table 1).

In this white precipitate, spherules, aggregates of spherules, and a small amount of powdery proboscis were already observed when observed under a jaw microscope. Next, while occasionally stirring the contents of each Cenola Rubble Flask,
Further [heated at SO℃Ki for 80 minutes, then heated to 110-
8! The reaction product was washed with warm water at 40-45°C for 15 minutes at 60°C for 30 minutes in a mixed aqueous solution consisting of a5 heavy 'It- ammonia and 50% methanol. It was then washed again with warm water at 40-45°C and dried at 80°C for 2 hours. Properties of reaction products obtained from mixed aqueous solutions of hydrochloric acid and formaldehyde of various compositions are listed in Table 2.

+21 On the other hand, I conducted an experiment below the grace of comparison. Distilled nine phenol 282f into a 1t rubble flask.
and 3774'#fk (D hol-=ry369f! and 26 wt.- of ammonia water 150f't-, heated from room temperature to 70°C in 60 minutes with stirring, and further heated to 70-78°C. The temperature was stirred and heated for 90 minutes.Then, it was allowed to cool, and while adding methanol from Boot little by little,
Dehydration was carried out by azeotropic distillation under a reduced pressure of 0 wHg, methanol (t)OOf was added as a solvent, and a yellow-brown transparent resol resin rI11 solution was taken out.

When a portion of the thus obtained resol resin was desolvated under reduced pressure, it foamed violently and became glued. 1 of this ruru compound! The foam was thermally cured for 60 minutes at a temperature of 160° C. under nitrogen gas, and the resulting hardened foam was completely crushed to obtain a small amount of powder that passed through a 150-meter mesh sieve. In this case, the thermosetting resol resin is extremely hard, and it is very difficult to obtain a powder of 150 mesh size even using various types of crushers, Gale mills, or vibrating mills for fluorescent X-rays. The thermosetting resol resin powder thus obtained was subjected to a treatment under the same conditions as described above.
It was treated with a mixed aqueous solution consisting of 50 wt. of ammonia and 50 wt. of methanol, washed with warm water, and then dried.

The properties of the samples thus obtained are shown in Table 2.
Described as mourning.

Next, add phenol 31 to a 1 ton rubber flask.
0F, 37 g#- formalin 370 f.

Add 1.5 f of succinic acid and 390 f of water, raise the temperature to 90°C Kt for 60 minutes without stirring, and stir and heat at a temperature of 90 to 92°C for 60 minutes. Next, 35% by weight of hydrochloric acid 1.
Of was added and further stirred and heated at a temperature of 9G to 92°C for 60 minutes. Next, 5002 ml of water was added and cooled, the water was removed through a siphon, heated under a reduced pressure of 30wmHQ, PK was raised and leaked at a temperature of 100°C for 3 hours, and the pressure was reduced and heated at a temperature of 180°C for 3 hours. did. 9) The rack resin is obtained.

Upon cooling, a tan solid was obtained. The softening temperature of this product was 78 to 80°C, and the free phenol content determined by liquid chromatography was 176% by weight.

The above Norac tree was crushed and mixed with 15% methylenetetramine by weight, and the mixture was heated in nitrogen gas with 16% methylenetetramine.
It was heat cured at a temperature of 0° C. for 120 minutes, then ground in a ball mill and passed through a 150 Tyler Messier sieve.

The powder thus obtained was subjected to α5 under the same conditions as described above.
It was treated with a mixed aqueous solution consisting of 50 parts by weight of ammonia and 50 parts by weight of methanol, washed with warm water and then dried. The properties of the sample thus obtained are listed in Table 2 as 8wnA22.

JK, the above? The rack resin has a pore diameter of α2S and a pore pH of 2.
Melt spinning was carried out using a No. 0 spinneret at a temperature of 136 to -38°C. The obtained spun ice having an average fineness of 21 de-L was mixed with a mixed aqueous solution of 18% by weight of hydrochloric acid and 18% by weight of formaldehyde at a temperature of 0-11'C.
The sample was immersed for 0 minutes, then raised to a temperature of 97°C over 5 hours, and maintained at a temperature of 9.7 to 98°C for 10 hours.

The thus obtained cured nogelac fibers were mixed with 50 g of ammonia and 50 g of 1 liter of αS1j view in warm water under the same conditions as described above.
treated with a mixed aqueous solution of methanol, washed with warm water, and then dried. This material was ground with a ball mill. tSO Tyler Mesh lII! The properties of the particles that passed through were listed in Table 2 as Ru%Affi3.

(3) Table 1 shows the hydrochloric acid and formaldehyde used, the total weight of hydrochloric acid and formaldehyde (11 L), the ratio of the weight of the salt beak-formaldehyde solution to the total weight of phenol and urea (9), and the ratio of formaldehyde (mol) to phenol (mol) and urea. (mol) and the total molar ratio is shown. Table 2 also shows the 0
, the content of particles of 1-S Oμ and 0.1-100 μ, the amount of the obtained KRttso Tyler mesh passing through a sieve (150 mesh arms) and the infrared absorption spectroscopy of the obtained sample. 960~10 by
20cm+-', 1280=1360m-' and 1
14 of the absorption intensity at 580-111SOs+-' K
The absorption wavelength intensity ratio (IR intensity ratio) to the absorption intensity of SO~1500c*-'' is 9.

In the experiments with R% Totsuta 1.2, @, 17, and 20 in Table 1, many sticky resins and hard large lumps or plate-like materials were formed at the bottom of the vine flask.

Also, R%nmu 1.2 and! In O's experiment, the solid matter was 49% from the 259% phenol and txt urea used.
K was obtained in an amount less than f.

R55Al, No. 2 for 2.3.6.1 and 20
90, 1~50μ and (Ll~100μ) are listed in the table.
Particle content (-) and 150 mesh/#s (weight 1
The numerical value 1) is a value based on granular or powdery materials relative to dead metal solids, including adhesive resins, lumps, and plate-like materials. However, in these experiments, the content of αl~50 particles and al~100s particles (96) and 15
The values for 0 Metsuyunos (heavy arrogance) are shown in parentheses in Table 8 and are good values.

From the above experimental facts including the results listed in Table 1, R
5nA1. R13,6,17Th! Beauty! 0 is not recommended as a manufacturing method. However, even if these manufacturing methods are used, if only the granular or powdered materials produced are considered, these granular or powdered materials are sufficiently suitable for use as the granular or powdered nitrogen-containing resin used in the present invention. It has the following characteristics.

FIG. 1, attached on the same page, shows an infrared absorption spectrum diagram of the granular or powdery material obtained in Run 12. In addition, Figure 1 also shows the absorption intensity D from the infrared absorption spectrum diagram.
This figure illustrates how to find ri and th, which are required when finding t. A baseline is drawn at a certain peak, and tν and t& at that wavelength are determined by K as shown in the figure.

Reference example 2 Room temperature is 21~! ! A mixed aqueous solution consisting of 18 weight portions of hydrochloric acid and 11 weight portions of formaldehyde was placed in each of six Got reaction vessels in a room at 2°C. In each flask! ! While stirring at a temperature of 3°C, 30% by weight of phenol - 1% by weight of urea and 1% by weight of formaldehyde
Add a mixed aqueous solution of 1 weight to each *&34 #S! !
gKfS LOO noodles, t0814, (L74Kf o!bi a4sKt7x+got.The bath ratio in this case is 7.0S each
115,lλ5,! (Lo.

2&0 and 4&0 for six nines. In either case, when the mixed aqueous solution was continued to be stirred after being added, it suddenly became cloudy in 60 seconds. Stirring was stopped as soon as the mixture became cloudy, and the mixture was allowed to stand for 3 hours. The internal temperature gradually rises, and 30 minutes after it becomes cloudy, K becomes a white slurry or 11
@Autumn crops were observed. The contents of each were then washed with water while stirring. In this case, the system with a bath ratio of 7.0 has a stirring bar K
A large amount of 11 lll-shaped cured material fused together, making stirring extremely difficult.9.

The contents were then dissolved in a 13 wt.
Treat at ℃ for 3 hours with slow stirring, wash with water and dehydrate. The resulting granular, powdery or lumpy material was lightly kneaded by hand and dried at a temperature of 40°C for 3 hours. The moisture content after drying was less than αS weight. The contents are R5n1 & 31.32. in descending order of reaction bath ratio.
33.34.3s and 36.

Table 3 shows the temperature peak reached in the reaction system from the start of the reaction until 3 hours gi after it became cloudy, the yield of the reaction product, and the microscopic
#i Observation of presence or absence of spherical-order particles during reaction 5! - Content rate of 1150 Tyra-Metsushie passing through, 150
The bulk density of the mesh-based product, the heat-fusibility of the reaction product at 109°C, the methanol solubility, and the free phenol content are shown.

In Table 3, RsKAllS21! The free phenol content of Snow 3 and Snow 3 (comparative example, see Table 1) is the value measured for the resol resin and Norac resin before heat curing, and is shown in parentheses.

In Table 3, the RIm 31 experiment produced sticky resin and lumps amounting to about 8011:1 of the total solids formed at the bottom of the flask. The granular or powdery matter accounts for approximately 100% of the total solid matter produced. Approximately 85 of them passed through a 100 mesh sieve. In addition, R5
The presence or absence of spherical-order particles in 5431 is small, which means that the proportion of granular or powdery substances in the solid matter is approximately! O Due to rumors and small things. Therefore, although the R9L%All method is not suitable for Ifi deposition as a 11-use method, the produced granules or powders have sufficient characteristics of the granules or powders preferably used in the present invention. Furthermore, Ru
All of the granular or powdered materials of 5A31 to 36 have a particle size of (Ll-100).

Reference example 3! T's 7) A friend in a mother's flask! A mixed aqueous solution of 0% by weight of hydrochloric acid and 8% by weight of formaldehyde was stirred at 1250ft at 24°C, and a solution of phenols and nitrogen-containing compounds diluted to 20 to 80% by weight with 37% by weight of formalin was mixed with phenol. and nitrogen-containing compounds were adjusted so that the total amount was SOt and added to the bath. At the same time as the solution was added, it became cloudy (immediately changed color to white, pink, or brown, which is a precaution).
Stirring was stopped in seconds. After stopping the stirring, let it stand for 60 minutes, then raise the temperature to 75℃ in 30 minutes while stirring again @73~
The temperature was kept at 6°C for 60 minutes. Each reaction product was washed with water and then dissolved in a mixed aqueous solution consisting of a3 weight of ammonia and 60 weight of methanol at a temperature of 45'C.
After treatment for 0 minutes and washing with water, it was dried at a temperature of 80° C. for 3 hours.

Table 4 shows the types and proportions of the phenols and nitrogen-containing compounds used, the concentration of the diluted solution of the phenols and nitrogen-containing compounds used in formalin, and the addition of this diluted solution 6
The color of the reaction product after 0 minutes, the yield of the reaction product based on the total amount of phenols and nitrogen-containing compounds used, the proportion of groups in the reaction product (groups contained in Ll ~ 50μ particles, 150% of the reaction product The mesh pass amount and infrared absorption spectrum intensity ratio are shown.

Reference Example 4 Six 12 separable flasks were each filled with 18 weight -
1,000 ft of a heated aqueous solution at 18 DEG C. containing 10% hydrochloric acid and 9% formaldehyde by weight was put into the tank.

The room temperature is 18'C. While stirring each of these, first, 15 ft of urea was dissolved, and then 19 k of a heated diluent solution containing 80 couls of phenol and 5 weight of formaldehyde was added to each. In both cases, the stirring tube stopped and stood still for 10 seconds after adding the diluted liquid, but suddenly became cloudy 13 to 1 seconds after stopping the stirring, and a milky white product was observed.

The temperature of each liquid gradually rose from 18℃, and after adding the diluted liquid, the temperature rose gradually from 18℃.
It reached a peak of 31-32°C in 7 minutes and then dropped again.

After adding the diluted solution, α5 hours (Run Tsuta 81), 1 hour (
Rss4ei2), 3 hours (RsnA@A), 6 hours (
R attack% shop 64), 24 hours (R%%A65), 71! Time (R% Duck A66) After being left at room temperature, the contents were washed with water,
After treatment in ays gravimetric ammonia water at a temperature of 15-17°C for 3 hours, washing with water, then washing thoroughly with water and incubating at 40°C am for 6 hours.
Dry for an hour.

Table 5 shows the 160 tyre-mesh passing rate of the obtained dry sample, the JR intensity ratio of 960 to 10110 inertia-1,
methanol dissolution amount, free phenol content 11 ft.

fM, RsnAfJl ~R5n16@@f) All samples are thermal axis bonding test N! At 100℃, fusion was performed for 5 minutes.9.

Reference Example 5 Into a 10007 reaction vessel equipped with a stirring bar, 115 weight -
of hydrochloric acid and &6 weight of formaldehyde)'1
17. Pour the heated aqueous solution at 1 G°C while stirring the heated aqueous solution.
40v4 of a mixed aqueous solution consisting of urea and nohydroquinone hx020-10x was added.

The entire amount of the warmed aqueous solution was added and stirred for 20 seconds, after which stirring was stopped and the mixture was allowed to stand for 2 hours. In the reaction vessel, severe white turbidity was observed 35 seconds after the entire amount of the mixed aqueous solution was added, and the next IN
As K-white granules are formed, the internal temperature gradually decreases to 3&S'.
It ascended to C and descended again. Next, while stirring the mixed aqueous solution system of the reaction product again, open the pulp attached to the bottom of the reaction vessel and take out the contents, and use a Nomex nonwoven fabric to separate the reaction product, the hydrochloric acid, and formaldehyde. Separate the mixed aqueous solution consisting of the mourning.

The reaction product thus obtained was washed with water, dehydrated, and then heated to α at 18°C.
After being immersed in a 5-fold 9% ammonia aqueous solution for a day and night, it was washed again with water and dehydrated to obtain 29 L of a reaction product with a water content of lIs weight.
9. Gain and mourn.

The reaction product zO obtained by the above method was heated at a temperature of 40°C for 3
After drying for several hours, sample 17- was obtained (R% Tomo 67).

Table 6 shows the content of αl-50 μ and 0.1-100 μ particles, 150
When passed through a Tyler mesh sieve, it showed a good 4t (lso mesh) and methanol solubility.

Implementation 991 Commercially available clay (Ninsei clay, moisture content 34 wt.) alone (Rs.
sA? O), and 184 parts by weight of the above clay,
Above Rs%A1! ! 3 parts by weight (RssA?1) and 1 part by weight (RssA?1) of the granular or powdered wood obtained in
) 8), 3 parts by weight (RssA) 3), 6 parts by weight (R1&
%A? 4), 10 parts by weight (R Kamo Tei Mu ys) and!
The mixture containing O weight part (Rss muff 6) was thoroughly kneaded by hand. The dimensions of these viscosities alone and kneaded products are width lam
Five molded products were molded for each using watercolor with a thickness of 10 cm, a thickness of 10 cm, and a length of 100 cm. Next, these molded products were dried at room temperature for 2 days, and then ground to a shape with dimensions of 13 cm in width, 6 cm in thickness, and 80 cm in length, and then dried in a dry oven at 50°C for 8 hours. It was used as a precursor for firing. These precursors were placed in the center of an Al2-silica furnace tube, and the temperature ranged from room temperature to 1600°C while flowing nitrogen gas of 1'Cl1d/- for 1 minute across the cross section of the furnace. It took 8 hours to raise the temperature to 1,800° C., maintained at a temperature of 1,800° C. for 3 hours, and then slowly cooled it down to take out the fired test piece.

Table 7 shows the product loading of R55411 used as well as the appearance, length retention (relative to the precursor) and strength of the fired specimens.

Example 2 Denken: A book containing 7 parts by weight of water to 100 parts by weight of a mixture consisting of 75 parts by weight of alumina, 15 parts by weight of silicon carbide, 2 parts by weight of natural graphite, and 8 parts by weight of metallic silicon.
Rt Toki A? ? ), and a mixture (8% 847g) Q was prepared. Each of these formulations was molded under a pressure of 5 tons/- to produce 15 test pieces for each of the nine formulations each having dimensions of 5 fl in width, 5 to 6 m+ in thickness, and 50 mm in length. Next, these test pieces were placed in a coke oven filled with coke powder for 800 min.
It was baked for 5 hours at a temperature of °C.

Table 8 shows the compressive strength and crack incidence determined for the two types of test specimens obtained by the above method. Compressive strength [
is the average value obtained for the samples cut from each test piece, and the crack occurrence rate is the average value obtained for the samples cut from each test piece. The following is expressed as the number of specimens generated.

Table 8 Example 3 R% as binder for 10Qfi amount part on diatomaceous material
? Product of 1467 (R1 Mu?I), 72s Tatedoro 2! (R%% AJIO), 8-nylo 7 powder (RmsA81), which was prepared by blending 15% by weight of hexamethylenetetramite with the uncured resin obtained in and metallic aluminum powder (Rs%I&@2) t- were prepared, each containing 7 parts by weight. These compounds are heated using a press material.
! Molded at a temperature of 250°C under a pressure of Go-500Kt/-, and the dimensions of each compound are width loom and length 1.
00m5+, thickness 8-1 (5 molded plates of 1 m were created.

Table 9 shows the type of Kti binder and the bulk specific gravity, compressive strength, and thermal conductivity of the obtained molded plate. Table 9 also shows the compressive strength and thermal conductivity of each molded plate after heat treatment at 630° C. for 5 minutes in a nitrogen gas atmosphere.

Example 4 Resol solution obtained with 8%% A31, Nogalac tree obtained with 8% mA22 (hexamethylenetetraden Is weight - blended product) and Rs%/
10 parts by weight of each of the 64 products were added 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 400111/- for 30 minutes. After removing the frame, hold it at 170℃ for 24 hours to complete curing, and the dimensions are outer diameter 510 m, thickness 204-1, hole diameter 304 m1.
Manufactured a grinding wheel for.

Table A Table 10 shows the type of phenolic resin used and the obtained grinding wheel at a grinding wheel circumferential speed of 4.800y+s/min and a pressing pressure of 5oo.
The property t1@ of the grindstone when tested under the condition of Kf is shown.

Example 5 Commercial special grade C passed through 1llt of 300 meshes
r5Al@O,, Al (OH), f 430, 50 each and! An equal amount of methyl alcohol was added to the dry warmed mixture at a ratio of parts by weight of O, and the mixture was wet-pulverized and mixed using a vibrating mill. During the wet mixing, 0.25 parts by weight of wax (8%% A36) or A's duck rum 4 which had been passed through SOO mesh in advance was added to 100 parts by weight of the dry mixture.
0 product αzsii (RssA8?) was added in each case. The resulting mixture was then mechanically dried and further KI
Heat treatment was performed at a temperature of O-0°C for 24 hours. Next, each mixture was molded under a pressure of 3 tons/d, and the dimensions were 56 x 3w.
A +XSam test piece was prepared. While continuing to feed hydrogen passed through hot water heated to 80" CK to each test piece thus obtained, the temperature was raised from room temperature to 11150 °C [K] over 24 hours. The sample was maintained at that temperature for 6 hours and then allowed to cool to obtain a fired test piece.

Table 11 shows the types of additives used in the various molded products obtained by the above method, as well as the apparent density, bending strength, and electrical resistivity at 700°C and 1000''CK of the fired test pieces.

In Table 11, the electrical resistivity at 700°C and 1000°C was determined by attaching trap lead wires (platinum wire) at 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 and measurements were taken.

Except for these measurement conditions, the measurement was carried out in accordance with a normal electrical resistivity measurement method.

EXAMPLE A mixture was prepared consisting of 134 parts by weight of the same clay used in Example 1 and 100 parts of silica powder passed through a 100-mesh sieve. This mixture itself (8%%A
38) and this mixture has A! 5sA35 product t-
A molded product was prepared in the same manner as in Example 1 for 9 (8wn1689) IIC with the addition of 15 parts by weight. Obtained. Each molded product t
! After air drying for a day, dry at SO℃ for 24 hours. Next, each of the nine test pieces obtained was placed in a furnace, and it took 6 hours to bring the temperature of the furnace from room temperature to 20°C while blowing a warming gas consisting of no volume of hydrogen chloride and 80 volumes of nitrogen. The temperature was raised by heating, maintained at the same temperature for a period of time, and then the blowing gas was switched to nitrogen gas only and cooling was continued while blowing to obtain a fired test piece.

Table 12 shows the color tone, hardness, and compressive strength tf of the obtained fired test pieces.

Table lz

[Brief explanation of the drawing]

FIG. 1 of the accompanying drawings is an infrared absorption spectrum diagram of an example of a granular or powdered nitrogen-containing phenol formaldehyde resin used in the present invention. FIG. 1 also illustrates a method for determining the absorption intensity at a specific wavelength of the peak. Patent applicant Kanebo Co., Ltd. (and 2 others)

Claims (1)

[Scope of Claims] 1, 111 A granular or powdery resin comprising a phenol, a nitrogen-containing compound having at least two active hydrogens, and a condensate with an aldehyde, The purpose is spherical particles with a particle size of αl to 100 cm.
In the infrared absorption spectral of the resin by the KB de-tablet method, the maximum absorption intensity in the range of 1450-1500yIM-' (7) is 1 [tDxas. O.1 and 960~
The thickest absorption strength in the range of 1020-1 If t”
D@11@ ~t+no When expressed as %, D@@11-1・! 6/ DI411)~1!1(1
a granular or powdery nitrogen-containing phenol-aldehyde resin with G = α1-10; and (2) an inorganic material powder, and the nitrogen-containing phenol-aldehyde resin is A composition characterized in that it contains less than 11 - by weight based on the total amount of resin and mineral powder. z The composition according to claim 1, wherein at least 30 particles of the nitrogen-containing resin in the form of core particles or powder consist of spherical-order particles having a particle size of 0.1 to 1 oot chrome and secondary agglomerates thereof. 1. The granular or powdered nitrogen-containing resin has an infrared absorbing sulfur content of 1280 to 181 by the KBr tablet method.
The highest absorption intensity in the range of 10cHM-' (absorption peak associated with carbon-nitrogen bond IC41tli) is ! ,
. When expressed at ~3.6°, D□-〇~l sI, e/' DI41111-J @
The composition according to claim 1 or 2, wherein @@ = a"' ring 'L'. ζ The granular or powdered nitrogen-containing resin has a D・60～1・w
e/D+n・〜…・forceH) l! ! ~α6. The composition according to any one of claims 1 to 3. 5. The granular or powdered nitrogen-containing resin has a DI of 18 (1 to
l sse /D3416~11@@ax~t. The composition according to any one of claims 1 to 4. 6. The fi granular or powdered nitrogen-containing resin has D+tao, B
es/Z)+ame~loe is a, S~1・
The composition according to any one of claims 1 to 8, which is S. 1. The granular or powdered nitrogen-containing resin contains at least 5% of the total
7. The composition according to any one of claims 1 to 6, wherein the grain size is such that it can pass through a 150-meter mesh sieve. & The granular or powdered nitrogen-containing resin has a free phenol content of 50% as measured by liquid chromatography.
The composition according to any one of claims 1 to τm, which has a content of 0 ppm or less. & The composition according to any one of claims 1 to 8, wherein the granular or powdered nitrogen-containing resin contains at least 1 weight of nitrogen. 1 (L Nucleic granular or powdered nitrogen-containing resin contains nitrogen from 2 to
10. A composition according to any one of claims 1 to 9, having a weight of 30% by weight. IL 11 The granular or powdered nitrogen-containing resin is one that 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 1O. lλ When the granular or powdered nitrogen-containing tree Tm1Ottz is heated under reflux in substantially anhydrous methanol bO〇-, in the following formula, W6 is the 11L amount (f) of the 11 pilgrims used, W,
is the weight (f) of the resin remaining after heating and refluxing, S is the methanol dissolution of the resin [(weight*'s>), and the methanol solubility represented by is !0ff- or more, Claim 1 - The composition according to any one of rings 11. The granular or powdered nitrogen-containing resin has a temperature of 160° C. [KS] according to the heat fusion measurement method described in the main text, and when the resin is kept at a temperature of 160° C. The composition according to any one of claims 1-11). 14. The composition according to claim 1, wherein the inorganic material is an inorganic material that can be used as a raw material for ceramics. The composition according to claim 1, which is a mixture or an alloy. 1 & The above inorganic material is a metal oxide, a composition containing a metal oxide as a main component, a metal hydroxide, a metal sulfide, a gold member carbide, a gold member nitride, an inorganic acid salt of a metal, an inorganic complex salt of a metal, or a complex salt of a metal. 15. The composition according to claim 1 or 14, which is a salt. 17. The composition according to any one of claims 1 to 1., wherein the composition further contains an auxiliary material. 1& A composition according to any one of claims 1 to 1τ, wherein the composition is in a molded form 11.