JPS6230211B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides novel granular or powdered phenol.
This article relates to formaldehyde resin and its manufacturing method. More specifically, the present invention provides a novel granular or powdery phenol-formaldehyde resin that has good storage stability and flow characteristics, has heat-fusibility and reactivity, and is suitable as a molding material, and a novel Regarding the manufacturing method. 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 and pentamers in which phenols are 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. However, when novolak resin is used as a molding material, in the former case, the molded product may foam due to ammonia generated by the decomposition of hexamine, and undecomposed hexamine and by-product organic bases may remain in the molded product. As a result, there are disadvantages such as deterioration of the physical properties of the molded product and a long time required for the curing reaction.Furthermore, in the latter case, the crosslinking reaction progresses excessively only in the parts that come in contact with paraformaldehyde or acid catalyst, resulting in uniformity as a whole. It is difficult to form a crosslinked structure, and the acid catalyst and paraformaldehyde remain, resulting in deterioration of physical properties over time, or decomposition of these components during curing, resulting in problems such as foaming. In addition, residual hexamine, acid catalysts, paraformaldehyde, etc. not only cause disadvantages such as deterioration of other resins when the novolac resin is mixed or used in combination with other resins, but also novolac resins are susceptible to reactions with excess phenol. They also have the disadvantage of containing relatively large amounts of free phenol (for example about 0.5-2% by weight). 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 7-10 methylene phenol 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, as is clear from the above manufacturing method, cured novolac resin fibers require an extra step to form a highly condensed novolac resin, and even if the fibers are pulverized and externally hardened, they will not harden. It is almost impossible to allow the reaction to proceed uniformly inside the fibers, and on the other hand, cutting or crushing the hardened fibers is not only expensive but also granular or powdery with good flow characteristics. It cannot be assumed. In addition, conventionally known resol resins are prepared in the presence of a basic catalyst (approximately 0.2 to 2%) such as sodium hydroxide, ammonia, or an organic amine in an excess of formaldehyde, such as at a molar ratio of phenol to formaldehyde of 1:1 to 2. It is produced by reacting under the following conditions. The resol resin thus obtained is mainly composed of mono- to trimer of phenol having a relatively large amount of free methylol groups, and has extremely high reactivity, so it is usually prepared as a water or methanol solution with a solid content of 60% or less. It is stored in the refrigerator, but its shelf life is about 3 to 4 months at most.
When molding and curing such a resol resin, water or alcohol is removed, and if necessary, the resin is heated in the presence of an acid catalyst. This curing reaction rate is extremely fast, and gelation occurs within several tens of seconds at 150°C, for example. As is clear from the above, resol resin is extremely reactive and cannot be made into a stable solid substance in the form of granules or powder, and its cured product has a highly advanced three-dimensional structure. Therefore, it is extremely hard to make molding materials into minute particles or powder (Japanese Patent Publication No. 53-12958).
issue). 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 the method has been announced (Special old 1977-
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, which has the disadvantage of reducing the performance of the resulting molded product. 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
No. 13491), which corresponds to a so-called cured resol resin product, has no reactivity and furthermore contains salts, acids, and other protective colloids, which has the disadvantage of deteriorating the performance of the resulting molded product. Therefore, the first object of the present invention is to have a resin that has high storage stability, good flow characteristics, and has reactivity when molded or heated by itself or when mixed with other resins. The object of the present invention is to provide a phenol-formaldehyde resin in the form of particles or powder that has a reactivity that gives a self-curing resin when heated. A second object of the present invention is to provide a solid material in the form of extremely fine particles or powder, which has good flow characteristics, can smoothly pass through, for example, a micro nozzle in injection molding even in an unmolten state, and which can react. An object of the present invention is to provide a phenol-formaldehyde resin that can be used as a filler. A third object of the present invention is to provide a granular or powdery phenol that has heat-fusibility and reactivity when heated at, for example, 100°C or lower, and can therefore be suitably used as a binder for base materials that cannot withstand high-temperature treatment.・Providing formaldehyde resin. The fourth object of the present invention is that the free phenol content is
The object of the present invention is to provide a granular or powdery phenol-formaldehyde resin that has a small amount of 500 ppm or less and is therefore safe and easy to handle. A fifth object of the present invention is to not only have good storage stability at room temperature, but also to improve heat resistance, heat insulation, mechanical properties and/or
Another object of the present invention is to provide a granular or powdery phenol-formaldehyde resin that can form a molded article with excellent electrical properties. Another object of the present invention is to provide a new industrial method for producing a new granular or powdered phenol-formaldehyde resin having the various advantages mentioned in the first to fifth objects above. Further objects and advantages of the present invention will become apparent from the following description. According to the present invention, the above objects and advantages include a granular or powdered resin comprising a condensate of phenols and formaldehyde, (1) the condensate comprising substantially carbon, hydrogen and oxygen; (2) It contains a methylene group, a methylol group, and a trifunctional residue of a phenol as the main bonding unit, and (3) The trifunctional residue is a 2-functional residue of a phenol.・4
and a methylene group at one position in the 6-position and a methylol group and/or at least one other position.
(4) In the infrared absorption spectrum by KBr tablet method, the absorption intensity at 1600 cm ^-1 (absorption peak attributed to benzene) is D ₁₆₀₀ and 990 to 1015 cm ^-1 (absorption peak attributed to methylol group). The largest absorption intensity in the range of absorption peaks
D _{990 ~ 1015} , When the absorption intensity of 890 cm ^-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 to 1.0, and () the granular or powdered resin contains (A) spherical primary particles and secondary aggregates with a particle size of 0.1 to 150 microns, and (B) at least 50% by weight of the total (C) has a free phenol content of more than 50 ppm as measured by liquid chromatography;
Granular or powdered phenol characterized by having a content of 500 ppm or less.
This is achieved using formaldehyde resin. According to the research conducted by the present inventors, the above-mentioned novel granular or powdery phenol-formaldehyde resin of the present invention has the following composition: (1) the following composition, hydrochloric acid (HCl) concentration of 5 to 28% by weight, formaldehyde (HCHO); Concentration is 3-25
% by weight, and the total concentration of hydrochloric acid and formaldehyde is 15-40
% by weight of a hydrochloric acid-formaldehyde bath, (2) the following formula (A), bath ratio = weight of the above hydrochloric acid-formaldehyde bath/weight of phenols... (A) is at least 8 or more. (3) contacting the phenols with the hydrochloric acid-formaldehyde bath, and continuing the contact until the phenols form a white cloud after contact with the bath, and then maintain at least a pink color. It has been found that it can be produced by carrying out the reaction in such a way that a granular or powdery solid is formed, and by maintaining the temperature in the reaction system below 45° C. during this contacting. The method of the present invention will first be explained in detail below. [Method of the present invention] According to the method of the present invention, as described above, (1) the following composition, (a) a hydrochloric acid (HCl) concentration of 5 to 28% by weight, and (b) a formaldehyde (HCHO) concentration of 3 to 28% by weight.
25% by weight, and (c) the total concentration of hydrochloric acid and formaldehyde is 15~
Using a hydrochloric acid-formaldehyde bath with a concentration of 40% by weight, (2) the following formula (A), bath ratio = weight of the above hydrochloric acid-formaldehyde bath/weight of phenols... ...(A) is at least The phenols are brought into contact with the hydrochloric acid-formaldehyde bath while maintaining the pH at 8 or more, preferably 10. As for the composition of the hydrochloric acid-formaldehyde bath in (1) above, in addition to the three conditions (a), (b), and (c) above, the further condition (d) is: formaldehyde in the bath/contact with the bath. It is preferable that the molar ratio of the phenols used is at least 2 or more, particularly 2.5 or more, especially 3 or more. The upper limit of the molar ratio in the above condition (d) is not particularly limited, but it is preferably 20 or less, especially 15 or less, and it is not economically advisable to increase the molar ratio more than this; When it is less than 2.5, especially less than 2, the reaction rate decreases and it becomes difficult to obtain uniform and fine granular or powdery resin. A particularly preferred range of the above molar ratio is 4-15. The above molar ratio is 2 or more, especially 2.5
The above is particularly effective when the bath ratio in (2) above is relatively low, for example, when the bath ratio is 8 to 10. In the present invention, the phenols are brought into contact with the hydrochloric acid-formaldehyde bath having the bath composition (1) above by maintaining the bath ratio to be 8 or more, preferably 10 or more relative to the weight of the phenols. let An important feature of the present invention is that the bath of a hydrochloric acid-formaldehyde aqueous solution having a fairly high concentration of hydrochloric acid (HCl) and containing an excess of formaldehyde relative to the phenols is preferably used at a bath ratio of 8 or more.
The purpose is to bring it into contact with phenols at a large ratio of 10 or more. As mentioned above, such phenol-formaldehyde reaction conditions are fundamentally different from the reaction conditions for the production of conventionally known novolac resins and resol resins. The hydrochloric acid (HCl) concentration of the hydrochloric acid-formaldehyde bath used in the present invention is preferably 10 to 25% by weight, particularly 15 to 22% by weight, and the formaldehyde (HCHO) concentration of the bath is 5 to 20% by weight, particularly 7 to 15% by weight is preferred, and the total concentration of hydrochloric acid and formaldehyde in the bath is preferably 20 to 35% by weight, especially 25 to 32% by weight. The bath ratio represented by the above formula (A) when the hydrochloric acid-formaldehyde bath and the phenols are brought into contact is preferably 10 or more, particularly 15-40. In the method of the present invention, phenols are brought into contact with the above-mentioned hydrochloric acid-formaldehyde bath, and after the phenols come into contact with the bath, white turbidity is formed, and then at least pink particles or Do this so that a powdery solid is formed. During this contact, the temperature within the reaction system is maintained at a temperature below 45°C. The contact between the hydrochloric acid-formaldehyde bath and the phenols is such that the phenols are added to the hydrochloric acid-formaldehyde bath to first form a clear solution, then a cloudy state, and then at least pink granules or powder. It is preferable to carry out the process in such a way that a solid substance having a shape of 1.5 mm is formed. At this time, before adding phenols to the bath to create a white cloud, the bath is stirred so that the added phenols and the bath form a transparent solution as uniform as possible, and the white cloud is formed. It is preferable not to apply mechanical shearing force, such as stirring, to the bath (reaction liquid) during the period after the formation of a pale pink solid substance. The phenol to be added may be the phenol itself, but it is preferable to dilute the phenol with formalin, an aqueous hydrochloric acid solution, water, or the like. Particularly preferably, it is used after being diluted with water. In particular, formaldehyde concentration is 3 to 44% by weight,
Preferably, the phenols are diluted with a 20-40% by weight formalin solution to reach a phenol concentration of 50-95%.
Preferably, a dilute solution of 70 to 90% by weight is used. However, in this case, the bath composition after adding this diluted phenol solution to the hydrochloric acid-formaldehyde bath is the same as the above (a), (b), and (c), preferably the above (a), (b), and (c). It is necessary to control so that conditions (d) and (d) are satisfied. Furthermore, the temperature of the hydrochloric acid-formaldehyde bath when adding phenols (or their diluted solutions) is 40°C.
℃ or less, preferably 5 to 35℃, particularly preferably 10℃
~30℃. If the temperature of the bath exceeds 40°C, the reaction rate between phenols and formaldehyde increases, so the highly reactive granular or powdered resin of the present invention with a methanol solubility of 20% by weight or more, as defined later, is produced. It becomes difficult to do. Embodiments of the present invention will be described below. In this embodiment, a phenol or a phenol diluted with water or an aqueous solution of the formaldehyde is added to the hydrochloric acid-formaldehyde bath at 40°C or lower to form a transparent solution, and then a white turbidity is formed in the transparent solution. Then, a pink granular or powdery phenol-formaldehyde resin is formed. In the case of this embodiment 2, it is particularly advantageous to add the phenols or diluted solutions thereof to the hydrochloric acid-formaldehyde bath to first form a homogeneous solution, from which a white turbidity is formed, and then to form a pink microsolid. By controlling the production of a solid substance, it is possible to form a granular or powdery solid substance with an extremely small average particle size. Furthermore, in order to form a homogeneous solution by adding phenols or a diluted solution thereof to a hydrochloric acid-formaldehyde bath, it is preferable to stir the mixture, but this stirring should preferably be carried out before or after the formation of white turbidity. It is preferable to stop immediately. This is because if stirring is continued even after the formation of white cloudiness, the cloudy particles will aggregate into a cake-like shape, and the yield of fine particles will decrease accordingly. Furthermore, the temperature of the hydrochloric acid-formaldehyde bath when adding the phenols or their diluted solutions is 10
When the temperature is lower than 5°C, especially lower than 5°C, and the phenols or their diluted solutions are added all at once to such a large amount of bath, a homogeneous solution is formed by continuing stirring. However, the lower the bath temperature, the lower the reaction rate between phenols and formaldehyde, so it takes a long time to form a white cloud, and the white cloud grows and becomes pink. The time required to form a granular or powdery solid with a stable color also becomes long. Therefore, when stirring is stopped after white turbidity is formed, the white turbidity settles to the bottom of the bath before it grows into stable pink particles, and in this precipitated and accumulated state, phenols and formaldehyde condensate. As the reaction progresses, cake-like or plate-like lumpy solids are formed, which reduces the yield of the desired granular or powdered product. For the above reasons, the temperature of the hydrochloric acid-formaldehyde bath is maintained at 5 to 35°C, especially 10 to 30°C, and phenols or diluted solutions thereof are added to the bath at such temperature, and the desired granular or powdered products are prepared. It is preferable to maintain the temperature within the reaction system at 45° C. or lower until . Keep the external temperature of the reaction system below 35°C, especially between 5 and 5°C.
By setting the temperature to 25℃, the temperature inside the reaction system is 45℃.
It becomes easier to maintain below. In this manner, the desired amount of phenols is added to the bath in batches to form a homogeneous solution, which then produces a white turbidity, which is then converted into a pink fine granular or powdery solid. It is possible to make it grow smoothly. The reaction between the hydrochloric acid-formaldehyde bath and phenols of the present invention is a relatively mild exothermic reaction, so by cooling if necessary, the desired reaction can be carried out without cloudy precipitation or accumulation. can. When white turbidity is first formed in the method of the above embodiment, the white turbidity changes to a milky white color over time, and usually the entire reaction solution in the bath becomes a fairly thick milky white color, and then becomes a pale pink color, and furthermore as time passes. It turns into a deeper pink color. As mentioned above, when the white turbidity is kept in the bath after the white turbidity is formed, it changes to a milky white color and then changes from pale pink to deep pink granular or powdery solid. At some point in time, the exothermic reaction substantially ceases. Once the exothermic reaction has stopped, the granular or powdered solid will be in a stable state, and once this state has been reached, the bath may be stirred again. In the method of the above aspect, the granular or powdered solid material that has completed the desired reaction after the formation of white turbidity is
Since the curing reaction has not progressed sufficiently, it exhibits heat fusion properties in the 100°C heat fusion test described below. Phenol is most suitable as the phenol used in the present invention, but any phenol containing at least 80% by weight, especially at least 85% by weight, such as o-cresol, m-cresol, p-cresol, bis-cresol, etc. -Phenol A, o-, m- or p- _C2 to _C4 alkylphenol, p-phenylphenol, xylenol, resorcinol, etc. may be a mixture with one or more known phenol derivatives. The granular or powdery solid phenol-formaldehyde resin produced in the bath as described above and on which the desired reaction has been completed is separated from the hydrochloric acid-formaldehyde bath, washed with water, and preferably The desired product can be obtained by neutralizing the hydrochloric acid with an alkaline aqueous solution and washing with water. As the aqueous alkali solution, for example, an aqueous alkali metal solution, particularly an aqueous ammonia solution is preferable. The concentration of ammonia is 0.1-5% by weight, especially 0.3
~3% by weight is suitable. The neutralization with the aqueous alkaline solution is advantageously carried out at a temperature below 50°C, preferably between 10 and 40°C. The granular or powdered solid material that has been subjected to the water washing treatment or the subsequent neutralization and water washing treatment may be dehydrated and used as it is for final use, or it may be processed in a conventional manner at a temperature lower than the heat fusion temperature. For example, after drying at 40 to 50°C, it can be used for final use. Moreover, before or after drying, the product can be made into a product by being lightly pulverized using an arbitrary pulverizer. [The granular or powdered resin of the present invention] According to the present invention, there is provided a granular or powdered resin comprising a condensate of phenols and formaldehyde, wherein () the condensate comprises (1) substantially It is composed of carbon, hydrogen, and oxygen atoms, (2) it contains trifunctional residues of methylene groups, methylol groups, and phenols as the main bonding units, and (3) the trifunctional residues are phenols 2 and 4
and a methylene group at one position in the 6-position and a methylol group and/or at least one other position.
(4) In the infrared absorption spectrum by KBr tablet method, the absorption intensity at 1600 cm ^-1 (absorption peak attributed to benzene) is D ₁₆₀₀ and 990 to 1015 cm ^-1 (absorption peak attributed to methylol group). The largest absorption intensity in the range of absorption peaks
D _{990 ~ 1015} , When the absorption intensity of 890 cm ^-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 to 1.0, and () the granular or powdered resin contains (A) spherical primary particles and secondary aggregates with a particle size of 0.1 to 150 microns, and (B) at least 50% by weight of the total (C) has a free phenol content of more than 50 ppm as measured by liquid chromatography;
Granular or powdered phenol characterized by having a content of 500 ppm or less.
Formaldehyde resin is obtained. The above granular or powdery phenol-formaldehyde resin of the present invention (hereinafter referred to as the product of the present invention)
The above () and () specifications are both based on the measurement method described below. The first feature of the product of the present invention is that it is a cured product of a conventionally known novolac resin or a cured product of a resol resin, which is extremely difficult to crush, but is forcibly crushed, or a cured product of a conventionally known cured novolac resin. These are spherical primary particles and their secondary agglomerates as specified in () and (A) above, and have a particle size of 0.1 to 150 microns, preferably 0.1 to 100 microns. This fact is shown in attached drawings 1A and B.
This is clearly shown in the optical micrographs and scanning electron micrographs shown in Figures 2A and 2B. As shown in Figures 1 and 2 above, the granular or powdered resin product of the present invention usually has at least 30%
Preferably, at least 50% consists of spherical primary particles and secondary agglomerates thereof having a particle size of 0.1 to 150 microns, more preferably 0.1 to 100 microns. This 30%
The expression 50% means 30% or 50% of the total number of particles (including secondary aggregates) in one field of view of an optical microscope with a magnification of 100 to 1000 times, as defined in the particle size measurement method below. It means %. Particularly preferred products of the invention are those in which 70 to substantially 100% of the granular or powdered resin has a particle size of 0.1
It consists of spherical primary particles of ~150 microns and their secondary aggregates. Particularly preferred is that at least 30%, in particular at least 50%, of the number of particles in the field of view of an optical suspension microscope according to the above definition (as the average value of 5 fields) is 0.1
It consists of spherical primary particles and their secondary aggregates in the range of ~100 microns, more preferably 0.1-50 microns. The reason why each particle of the granular or powdered resin product of the present invention is composed of spherical primary particles of extremely small particle size and secondary aggregates thereof as described above is because the method of the present invention is as described in the above manufacturing method of the product of the present invention. According to the authors, phenols (or diluted solutions thereof) are added to a hydrochloric acid-formaldehyde bath to form an at least partially homogeneous solution, then a white cloud is generated, and the extremely small cloudy particles are subjected to a stable and hardening reaction. This is thought to be due to the growth of pink granular or powdery microparticles that have progressed to a certain extent. As described above, the granular or powdered resin product of the present invention is formed mainly of the above-mentioned spherical primary particles and microparticles of secondary aggregates thereof, and therefore, the above-mentioned () and (B) as specified in , at least 50% by weight of the total, preferably 70% by weight, particularly preferably at least 80% by weight of the total.
% by weight passes through a 100% Tyler mesh sieve.
This indication that the granular or powdered product of the present invention passes through the sieve means that the granular or powdered product of the present invention is lightly massaged by hand or passed through the sieve with a brush-like object. Avoid applying any force that does not forcefully destroy the particles (including secondary aggregates), such as lightly pressing or smoothing the particles on top, or tapping them with your hand. It's not a thing. The granular or powdered product of the present invention further has a free phenol content of more than 50 ppm and less than 500 ppm as measured by liquid chromatography, as specified in () and (C) above, and a suitable product is The free phenol content exceeds 50 ppm
400ppm or less, especially more than 50ppm and 300ppm or less. The reason why the free phenol content of the product of the present invention is so small is that, as described in the manufacturing method of the product of the present invention, phenols or a diluted solution thereof are added to the hydrochloric acid-formaldehyde bath, and at least partially After forming a homogeneous solution, phenols,
In particular, it is believed that substantially all of the phenols involved in the formation of the product of the present invention react with formaldehyde. While the granular or powdered product obtained by the method disclosed in Japanese Patent Publication No. 53-42077 contains an extremely large amount of free phenol, ranging from 0.3 to about 6% by weight, the granular or powdered product of the present invention contains The free phenol content is low, a fact which is an important advantage for granular or powdered products of this type. Furthermore, as specified in () and (3) above, the resin constituting the granular or powdered product of the present invention has an infrared absorption spectrum of D _{999 - 1015} /D ₁₆₀₀ = 0.2 - 9.0, D ₈₉₀ /D ₁₆₀₀ = 0.09 to 1.0. The product of the present invention preferably has _{D990- D1015} / _D1600 of 0.2-5.0, particularly 0.3-4.0, and _D890 / _D1600 of 0.1-0.9, particularly 0.12-0.8. In the infrared absorption spectrum, the D ₁₆₀₀ peak shows absorption attributed to the benzene nucleus,
It is already widely known regarding phenol-formaldehyde resins that the peaks D _{990 to 1015} show absorptions attributed to methylol groups, and the peak D ₈₉₀ shows absorptions attributed to isolated benzene nuclei and hydrogen atoms. The fact that the product of the present invention exhibits a characteristic value of _D990-1015 / _D1600 = 0.2-9.0 means that the product of the present invention contains at least a certain amount of methylol groups, and the methylol group content varies considerably. This shows that it can be adjusted to Especially D _990~1015 = 0.2~5.0, especially 0.3~4.0
Preferred products of the invention contain moderate concentrations of methylol groups and are more stable. Furthermore, the fact that the infrared absorption spectrum of the product of the present invention shows D ₈₉₀ /D ₁₆₀₀ = 0.09 to 1.0, and the more preferred product exhibits a characteristic of D ₈₉₀ /D ₁₆₀₀ = 0.1 to 0.9, especially 0.12 to 0.8, The product exhibits the fact that the reactive sites (ortho and para positions) of the phenol molecules involved in the reaction are moderately blocked, possibly by methylo-groups. Cured products of conventionally known resol resins are generally
Both or one of D _{990 to 1015} /D ₁₆₀₀ and D ₈₉₀ /D ₁₆₀₀ is lower than the lower limit of the above characteristic value of the product of the present invention, and the novolac resin cured with hexamine also has D ₈₉₀ /D ₁₆₀₀ . The characteristic values are generally lower than the lower limit of 0.09 for the products of the present invention. Further, the granular or powdered resin product of the present invention preferably has a methanol solubility of 20% by weight or more, preferably a methanol solubility of 30% by weight or more, particularly 40% by weight or more. This characteristic indicates the fact that the product of the invention contains a large amount of relatively low molecular weight condensates that are soluble in methanol. The granular or powdered resin product of the present invention is characterized by having the characteristics ()(1), (2), (3), (4) and ()(A), (B), and C described above. do. The granular or powdered resin of the present invention has a particle size of 0.1 to
Contains spherical primary particles of 150 microns, preferably 0.1 to 100 microns, and secondary aggregates thereof (conditions in ()(A) above), preferably containing at least 50% of these, and at least 50% by weight thereof. Preferably, at least 70% by weight of the resin has a size that allows it to pass through a 100-meter mesh sieve (conditions () and (B) above), so it has extremely good fluidity and is comparatively superior to, for example, other resins. It can be mixed in large quantities, and even when mixed with other resins and used, for example, as an injection molding material, it can be extruded smoothly even in an unmolten state without clogging the nozzle.
In addition, since at least many of the products of the present invention have extremely small spherical primary particles as a basic component, cured molded products containing these as a reactive filler or reactive matrix have excellent mechanical properties. properties, especially strong resistance to compression.
The granular or powdered resin product of the present invention is made by growing white cloudy microparticles, which are the initial reaction product of phenols, further reacting with formaldehyde, so it is extremely stable at room temperature, and it itself contains a considerable amount of methylol groups. It is reactive when heated, and can be used by itself or with molding materials such as resol resin or other resins or rubber, such as asbestos, wood flour, linter pulp, glass, silica, and coconut husk. It exhibits reactivity when mixed with fillers such as, molded, and heated to harden, and as shown in the reference examples below, it has excellent not only physical and mechanical properties but also heat insulation, heat resistance, and other electrical properties. Excellent molded products can be formed. The granular or powdered resin of the present invention further has a free phenol content of more than 50 ppm and less than 500 ppm, preferably more than 50 ppm and less than 400 ppm, especially 50 ppm.
Exceeding 300ppm or less (above ())
(C) conditions). Because of this low phenol content, the granular or powdered resin of the present invention is extremely easy to handle and safe. Also,
Therefore, for example, even when used as a binder for the production of asbestos paper, synthetic fiber paper, or other non-woven fabrics, the amount of free phenol generated not only in the product but also in waste liquid or during processing. is small. In addition, since it contains almost no free phenol, there is almost no side reaction caused by phenol when mixed with other resins and molded, and there is also no possibility of deterioration of the physical properties of the molded product. Contains no free phenols. The granular or powdered resin of the present invention itself has a
Shows a light reflectance of ~70. The granular or powdered resin of the present invention can be obtained in accordance with the above-described production method of the present invention in which the curing reaction has not proceeded sufficiently. As a result, the granular or powdered resin of the present invention has a thermal property of 100% according to the heat fusion measurement method described later.
When pressurized for 5 minutes at a temperature of .degree. C., the material substantially melts or fuses to form a lump or a plate. According to elemental analysis, the granular or powdered resin of 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). Further, as is clear from the above-mentioned production method of the present invention, the granular or powdered resin of the present invention can be produced by the production method of the present invention which does not substantially contain a nitrogen-containing basic compound or a hydrophilic polymer compound in the reaction system. Since it is produced by the above method, it usually does not substantially contain nitrogen-containing basic compounds or hydrophilic polymer compounds. For this reason, when the granular or powdered product of the present invention is molded by itself or mixed with other resins or rubbers, etc., and is heated and cured, the physical properties of the molded product may be reduced or deteriorated. There is no fear. As mentioned above, the granular or powdered phenol-formaldehyde resin product of the present invention is extremely fine, has good storage stability and flow characteristics, has a low free phenol content, and contains a certain amount of methylol groups. Therefore, it has the excellent characteristic of being reactive when molded and heated by itself or mixed with other resins or rubbers, especially when heated by itself to give a self-curing resin. have. Thus, the granular or powdered resin products of the present invention are particularly useful as thermal or thermal insulating molding resins or binders thereof, or as reactive fillers. Examples of the present invention will be described below. 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 approximately 0.1 g sample was 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 dry 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 passed through 100 Tyler mesh = ω ₀ - ω ₁ / ω ₀ × 100 (weight%) ω ₀ : Input amount (g) ω ₁ : Amount remaining on the sieve without passing through the 100 Tyler mesh sieve (g ) 3 Determination of free phenol content Approximately 10 g of a sample passed through a 100-meter mesh is accurately weighed and heated under reflux for 30 minutes in 190 g of 100% methanol. Glass filter (No.3)
The filtrated solution was subjected to high performance liquid chromatography (6000A, manufactured by Waters, USA) to quantify the phenol content in the solution, 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 rate: 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). 4. Measurement of infrared absorption spectrum and determination of absorption intensity Using an infrared spectrophotometer (Model 225) manufactured by Hitachi, Ltd., the infrared absorption spectrum was measured for a measurement sample prepared by the usual KBr tablet method. 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 _tp , and the transmittance at the baseline at that wavelength is represented by tb, then the absorption intensity D at that specific wavelength is given by the following formula. D=logtb/tp 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 ₁₆₀₀ ). 5 Thermal adhesiveness at 100°C Approximately 5 g of the sample passed through a 100-meter 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. 6 Methanol solubility (S) 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 was determined using the following formula. Methanol solubility (S, weight %) = W ₀ - W ₁ /W ₀ ×
100 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) Example 1 (1) In a separable flask (2), various compositions of hydrochloric acid and formaldehyde (see Table 1) were added. 1,500 g of a mixed aqueous solution at 28°C consisting of
90% by weight phenol aqueous solution (22℃), respectively
55.6g was added. After adding and stirring for 30 seconds,
It was left to stand for 120 minutes. While standing for 120 minutes,
Some of the contents in each separable flask remained transparent (Run No. 1 in Table 1), while others changed from transparent to cloudy (Run No. 9 in Table 1). , 18 and 20), and some changed from transparent to cloudy and then turned pale pink (Run No. 2-8, 10-17 in Table 1).
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. In these experiments, during 120 minutes of standing, the temperature within each reaction system gradually increased due to exotherm (peak temperature 31.5° to 39.5°C).
Then it descended again. Each of the reaction products thus obtained was washed with water, then treated in a 0.5% by weight ammonia aqueous solution at 22°C for 3 hours with gentle stirring, washed again with water, dehydrated, and dried at a temperature of 40°C for 5 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 369 g of 282 and 37% by weight formalin and 150g of 26% by weight ammonia water, raise the temperature from room temperature to 70°C 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 transparent yellow-brown resol resin solution was taken out. The free phenol content determined by liquid chromatography was 3.4% by weight. 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 thermosetting resol resin powder thus obtained was treated with a 0.5% by weight aqueous ammonia solution, washed with water, dehydrated, and then dried under the same conditions as described above. The properties of the samples thus obtained are shown in Table 2 by Run No.
It was listed as 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. Moreover, the methanol solubility was 100% 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 0.5% by weight aqueous ammonia solution, washed with water, dehydrated and then dried under the same conditions as described above. Run the properties of the sample thus obtained.
It is listed in Table 2 as 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 fibrous degree
A spun yarn of 2.1 denier was immersed in a mixed aqueous solution containing 18% 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 cured novolak fiber thus obtained was washed with water under the same conditions as described above, and then treated with a 0.5% by weight ammonia aqueous solution.
It was washed with water, dehydrated, and then dried. This material was ground in a ball mill. The properties of what passed through the sieve of 100 Tylers were determined as Run No. 23.
It is listed in the table. (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. Table 2 also shows 1-50 μ, 1-100 μ, and 1-1 μ by microscopic observation of the obtained samples.
Content of 150 μ particles, amount of sieve passing through a 100-meter mesh (100 mesh passes), 990 to 1015 cm ^-1 and 890 cm ^-1 by infrared absorption spectroscopy of the obtained sample of
Absorption wavelength intensity ratio (IR intensity ratio) to 1600cm ^-1
and methanol solubility.

【table】

【table】

[Table] It was difficult to extract powdery or powdery solids from Run Nos. 1, 9, 18, and 20 in Table 1. Also Run No.2, 3, 6 and 17
In this experiment, a lot of sticky resin and lumps were formed at the bottom of the detachable flask. 1-50μ, 1-100μ and 1 listed in Table 2 for Run No. 2, 3, 6 and 17 experiments.
The values for the content (%) of ~150 micron particles and 100 mesh pass (% by weight) are for the adhesive resin and the granular or powdery material relative to the total solids including lumps and platelets. However, in these experiments, only 1 to 50 microns of the granular or powdered solids produced,
Content (%) of 1-100μ and 1-150μ particles
and 100 mesh pass (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, 9, 17, 18 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. There is. (3) Figure 1B of the attached drawings shows a scanning electron micrograph (1000x magnification) of the granular or powdery material obtained in Run No. 12 above. Further, Figure 1A of the attached drawings shows an optical micrograph (400x magnification) of the granular or powdery material obtained in Run No. 12. Example 2 In a room with a room temperature of 21 to 22°C, 8 kg of a mixed aqueous solution consisting of 20% by weight hydrochloric acid and 10% by weight formaldehyde was placed in each of 6 of 10 reaction vessels. Then, in each flask, add 80% by weight of phenol and formaldehyde while stirring at a temperature of 20 °C.
1.43Kg and 1.18Kg of mixed aqueous solution consisting of 3.7% by weight, respectively.
Kg, 0.08Kg, 0.55Kg, 0.34Kg and 0.23Kg were added. The bath ratios in this case are 7.3, 8.8, 12.8, respectively.
They were 18.4, 29.9 and 43.7. In either case, when stirring was continued after adding the phenol mixed aqueous solution, the mixture suddenly became cloudy in 50 to 170 seconds. As soon as the mixture became cloudy, stirring was stopped and the mixture was allowed to stand for 3 hours. 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. The contents of each were then washed with water while stirring. In this case, in the system with a bath ratio of 7.3, a large amount of resin adhered to the stirring rod, making stirring difficult. The contents were then dissolved in a 0.3% by weight aqueous ammonia solution.
The mixture was treated at a temperature of 30°C for 2 hours with gentle stirring, washed with water, and then dehydrated. 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 0.5% by weight or less in all cases. The contents are Run No. 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 3 hours after it becomes cloudy, the yield of the reaction product, the presence or absence of spherical primary particles as observed by microscopy, and the proportion of 100 tyers in the reaction product. The content of the mesh-passed product, the bulk density of the 100-mesh-passed product, the heat-fusibility of the reaction product at 100°C, the amount of methanol dissolved, and the free phenol content are shown.

[Table] In Table 3, Run No. 21, 22 and 23 (1st
The free phenol content of Comparative Example (see Table) is the value measured for the resol resin and novolak resin before heat curing, and is shown in parentheses. In Table 3, in the experiment of Run No. 31, sticky resin and lumps amounted to about 80% of the total solids formed at the bottom of the flask. Granules or powders accounted for only about 20% of the total solids produced, but about 85% of them passed through a 100 mesh sieve. 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 20%. 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. Example 3 In each of six separable flasks, 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 diluent, 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 rises from 25℃, and reaches 35 to 36℃ in 16 to 17 minutes after adding the diluent.
reached its peak and then fell again. After adding 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, then 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 of the samples from Run No. 41 to Run No. 46 were fused at 100° C. for 5 minutes in the thermal fusion test. Figures 2A and 2B show an optical micrograph and a scanning electron micrograph of Run No. 44. Further, FIG. 3 of the attached drawings shows an infrared absorption spectrum diagram of the granular or powdered resin of Run No. 44. Furthermore, FIG. 3 illustrates how to obtain t _p and t _b , which are necessary when obtaining the condensation intensity D from an infrared absorption spectrum diagram. Draw a baseline at a certain peak, and at that wavelength t _p and t _b
can be obtained as illustrated.

[Table] Seven separable flasks of Example 4-2 were prepared, and 1.5 kg of a mixed aqueous solution consisting of 18% by weight hydrochloric acid and 9% by weight formaldehyde was placed in each flask. Immerse the separable flask in ice water, water, or hot water to adjust the internal temperature of the mixed water to 2° to 3°C (Run No. 51), 7° to 8°C.
℃ (Run No.52), 13~14℃ (Run No.53), 27~28℃
(Run No. 54) and 32 to 33°C (Run No. 55). Next, while stirring each mixed aqueous solution, 50 g of phenol aqueous solution diluted with water was added at once to each mixed aqueous solution, stirring was stopped, and the mixture was allowed to stand for 5 hours. Thirty minutes after the stirring was stopped, the cooling water, hot water, etc. in the separable flask were removed. The contents of each product produced in the above method were washed with water, and then dissolved in a 0.1% by weight aqueous sodium hydroxide solution at a temperature of 20°C.
25 hours, and then in 1% by weight ammonia water for 25 hours.
℃ temperature for 2 hours, washed with water again, and then washed with water and dehydrated. The reaction product thus obtained was lightly massaged by hand and dried at a temperature of 45° C. for 5 hours. Table 5 shows the concentration of the phenol aqueous solution added, the maximum temperature reached in the reaction system, the methanol solubility of the obtained product, and the amount of 100 mesh passes.

[Table] Example 5 800 kg of a mixed aqueous solution at 18°C consisting of 18.5% by weight hydrochloric acid and 8.5% by weight formaldehyde was placed in a 1000°C reaction vessel equipped with a stirring bar, and the mixed aqueous solution was heated at 20°C while stirring. 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. Inside 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 product 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 reaction product, the hydrochloric acid, and formaldehyde. The mixed aqueous solution was 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.
60). Table 6 shows the content of 0.1-50μ and 0.1-100μ particles as determined by microscopic observation of the dried sample thus obtained;
Shows 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. Ta.

[Table] Example 6 18% by weight in three 1 separable flasks
of hydrochloric acid, 10% by weight of formaldehyde and 5% by weight of zinc chloride in an aqueous solution at 22°C.
I added each. While stirring, 25 g of a mixed aqueous solution containing 90% by weight of the phenols listed in Table 7 and 10% by weight of 37% formalin was added to each of these at room temperature, and 30 seconds after the addition, both were stirred. has been stopped. After stopping the stirring and allowing it to stand for 2 hours, the contents were taken out, washed with water, treated in a 1% by weight ammonia aqueous solution at a temperature of 22°C for 3 hours, and then washed with water.
Dehydrated and dried at a temperature of 40°C for 5 hours. Table 7 shows the composition of the phenols used, the time at which cloudiness started after administration, the elemental analysis value of the obtained product, and the amount passed through a 100-mesh sieve.

[Table] Reference Example 1 A certain amount of the product of Run No. 35 of Example 2 was placed between a press machine and treated for 30 minutes under a gauge pressure of 50 kg using a mold preheated to 100°C. Ten test pieces with dimensions of 10 mm in width, 80 mm in length, and 5 mm in thickness were created (Run No. 71). On the other hand, a control test piece was prepared as follows. A part of the resol resin (uncured product) solution used in Run No. 21 of Example 1 was put into a vat, and the solvent was removed under reduced pressure (it foamed violently at first, but the foaming started to decrease), and then it was taken out from the vat. Air-dried for a day.
Ten test pieces were made from this material under the same conditions and method as above (Run No. 72), except that it was crushed in a mortar and then heated at a temperature of 150°C (because molding was difficult at 100°C). Also, the same as above except that the novolak resin (uncured material) used in Run No. 22 of Example 1 was crushed in a mortar, 15% by weight of hexamethylenetetramine was mixed, and the mixture was heated at a temperature of 150°C. Ten test pieces were created using the following conditions and method (Run No. 73). Table 8 shows the appearance of the molded products of Run No. 71 to 73, the density determined by the milk sedimentation method, and the results of five test pieces cut into 10 mm lengths from each test piece using a compression tester. Compressive strength, compressive strain, and stickiness (Stickiness; compressive strength x compressive strain) measured according to JIS-K-6911-1970 are shown as average values for five test pieces. The dimensions of the test pieces were accurately measured using calipers before the compression test.

[Table] Reference Example 2 Five test pieces each of Run No. 71 to 73 of Reference Example 1 were heated from room temperature to 1000℃ for 24 hours under nitrogen gas flow.
The temperature was raised over time, maintained at a temperature of 1000°C for 1 hour, and then allowed to cool. Run the test pieces created by carbonization and firing in this way from Run No. 71 to 73 in order.
No. 81 to 83. Table 9 shows the number of carbonized and fired products obtained by the above method (good products) with almost no gas blisters or cracks observed, the density of the crushed samples measured by the milk sedimentation method, and the carbonization yield (using the ) and bending strength.

[Table] Reference Example 3 To 60 parts by weight of the product of Run No. 52 obtained in Example 1,
As fillers, 40 parts by weight of each of asbestos (Run No. 84), wood flour (Run No. 85), or 6-nylon (Run No. 86) were mixed. For comparison, asbestos (Run No. 87), wood flour (Run No. 88), or 6-nylon (Run No. 89) were mixed, air-dried for a day and night, and the resol resin was further desolvented at a temperature of 80° C. for 30 minutes to obtain a mixture. Furthermore, for comparison, asbestos (Run No. 90) and wood flour (Run No. 91) were added as fillers to 60 parts by weight of a mixture of the novolak resin obtained in Run No. 22 of Example 1 and 10% by weight of hexamethylenetetramine. ) or 6-nylon (Run No. 92) in an amount of 40 parts by weight. A fixed amount of each of the nine types of mixtures obtained by the above method was placed in a mold that had been preheated to 160°C between heating press machines, and pressed at a gauge pressure of 40 kg for 30 minutes. However, 15 test pieces each having a width of 12 mm, a length of 120 mm, and a thickness of 7 mm were obtained. Table 10 shows the types of resins and fillers used, the average bending strength of each of the five molded products obtained, and the test specimens heated at 110°, 120°, 130°, 140° in a dryer.
The heat resistance temperature is the maximum temperature at which no cracks or gas bubbles are observed when treated at temperatures of 150°, 160°, 170°, 180°, 190° and 200°C for 24 hours.

【table】 [Brief explanation of the drawing]

Figures 1A and 2A of the accompanying drawings are optical micrographs (magnification) of the granular or powdery product of the present invention.
400 times). Figures 1B and 2 of the accompanying drawings
Figure B is a scanning electron micrograph (1000x magnification) of the granular or powdery material of the present invention. FIG. 3 is an infrared absorption spectrum diagram of the granular or powdery material of the present invention. Note that FIG. 3 also illustrates a method for determining the absorption intensity at a specific wavelength of the peak. In addition, in the photographs of Figures 1A and 2A,
The minimum division of the scale is 10μ.

Claims (1)

[Scope of Claims] 1. A granular or powdered resin consisting of a condensate of phenols and formaldehyde, wherein () the condensate is (1) substantially composed of carbon, hydrogen, and oxygen atoms; , (2) Contains a methylene group, a methylol group, and a trifunctional residue of phenols as the main bonding unit, (3) The trifunctional residue contains 2 and 4 phenolic residues.
and a methylene group at one position in the 6-position and a methylol group and/or at least one other position.
(4) In the infrared absorption spectrum by KBr tablet method, the absorption intensity at 1600 cm ^-1 (absorption peak attributed to benzene) is D ₁₆₀₀ and 990 to 1015 cm ^-1 (absorption peak attributed to methylol group). The largest absorption intensity in the range of absorption peaks
D _{990 ~ 1015} , When the absorption intensity of 890 cm ^-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 to 1.0, and () the granular or powdered resin contains (A) spherical primary particles and secondary aggregates with a particle size of 0.1 to 150 microns, and (B) at least 50% by weight of the total (C) has a free phenol content of more than 50 ppm as measured by liquid chromatography;
Granular or powdered phenol characterized by having a content of 500 ppm or less.
Formaldehyde resin. 2. The granular or powdered resin has at least 30
% of spherical primary particles and secondary aggregates thereof having a particle size of 0.1 to 150 microns. 3. The granular or powdered resin has at least 50
% of spherical primary particles and secondary aggregates thereof having a particle size of 0.1 to 150 microns. 4. The granular or powdered resin according to claim 1, in which 70 to 100% of the granular or powdered resin consists of spherical primary particles with a particle size of 0.1 to 150 microns and secondary aggregates thereof. 5. The granular or powdered resin according to any one of claims 1 to 4, which has a size that allows at least 70% by weight of the total weight to pass through a 100-meter mesh sieve. 6. The granular or powdered resin according to any one of claims 1 to 4, which has a size that allows at least 80% by weight of the entire resin to pass through a 100-meter mesh sieve. 7 The resin has a free phenol content of more than 50 ppm as measured by liquid chromatography.
The granular or powdered resin according to any one of claims 1 to 6, which has a content of 400 ppm or less. 8 The resin has a free phenol content of more than 50 ppm as measured by liquid chromatography.
The granular or powdered resin according to any one of claims 1 to 6, which has a content of 300 ppm or less. 9. The granular or powdered resin according to any one of claims 1 to 8, wherein the resin has _D990-1015 / _D1600 = 0.2-5.0 in an infrared absorption spectrum measured by a KBr tablet method. 10. The granular or powdered resin according to any one of claims 1 to 8, wherein the resin has _D990-1050 / _D1600 = 0.3-4.0 in an infrared absorption spectrum measured by a KBr tablet method. 11. The granular or powdered resin according to any one of claims 1 to 10, wherein the resin has a D ₈₉₀ /D ₁₆₀₀ =0.1 to 0.9 in an infrared absorption spectrum determined by a KBr tablet method. 12. The granular or powdered resin according to any one of claims 1 to 10, wherein the resin has D ₈₉₀ /D ₁₆₀₀ =0.12 to 0.8 in an infrared absorption spectrum measured by a KBr tablet method. 13 10 g of the resin was added to substantially anhydrous methanol.
When heated under reflux in 500 ml, the following formula S = (W ₀ - W ₁ ) / W ₀ × 100 In the formula, W ₀ is the weight (g) of the resin used, and W ₁ is the weight remaining after heating and refluxing. The weight (g) of the resin, S represents the methanol solubility (wt%) of the resin, and the methanol solubility represented by is 20 wt% or more. The granular or powdered resin described in . 14. The granular or powdered resin according to any one of claims 1 to 12, wherein the resin has a methanol solubility of 30% by weight or more. 15. The granular or powdered resin according to any one of claims 1 to 12, wherein the resin has a methanol solubility of 40% by weight or more. 16. The granular or powdery resin according to any one of claims 1 to 15, wherein the resin does not substantially contain a nitrogen-containing basic organic compound. 17. The granular or powdered resin according to any one of claims 1 to 15, wherein the resin does not substantially contain a hydrophilic polymer compound. 18 The resin essentially contains carbon,
Claims 1 to 17 consist of hydrogen and oxygen and have 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 granular or powdered resin according to any of the above. 19 When the resin is held at a temperature of 100°C for 5 minutes according to the heat fusion measurement method described in the text,
Claims 1 to 2 that are substantially melted or fused
The granular or powdered resin according to any one of Item 18. 20 (1) The following composition, hydrochloric acid (HCl) concentration 5 to 28% by weight, formaldehyde (HCHO) concentration 3 to 25
% by weight, and the total concentration of hydrochloric acid and formaldehyde is 15-40
% by weight in a hydrochloric acid-formaldehyde bath, (2) maintaining the bath ratio expressed by the following formula = (weight of the above hydrochloric acid-formaldehyde bath)/weight of phenols to be at least 8 or more, (3) Contacting the phenols with a hydrochloric acid-formaldehyde bath, and changing the contact so that after the phenols come into contact with the bath, a white turbidity is formed, and then at least a pink granular or powdery solid is formed. A granular or powdered resin made of a condensate of phenols and formaldehyde, characterized in that the temperature in the reaction system is maintained at 45°C during this contact, ) The condensate is (1) substantially composed of carbon, hydrogen, and oxygen atoms, and (2) contains trifunctional residues of methylene groups, methylol groups, and phenols as main bonding units. (3) The trifunctional residue is phenolic 2-4
and a methylene group at one position in the 6-position and a methylol group and/or at least one other position.
or a methylene group, and (4) In the infrared absorption spectrum by KBr tablet method, the absorption intensity at 1600 cm ^-1 (absorption peak attributed to benzene) is D ₁₆₀₀ and 990 to 1015 cm ^-1 (absorption peak attributed to methylol group). The largest absorption intensity in the range of absorption peaks
D _{990 ~ 1015} , When the absorption intensity of 890 cm ^-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 to 1.0, and () the non-granular powdered resin contains (A) spherical primary particles and secondary aggregates with a particle size of 0.1 to 150 microns, and (B) at least 50% by weight of the total (C) has a free phenol content of more than 50 ppm as measured by liquid chromatography;
A method for producing granular or powdered phenol/formaldehyde resin with a concentration of 500 ppm or less. 21 The concentration of hydrochloric acid in the hydrochloric acid-formaldehyde bath is 10
21. The method of claim 20, wherein the amount is ~25% by weight. 22. The method according to claim 20 or 21, wherein the formaldehyde concentration of the hydrochloric acid-formaldehyde bath is 7 to 15% by weight. 23. The method according to any one of claims 20 to 22, wherein the total concentration of hydrochloric acid and formaldehyde in the hydrochloric acid-formaldehyde bath is 20 to 35% by weight. 24. The method according to any one of claims 20 to 23, wherein the bath ratio is maintained at 10 or more. 25. The method according to any one of claims 20 to 24, wherein the bath ratio is maintained at 15 to 40. 26. The method according to any one of claims 20 to 25, wherein the phenols are added to the hydrochloric acid-formaldehyde bath and the bath is stirred to form a homogeneous transparent solution at a stage before white turbidity is generated. Method. 27. Claim 20: No mechanical shearing force is applied to the hydrochloric acid-formaldehyde bath during the period from the time when phenols are added to the bath until a pink solid is formed. ~2
The method described in any of Section 6. 28 Claim 20, in which phenols are diluted with water and added to the hydrochloric acid-formaldehyde bath.
28. The method according to any one of items 27 to 27. 29. The method according to claim 20, wherein the temperature of the hydrochloric acid-formaldehyde bath before contacting with the phenols is between 5 and 35°C. 30. The method according to claim 20 or 29, wherein the temperature of the hydrochloric acid-formaldehyde bath before contacting with the phenols is between 10 and 30°C. 31. The method according to any one of claims 20 to 30, wherein the phenol is phenol, metacresol, or a mixture thereof. 32. The method according to any one of claims 20 to 30, wherein the phenols are phenols. 33 Phenols containing at least 80% by weight of phenols and the following groups: o-cresol, m-cresol, p-cresol, bis-phenol A, o-, m- or p-
The method according to any one of claims 20 to 23, which is a mixture with at least one substituted phenol selected from _C2 - _C4 alkylphenol, p-phenylphenol, xylenol, resorcinol, and hydroquinone. 34. A solid substance of granular or powdery phenol formaldehyde resin obtained by the method according to any one of claims 20 to 33 is treated with the hydrochloric acid.
Separated from formaldehyde bath, washed with water,
The method according to any one of claims 20 to 33, wherein the attached hydrochloric acid is neutralized with an aqueous alkali solution and further washed with water. 35. The method according to claim 34, wherein aqueous ammonia is used as the alkaline aqueous solution. 36. The method according to claim 35, wherein the alkali metal hydroxide or ammonia concentration in the aqueous alkali solution is 0.1 to 5% by weight. 37. The method according to claim 36, wherein the concentration of the alkali metal hydroxide or ammonia in the aqueous alkali solution is 0.5 to 3% by weight. 38. The method according to claim 34, wherein the neutralization with the alkaline aqueous solution is carried out at a temperature of 50° C. or lower. 39 Neutralization with the aqueous alkaline solution at 10 to 40°C
35. The method according to claim 34, which is carried out at a temperature of .