JPS6235419B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a thermosetting resin composition containing a novel granular or powdery nitrogen-containing phenol aldehyde resin. More specifically, the present invention is directed to a thermosetting resin containing a novel granular or powdery nitrogen-containing phenol aldehyde resin that has good storage stability and flow characteristics and is reactive, and is suitable as a molding material. Regarding the composition. Conventionally, novolac resins and resol resins are known as typical phenolic aldehyde resins. Novolac resins usually have a molar ratio of phenol to formaldehyde, e.g. 1:0.7.
Under conditions of phenol excess such that ~0.9;
In the presence of an acid catalyst such as oxalic acid (usually 0.2
-2%) by reacting phenol with formalin. The novolac resin obtained by such a method is mainly composed of trimers to pentamers of phenols bonded mainly through methylene groups, contains almost no free methylol groups, and therefore cannot self-react by itself. It has no crosslinking properties and is thermoplastic. Therefore, the novolac resin is reacted under heat with a crosslinking agent which is itself a formaldehyde generator and also an organic base (catalyst) generator, such as hexamethylenetetramine (hexamine), or with a solid acid catalyst and paraformaldehyde, etc. A cured resin can be obtained by mixing with the resin and subjecting it to a heating reaction. Novolac resins are powdered and relatively easy to handle, and therefore can be mixed with a crosslinking agent and heated to form a cured resin as described above. However, since the reaction between the novolac resin and the crosslinking agent is slow, it takes a long time for hot molding to obtain a cured resin with sufficient crosslinking to give satisfactory performance. Often, the degree of crosslinking differs between the inside and outside, resulting in a cured resin product of non-uniform quality. Therefore, conventionally, cured resin products using novolac resin are made by mixing fillers such as kraft pulp, wood flour, or glass fiber into the novolac resin (usually containing hexamine) to form a precursor of the cured resin, which is then heated. Efforts have been made to manufacture cured resin products by molding. However, the time required for heat forming is still long;
In addition, since novolak resin has insufficient leakage properties to fillers, the resulting cured resin products often have voids between the cured novolak resin and the filler, which prevents the inherent superior properties of cured phenolic resins from being present. This results in a considerable sacrifice in electrical insulation, chemical resistance, etc. On the other hand, resol resins are also widely used as materials for cured phenolic resins, but since resol resins are self-curing resins, it is extremely difficult to turn them into powder without proceeding with a crosslinking reaction. Supplied as a solution in a solvent such as alcohol. Therefore, it is nearly impossible to manufacture cured resin products made of resol resin alone, and cured resin products using resol resin are limited to products containing fillers. Such products are manufactured by incorporating a filler into a resol resin solution, then removing the solvent to produce a precursor consisting of a solid mixture of the filler and resol resin, which is then thermoformed. Therefore, the biggest disadvantage of using resol resin as a material is that the precursor manufacturing process includes a step of removing the solvent, and that the solvent must be recovered. In addition, other resins such as epoxy resins and furan resins are also widely used as materials for producing cured products, but these resins are generally supplied as solvent solutions like resol resins, and like resol resins, the above-mentioned It has the following drawbacks. 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 to 10 phenol groups and methylene groups. A relatively high condensate bonded with A method of producing cured novolac resin fibers was proposed by proceeding the curing reaction from the outside of the fibers (Japanese Patent Publication No. 11284/1984). However, cutting or crushing the cured novolac fibers produced as described above is not only expensive, but also cannot be made into granules or powders with good flow characteristics. In addition, in recent years, a hydrophilic polymer compound is added to a condensate obtained by reacting phenols and formaldehyde in the presence of at least a nitrogen-containing compound, and the reaction is performed to produce granular or powdered resin. Although a method has been announced (Special Publication Act 1973)
42077), the non-gelled resin obtained by this method contains a large amount of free phenol, about 5-6% by weight (Examples 1 to 4), and the gelled product (Example 5) is extremely hard. Not only does it become a non-reactive resin, but since it contains a hydrophilic polymer compound, it has the disadvantage of lowering the performance of a curable resin molded article obtained by using it as a filler. Also, a method has been proposed in which the cured product of resol resin is made into granules or powder, but as mentioned above, resol resin is extremely reactive and cannot be made into a stable solid substance in the form of granules or powder. In addition, the cured product has a highly advanced three-dimensional structure and is therefore extremely hard, making it extremely difficult to use it as a molding material in the form of minute particles or powder (Japanese Patent Publication No. 12958/1983). 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), this corresponds to the so-called cured resol resin, and since it has no reactivity and contains salts, acids, and other protective colloids, it can also be used as a filler to form cured products. There are drawbacks that reduce the performance of the product. As mentioned above, attempts have been made to use phenol-formaldehyde resin as a filler in curable resin compositions. First of all, it is difficult to obtain a cured molded product in the form of a molded product, and it also has the problem that it contains substances that have an undesirable effect on the cured molded product. 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 curable resin composition containing a novel granular or powdery nitrogen-containing resin. Another object of the present invention is to provide a curable resin composition containing a granular or powdery nitrogen-containing resin having good flow characteristics or having good moldability. Still another object of the present invention is to provide highly reactive granular or powdery nitrogen-containing resins which can crosslink by themselves and react with other curable resins such as resol resins, novolac resins, epoxy resins or furan resins. The object of the present invention is to provide a curable resin composition containing the following: and thus imparting extremely homogeneous properties in the cured form. Still another object of the present invention is to provide a curable resin composition that is melted by heating and provides excellent wettability with various fillers in the cured form. Still another object of the present invention is to maximize the excellent performance of phenolic resins by providing them with excellent compressive strength, chemical resistance, electrical properties such as electrical insulation, heat resistance, or heat insulation properties in the cured form. The object of the present invention is to provide a curable resin composition that can be obtained. Further objects and advantages of the present invention will become apparent from the following description. According to the present invention, the objects and advantages of the present invention are as follows: (a) Condensation of phenols having the following properties (A) and (B) with nitrogen-containing compounds having at least two active hydrogens and aldehydes; (A) The condensate is (1) substantially composed of carbon, nitrogen, hydrogen and oxygen atoms, (2) methylene group, methylol group, a residue from which at least two active hydrogens have been removed from a nitrogen-containing compound and which is bonded to a methylene group at one of the 2, 4 and 6-positions and to a methylene group and/or a methylol group at the other two positions; It contains trifunctional phenol residues as the main bonding unit,
(3) In the infrared absorption spectrum of the resin by the KBr tablet method, the largest absorption intensity in the range of 1450 to 1500 cm ^-1 (absorption peak attributed to aromatic double bonds) is D _{1450 to 1500} , and D 960 to 1020cm
^-1 (absorption peak attributed to methylol group)
The largest absorption intensity in the range of
D _{960 to 1020} , when expressed as D _{960 to 1020} / D _{1450 to 1500} = 0.1 to 2.0, and (B) the granular or powdered nitrogen-containing resin has a particle size
(b) a curable resin other than the granular or powdery nitrogen-containing resin of (a) above, and/or (c) a filler material, containing spherical primary particles of 0.1 to 100 microns and secondary aggregates thereof; This can be achieved by a thermosetting resin composition characterized by containing at least. The curable resin composition of the present invention comprises the above (A) and
Contains granular or powdered nitrogen-containing phenol aldehyde resin specified in (B). Such granular or powdered nitrogen-containing phenolic aldehyde resins used in the present invention include phenols, or phenols containing at least 50% by weight of phenols, especially at least 70% by weight of phenols, such as o-cresol, m-cresol, p-cresol, etc. Cresol, bis-phenol A, o-, m- or p-
A condensate of a mixture with one or more known phenol derivatives such as C ₂ to C ₄ alkylphenol, p-phenylphenol, xylenol, and resorcinol, and a nitrogen-containing compound having at least two active hydrogens and an aldehyde. includes. The granular or powdery nitrogen-containing resin in the resin composition of the present invention has the properties (A) and (B) described above. In specifying (A) and (B) above, specifying that the particle size of the spherical primary particles and secondary aggregates of (B) is 0.1 to 100 microns, D _{960 to 1020} / of (A)
The specification of D _{1450 to 1500} = 0.1 to 2.0 is based on the measurement method described below. The first feature of the above granular or powdered nitrogen-containing resin is that it is extremely difficult to crush a conventionally known cured product of novolac resin or cured resol resin, but it can be forcibly crushed, or As specified in (B) above, most of them are spherical primary particles and their secondary aggregates, and the particle size is 0.1 to 100 microns. ,Preferably
Contains 0.1 to 50 microns. The above granular or powdered nitrogen-containing resin usually has at least 30%, preferably at least 50%, particle size.
It consists of spherical primary particles of 0.1 to 100 microns, more preferably 0.1 to 50 microns, and secondary aggregates thereof. This indication of 30% or 50% means that the magnification is 100 to 100%, as defined in the particle size measurement method described below.
It means 30% or 50% of the total number of particles (including secondary aggregates) in one field of view of a 1000x optical microscope. Particularly preferred is one in which 70 to substantially 100% of the granular or powdered nitrogen-containing resin consists of spherical primary particles and secondary aggregates thereof having a particle size of 0.1 to 100 microns. Particularly preferred is at least 30%, in particular at least 50% of the number of particles (as the average value of 5 fields) of the field of the optical micrograph according to the above definition.
The particles are comprised essentially 100% of spherical primary particles and secondary agglomerates thereof ranging from 0.1 to 50 microns, more preferably from 0.1 to 20 microns. As mentioned above, the above granular or powdered nitrogen-containing resin is formed mainly of the above spherical primary particles and microparticles of secondary aggregates thereof, so it is extremely small and has a small proportion of the total. In total, 50% by weight, preferably 70% by weight, and particularly preferably at least 80% by weight of the total passes through a 150 sieve mesh. Such an indication that the granular or powdered product passes through the sieve may be indicated by gently kneading the granular or powdered product by hand, or by brushing the granular or powdered product with the sieve. Do not apply any force that does not forcefully destroy the particles (including secondary aggregates), such as lightly pushing or smoothing the particles on the sieve, or tapping them with your hand. It does not exclude anything. The above granular or powdery nitrogen-containing resin further includes:
As specified in (A) above, in the infrared absorption spectrum, it has the following characteristics: _D960-1020 / _D1450-1500 = 0.1-2.0, preferably further _D1280-1360 / _D1450-1500 = 0.15-3.0 . Further, the preferable granular or powdery nitrogen-containing resin used in the present invention is D _960-1020 / D _1450-1500 = 0.15-0.6, preferably further D _1280-1360 / D _1450-1500 = 0.2-2.0 Particularly preferred ones have the following characteristics: D _960-1020 /D _1450-1500 = 0.2-0.4, and more preferably, D _1280-1360 /D _1450-1500 = 0.3-1.5. Further, the granular or powdery nitrogen-containing resin used in the present invention further has the maximum absorption intensity in the range of 1580 to 1650 cm ^-1 expressed as D _{1580 to 1650} in the infrared absorption spectrum by the KBr tablet method. D _{1580 ~ 1650} / D _{1450 ~ 1500} = 0.3 ~ 4.5 (preferably 0.75 ~ 2.0, particularly preferably 1.0 ~
1.5) It has the following characteristics in the infrared absorption spectrum. Generally, it is difficult to determine the attribution of various functional groups in a substance having a 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, from the infrared absorption spectra of phenol aldehyde resins and various nitrogen-containing compounds, the above absorption in the infrared absorption spectrum of the present invention shows that the absorption at 960 to 1020 cm ^-1 is a peak belonging to the methylol group, and the absorption at 1280 to 1360 cm ^- The absorption of ¹ is the peak assigned to the carbon nitrogen bond, and the absorption of 1450 ~
The absorption at 1500 cm ^-1 was determined to be the peak attributed to aromatic double bonds. In addition, although it is difficult to clarify the attribution of absorption between 1580 and 1650 cm ^-1 , the above ratio using the intensity of this absorption
The values D _{1580 to 1650} / D _{1450 to 1500} indicate values that can clearly distinguish the ratio in phenol-formaldehyde resins that do not contain nitrogen, so they are also used to specify the nitrogen-containing resin used in the present invention. It can be recognized as a characteristic absorption. One parameter for specifying the granular or powdery nitrogen-containing resin used in the present invention is the ratio of the above absorption intensities in the infrared absorption spectrum, for example D _960-1020 / D _1450-1500
The range of =0.1 to 2.0 means that the nitrogen-containing resin used in the present invention contains a considerable amount of methylol groups, and the content of methylol groups can also be adjusted within a certain range. It can be understood that it represents characteristic values associated with a certain structure. The granular or powdered nitrogen-containing resin used in the present invention usually has a free phenol content of 500 ppm or less as measured by liquid chromatography, and more preferred products have a free phenol content of 300 ppm or less, especially 100 ppm or less. It is. The granular or powdered resin obtained by the method disclosed in Japanese Patent Publication No. 53-42077 contains an extremely large amount of free phenol, ranging from 0.3 to about 6% by weight, whereas the granular or powdered resin used in the present invention The free phenol content of nitrogen-containing resins is extremely small. This fact provides an important advantage in use for this type of granular or powdered resin. It has also been found that many of the granular or powdered nitrogen-containing resins used in the present invention contain at least 1% by weight of nitrogen, preferably 2 to 30% by weight. 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 relatively, according to the manufacturing method described later. can. As a result, thermally, the granular or powdery nitrogen-containing resin used in the present invention has (a) It includes both (b) those in which at least a portion thereof is fused to form a lump or plate-like body, and (b) those that are not substantially melted or fused and take the form of granules or powder. When the solubility of the resin in (a) above, which has relatively high fusibility, is measured in methanol according to the test method described later, it has a solubility of 20% or more, even 30% by weight or more, and even more than 40% by weight. Included are resins that exhibit methanol solubility. The granular or powdery nitrogen-containing resin used in the present invention is characterized by having the properties (A) and (B) described above. The granular or powdered nitrogen-containing resin used in the present invention has a particle size of 0.1 to 100 microns, preferably
Contains spherical primary particles of 0.1 to 50 microns and secondary aggregates thereof (condition (B) above), preferably at least 50% and usually at least 50% by weight, preferably at least 70% by weight. Weight% is 150
Since it has a size that allows it to pass through a Tyler mesh sieve, it has extremely good fluidity and can be easily mixed with a curable resin and/or filler in a relatively large amount. Further, since at least many of the granular or powdery nitrogen-containing resins used in the present invention have extremely small spherical primary particles as a basic constituent, the thermosetting resin of the present invention containing these particles The cured moldings obtained by curing the composition exhibit excellent mechanical properties, in particular strong resistance to compression. The granular or powdered nitrogen-containing resin used in the present invention is extremely stable at room temperature, and since it itself contains a considerable amount of methylol groups, it exhibits reactivity when heated, and as shown in the examples below, it exhibits physical and A cured molded product is formed which has extremely excellent not only mechanical properties but also electrical properties such as heat insulation, heat resistance, electrical insulation, and chemical resistance. The granular or powdered nitrogen-containing resin used in the present invention further has a free phenol content of usually 500 ppm.
It is preferably as low as 300 ppm or less, particularly 100 ppm or less. Since the phenol content is extremely low, the granular or powdered nitrogen-containing resin used in the present invention is extremely easy to handle and is safe. This also means that since the thermosetting resin composition of the present invention has an extremely low free phenol content as described above, there will be fewer side reactions caused by phenols when obtaining these molded products. ing. 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 substantially no polymeric compounds. For this reason, when the thermosetting resin composition of the present invention is molded, heated and cured, there is no risk of deterioration or deterioration of the physical properties of the molded product. As mentioned above, the granular or powdered nitrogen-containing phenol aldehyde resin used in the present invention is
The thermosetting resin composition of the present invention is molded and heated because it is extremely fine, has good storage stability and flow properties, contains a certain amount of methylol groups, and usually has a very low free phenol content. It has the excellent feature of being reactive in some cases. Thus, among the granular or powdery nitrogen-containing resins used in the present invention, according to the heat fusion measurement method,
The resin of (a) above, which exhibits fusion properties at least in part when heated at 100°C for 5 minutes, can be used in the present invention to provide a cured molded product having particularly heat resistance, heat insulation properties, chemical resistance, or electrical insulation properties. (b) which gives a curable resin composition of the type and which shows no fusion property by the above measurement method.
The above resin provides the curable resin composition of the present invention, which provides a cured molded article particularly excellent in heat resistance, heat insulation, impact resistance, or compressive strength. The granular or powdery nitrogen-containing resin used in the present invention has the following composition: (a) Hydrochloric acid (HCl) concentration of 3 to 28% by weight, and (b) Formaldehyde (HCHO) concentration of 3 to 25% by weight.
% by weight and the concentration of aldehydes other than formaldehyde are 0 to 10% by weight, and (c) the total concentration of hydrochloric acid and formaldehyde is 10 to 10% by weight.
(2) Phenols and a nitrogen-containing compound having at least two active hydrogens are added to a hydrochloric acid-formaldehyde bath of 40% by weight according to the following formula (), bath ratio = weight of the above hydrochloric acid-formaldehyde bath/above. It can be produced by contacting them while maintaining the bath ratio represented by the weight of the phenols + the weight of the nitrogen-containing compound to be at least 8 or more. Regarding 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 (mol) in the bath/contact with the bath. It is preferable that the total molar ratio of phenols (moles) to nitrogen-containing compounds (moles) be at least 2 or more, particularly 2.5 or more, especially 3 or more. Above condition d)
The upper limit of the molar ratio of is not particularly limited, but is 20 or less,
It is preferable that the The upper limit of the molar ratio under the above condition (d) is not particularly limited, but is preferably 20 or less, particularly 15 or less. The above molar ratio is preferably 4 to 15, particularly preferably 8 to 10. The feature of the above production method is that a bath of a hydrochloric acid-formaldehyde aqueous solution with a fairly high concentration of hydrochloric acid (HCl) and an excess of formaldehyde relative to phenols and nitrogen-containing compounds is used at a bath ratio of 8. As mentioned above, it is preferable to contact the phenols and the nitrogen-containing compound at a large ratio of 10 or more. 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% by weight or more and the bath ratio is 8 or more, so that the total weight of phenols and nitrogen-containing compounds is The weight proportions of both hydrochloric acid and formaldehyde to the total amount of water are at least 24% by weight.
Furthermore, since the method of the present invention is carried out at a total concentration of hydrochloric acid and formaldehyde of 10% by weight or more as described above, the total weight of hydrochloric acid and formaldehyde is 80% by weight relative to the total weight of phenols and nitrogen-containing compounds.
% by weight or more. As mentioned above, such reaction conditions are fundamentally different from the reaction conditions for producing novolac resins and resol resins known in the art. When the phenols and the nitrogen-containing compound are brought into contact with the hydrochloric acid-formaldehyde bath, the bath ratio represented by the above formula () is preferably 10 or more, particularly 15-40. The phenols and the nitrogen-containing compound are brought into contact with the hydrochloric acid-formaldehyde bath so that after the phenols come into contact with the bath, a white turbidity is formed, and then a granular or powdery solid is formed. The contact between the hydrochloric acid-formaldehyde bath and the phenols and nitrogen-containing compounds 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 generate cloudiness, the bath is stirred so that the added phenols and nitrogen-containing compounds form a transparent solution as uniform as possible. In addition, during the period from the time when cloudiness occurs until solid matter is formed, mechanical shearing force such as stirring may be applied to the bath (reaction liquid) depending on the ratio of phenols and nitrogen-containing compounds and reaction conditions. It is preferable not to give it. The phenol to be added may be the phenol itself, or may be a phenol diluted with formalin, an aqueous hydrochloric acid solution, water, or the like. Furthermore, when adding phenols or phenols and nitrogen-containing compounds (or their diluted solutions), the temperature of the hydrochloric acid-formaldehyde bath or the temperature of the hydrochloric acid-formaldehyde bath in which the nitrogen-containing compound has been dissolved in advance is 90°C. Below, a temperature of 70°C or lower is particularly suitable. If the temperature of the bath is higher than 40°C, especially higher than 50°C, the reaction rate between phenols and nitrogen-containing compounds and formaldehyde will be high, so phenols or phenols and nitrogen-containing compounds should not be used in particular. It is preferable to add it to the bath as a dilute solution diluted with the formalin 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 and brought into contact with each other, especially in the form of a trickle of a diluted solution thereof or as fine droplets as possible. is preferable. When the bath temperature is 40°C or higher, especially 50°C or higher, 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 temperature. The reaction rate between the phenols and the nitrogen-containing compound increases, and after the contact, white turbidity is formed within a short period of time or instantaneously, and granular or powdery solids are rapidly formed. Keep the temperature of the hydrochloric acid-formaldehyde bath below 40℃.
Preferably 5° to 35°C, particularly preferably 10 to 30°C
The phenols and the nitrogen-containing compound are added to this bath as they are, or the diluted solution thereof, preferably a diluted solution of the phenol and the nitrogen-containing compound in water, is maintained at 50°C or less, preferably at a temperature of about 50°C or less after white turbidity is formed.
Granular or powdered solids that have completed the desired reaction at a temperature of 45°C or lower generally exhibit heat-fusibility in the 100°C heat-fusibility test described below, since the curing reaction has not progressed sufficiently. becomes. On the other hand, the temperature of the hydrochloric acid-formaldehyde bath was set to 40
℃ or less, preferably 15° to 35° C., add the phenols and nitrogen-containing compounds to be added to the bath as they are or substantially the entire amount of the diluted solution thereof under stirring to form a transparent solution, After that, white turbidity is produced in a non-stirring state, and then a light pink granular or powdery solid is produced without increasing the temperature, and this solid is heated to a temperature higher than 50°C, preferably 70° to 95°C. If the desired reaction is completed by heating to a temperature of 100
℃ decrease or substantially disappear, or exhibit heat fusion properties at higher temperatures, such as 200℃, or have substantially no thermal fusion properties even at such high temperatures. Become. In any of the above cases, the nitrogen-containing compound may be added in advance to the hydrochloric acid-formaldehyde bath, and then only the phenols may be added. As the phenol used in the above method, phenol is most suitable, but any phenol containing at least 50% by weight, especially at least 70% by weight, such as o-cresol, m-cresol, p-cresol, etc.
Even if it is a mixture with one or more of the known phenol derivatives such as cresol, bis-phenol A, o-, m- or p- _C2 - _C4 alkylphenol, p-phenylphenol, xylenol, resorcinol, etc. good. The nitrogen-containing compound used in the above method is a compound having at least two active hydrogens in the molecule, preferably an amino group having active hydrogen in the molecule,
A compound having at least one group selected from the group consisting of an amide group, a thioamide group, a urein group, and a thiouraine group is used. Examples of such nitrogen-containing compounds include urea,
Examples include thiourea, urea or methylol derivatives of thiourea, aniline, melamine, guanidine, guanamine, dicyandiamide, fatty acid amide, polyamide, toluidine, cyanuric acid, or functional derivatives thereof. 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 The desired product can be obtained by neutralizing the hydrochloric acid with an alkaline aqueous solution, such as aqueous ammonia or methanolic aqueous ammonia, and further washing with water. In this case, as a matter of course, if the resin has a relatively high methanol solubility, it is preferable to neutralize it with an alkaline aqueous solution. The curable resin composition of the present invention contains, in addition to the granular or powdery nitrogen-containing phenol aldehyde resin, at least one of another curable resin and a filler. Thermosetting resins are preferably used as such curable resins. Preferred examples of such curable resins include resol resins, novolac resins, epoxy resins, furan resins, melamine resins, urea resins, and unsaturated polyester resins. Among such curable resins, resol resins, novolac resins, epoxy resins and furan resins are particularly preferably used. The curable resin can be used alone or in combination of two or more. Further, filler substances can be included in the curable resin composition of the present invention for various purposes. For example, in order to strengthen the resulting cured molded product, or to impart dimensional stability, heat resistance, flame retardancy, moldability or processability, filler substances normally used for such purposes may be used. It will be done. Such a filling material may be an inorganic or organic material, and may be granular, powdery, or fibrous. For example, glass fiber
Fibrous inorganic substances such as carbon fiber or asbestos; carbon powder, silica, alumina, silica,
Alumina; granular or powdery inorganic substances such as diatomaceous earth, calcium carbonate, calcium silicate, magnesium oxide, clay, antimony oxide or shirasu balloons; organic substances such as wood flour, linters, pulp or polyamide fibers, etc. can. The thermosetting resin composition of the present invention contains a granular or powdery nitrogen-containing resin as described above, and at least one of a curable resin and a filler. The appropriate blending ratio of each of these components in the thermosetting resin composition of the present invention depends on the characteristics of the granular or powdered nitrogen-containing phenol aldehyde resin used, such as whether or not they are heat-fusible or not. Strictly speaking, it varies depending on the type of curable resin and filler material used. However, in the thermosetting resin composition of the present invention, the curable resin is generally added to the total amount of the curable resin and the granular or powdery nitrogen-containing phenol aldehyde resin in the thermosetting resin composition. It can be contained in an amount of 10 to 90% by weight, preferably 16 to 80% by weight, more preferably 24 to 70% by weight. Further, the thermosetting resin composition of the present invention generally contains 5% of the filler based on the total amount of the filler and the granular or powdery nitrogen-containing phenol aldehyde resin in the thermosetting resin composition. ~89% by weight, preferably 10-77% by weight, more preferably 15
It can be contained in an amount of ~63% by weight. The thermosetting resin composition of the present invention contains the following three aspects. These aspects will be explained below. The first embodiment contains all of the above three components: a granular or powdered nitrogen-containing phenolic aldehyde resin, a curable resin, and a filler material. The granular or powdered nitrogen-containing phenol aldehyde resin has a reactive methylol group as described above. Therefore, the cured product obtained from the above resin composition is a granular or powdery nitrogen-containing phenol.
It is believed that the structure is such that the aldehyde resin and the curable resin are intimately mixed and the filler material is dispersed in the cured matrix.
As the granular or powdered nitrogen-containing phenol aldehyde resin, those having the above-mentioned thermal fusibility
(a), (b) which does not substantially exhibit heat-fusibility, or a mixture thereof can be used. For materials with heat-fusible properties that account for major parts of the resin components used, the granular or powder-like form during heat molding will cause the particles to bond to each other due to melting and therefore harden. It is believed that the particles are either largely collapsed or form a continuous phase in the compact. On the other hand, in cases where the granular or powdered nitrogen-containing resin accounts for a minor part of the resin component used, the granular or powdered nitrogen-containing resin is
(b), the filler is cured and dispersed to form independent islands derived from individual particles or powdered nitrogen-containing resin in the cured matrix of the cured molded product. It is believed that it works as follows. In this first embodiment of the invention, the thermosetting resin composition of the invention contains each component in the proportions already described above. More specifically, under the condition that the total amount of each component is 100 parts by weight, the granular or powdered nitrogen-containing resin contains 10 to 85 parts by weight, preferably
20 to 75 parts by weight, especially 30 to 65 parts by weight, and the curable resin is 10 to 85 parts by weight, preferably 15 to 70 parts by weight,
In particular, 20 to 55 parts by weight, and the filler material is 5 to 55 parts by weight.
80 parts by weight, preferably 10-65 parts by weight, especially 15-50 parts by weight
Parts by weight. In this first embodiment, it is particularly preferred that the curable resin is a noresol resin, a novolac resin or an epoxy resin and the filler is glass fiber. The second embodiment is a resin composition containing a granular or powdered nitrogen-containing phenol aldehyde resin and a filler material, and substantially no curable resin. As the granular or powdery nitrogen-containing resin, the above-mentioned one (a) having thermal fusibility or a combination of (a) and (b) which does not substantially exhibit thermal fusibility can be used. When using a combination of (a) and (b), (a) is based on the total amount of granular or powdered resin and filler material.
It is preferably 25% by weight or more and used in a larger amount than (b). The granular or powdery nitrogen-containing resin (a) having fusion properties used in the present invention has a sufficient property that even if it is heat-molded, it still has the excellent properties originally possessed by the cured phenolic resin, such as electrical properties. gives a cured product that can be used as a product. As mentioned above, it is extremely difficult to make a cured molded product from resol resin by itself, and even if novolak resin can produce a cured molded product by itself, its quality is inferior. Considering this, it is a breakthrough in this technical field that the granular or powdered nitrogen-containing resin used in the present invention can easily provide a cured product that can be used as a product in a very short time. It can be said that this has brought about significant progress. The cured product obtained from the composition of Embodiment 2 is extremely homogeneous because the matrix is derived only from granular or powdered nitrogen-containing resin (does not contain curable resin), and therefore has excellent heat resistance and electrical insulation properties. It has particularly excellent properties. In this second embodiment, the thermosetting resin composition of the present invention contains each constituent component in the proportions already described above. More specifically, the total amount of each component
Under the condition of 100 parts by weight, the particulate or powdered nitrogen-containing resin is 20 to 95 parts by weight, preferably 30 to 90 parts by weight, more preferably 40 to 85 parts by weight, and the filler material is 5 to 80 parts by weight. parts, preferably 10 to 70 parts by weight,
More preferably, it is 15 to 60 parts by weight. In this second embodiment, glass fibers, shirasu balloons, pulp, carbon powder, calcium carbonate or polyamide fibers are particularly preferably used as the filler material. A third embodiment contains a granular or powdered nitrogen-containing phenol aldehyde resin and a curable resin,
The resin composition is substantially free of filler substances. In this third aspect, the above-mentioned material having heat fusibility (a), material having substantially no heat fusibility (b), or a combination thereof can be used. (b) or this (b) that does not substantially have thermal adhesive properties
It is preferable to use a combination of and (a). The material (b) having substantially no thermal fusibility is preferably used in an amount of 5 to 90% by weight, more preferably 10 to 80% by weight, especially 15 to 70% by weight of the entire resin component. In this third aspect, the thermosetting resin composition of the present invention contains each component in the proportions already described above. More specifically, under the condition that the total amount of each component is 100 parts by weight, the granular or powdered nitrogen-containing resin is 10 to 90 parts by weight, preferably 20 to 80 parts by weight, more preferably 30 to 70 parts by weight. part, and the curable resin is 10
~90 parts by weight, preferably 20-80 parts by weight, more preferably 30-70 parts by weight. In this third aspect, the curable resin is
Resol resins and novolac resins are particularly preferably used. As described above, the thermosetting resin composition of the present invention contains a granular or powdery nitrogen-containing phenol aldehyde resin. This granular or powdered nitrogen-containing phenol aldehyde resin has a very unique feature that, unlike novolac resin, it can be cured without using a crosslinking agent such as hexamine (it can be said to be self-curing in the sense that it can be cured without using a crosslinking agent). It has a similar reactivity. As is clear from what has already been described above, such characteristic reactivity shines when a cured product is produced from the thermosetting resin composition of the present invention. For example, a granular or powdery nitrogen-containing resin that has the property of being fused by heating reacts with a curable resin such as a novolac resin used or a polyamide fiber used as a filler during curing, and also acts as a crosslinking agent itself. Since it can be cured without the use of a compound, it can be cured uniformly, giving a homogeneous cured product that is extremely strongly cured. In addition, when curing granular or powdery nitrogen-containing resins that do not fuse when heated, they substantially retain their particle form and proceed to further harden within the particles themselves, at the same time reacting with other curable resins at the interface. Therefore, it exhibits an excellent effect as a filler in the cured product. Therefore, in this case as well, a very strongly cured and homogeneous cured product is obtained. In the thermosetting resin composition of the present invention, a granular or powdery nitrogen-containing resin, a curable resin, and/or a filler substance are mixed as they are, for example, using a V-type blender, if both are solid substances. When using a solvent solution of a curable resin such as resol resin or furan resin, it can be manufactured by mixing using a kneader, mixer, roll, etc., and then removing the solvent. can do. The thermosetting resin composition of the present invention may be, for example, 80 to
0.1 to 10 hours at a temperature of 250℃, sometimes 1 to 500 hours
It can be converted into a cured product by heat treatment under pressure of Kg/cm ² . Usually, a resin composition is molded and then heat-treated to obtain a cured product. The cured product obtained from the thermosetting resin composition of the present invention has superior properties such as compressive strength, chemical resistance, electrical properties such as electrical insulation, heat resistance, and heat insulation properties compared to conventional resin compositions using phenolic resins. It is superior to cured products obtained from commercial products. The resin composition of the present invention may contain various known additives such as ultraviolet absorbers, heat stabilizers, colorants, plasticizers, curing agents, accelerators, lubricants, modifiers, and the like, if necessary. The present invention will be described in more detail below with reference to Examples. In addition, the following various measurement methods and definitions are applied in this specification including the examples. 1. Method for measuring 0.1-100μ particles Sample approximately 0.1g of each sample. Such sampling is performed five times from different locations for one sample. 1 of each approximately 0.1 g sample sampled
Place each section on a glass slide for microscopic observation. 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 there are 10 to 50 particles or powdery substances and/or their secondary aggregates in the field of view under an optical microscope.
Try to do this for the locations that exist. 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 of 0.1 to 100μ is determined by the following formula. Content rate (%) of 0.1 to 100 μ particles = N ₁ /N ₀ × 100 N ₀ : Total number of particles whose dimensions have been read under the microscope field N ₁ : Of particles with dimensions of 0.1 to 100 μ out of N ₀ Number: The content of particles of 0.1 to 100μ is expressed as the average value of the results of five samples for one sample. 2 Measurement of infrared absorption spectrum and determination of absorption intensity (see Figure 1 of the attached drawings) Regarding the measurement sample prepared by the usual KBr tablet method using an infrared spectrophotometer (Model 225) manufactured by Hitachi, Ltd. Infrared absorption spectra were measured. The absorption intensity at a specific wavelength was determined as follows. In the measured infrared absorption spectrum diagram, draw a baseline at the peak whose absorption intensity is to be determined. If the permittivity at the apex of the peak is expressed as t _p and the baseline transmittance at that wavelength is expressed as t _b , the absorption intensity D at that specific wavelength is given by the following formula. D=logt _b /t _p Therefore, for example, the ratio of the absorption intensity of the peak between 960 and 1020 cm ^-1 and the absorption intensity of the peak between 1450 and 1500 cm ^-1 is calculated as the ratio of the respective absorption intensities calculated using the above formula ( D960~1020/D1450~1500). 3. Amount passed through a 150-meter mesh sieve After thoroughly massaging the dried sample by hand if necessary, accurately weigh about 10 g of it, and shake it in small portions over a 5-minute period using a 150-meter mesh sieve shaker (size of the sieve). ; 200mmφ, shaking condition; 200RPM), and shake for another 10 minutes after adding the sample. The amount of passage through the 150 Tyler mesh is calculated using the following formula. 150 Tyler mesh = ω ₀ - ω ₁ / ω ₀ × 100 Amount passed (weight%) ω ₀ : Input amount (g) ω ₁ : Amount remaining on the sieve without passing through the 150 Tyler mesh sieve (g ) 4 Determination of free phenol content Approximately 10 g of a sample passed through a 150-meter mesh is accurately weighed and heated under reflux for 30 minutes in 190 g of 100% methanol. The liquid passed through a glass filter (No. 3) was subjected to high performance liquid chromatography (6000A manufactured by Waters, USA) to quantify the phenol content in the liquid, and the free phenol content in the sample was determined from a separately prepared calibration curve. I asked for 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: 0.5 ml/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). 5. Heat fusion properties at 100°C Approximately 5 g of a sample passed through a 150 tile mesh was inserted between two 0.2 mm thick stainless steel plates, and this was heated to 100°C using a heat press machine (manufactured by Co., Ltd.). It was pressed with an initial pressure of 50 kg for 5 minutes using a single-action compression molding machine (manufactured by Shindo Metal Industry Co., Ltd.). 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) Approximately 10 g of the sample is accurately weighed (the accurately weighed weight is defined as W ₀ ), and heated under reflux for 30 minutes in approximately 500 ml of substantially anhydrous methanol. Glass filter (No.
3), and the filter residue sample was further washed on the filter with about 100 ml of methanol, and then the filter residue sample was dried at a temperature of 40° C. for 5 hours (the exact weight is defined as W ₁ ). Methanol solubility was determined using the following formula. Methanol solubility (S, weight %) = W ₀ − W ₁ /W ₀ ×100 7 Bulk density 100 that is cut off at the 100 ml mark
Pour the 100ml graduated sample into a 100ml graduated cylinder from 2cm above the rim of the cylinder. The bulk density is determined by the following formula. Bulk density (g/ml) = W (g)/100 (ml) W: Weight per 100ml (g) 8 Bending strength (Kg/cm ² ) and compressive strength (Kg/
cm ² ) Measurement was performed according to JIS-K-6911-1979. 9 Measurement of heat resistance temperature The test pieces are heat treated in a dryer at various temperatures for 24 hours. The highest temperature at which no cracks or gas blisters are observed in the test piece during this heat treatment is defined as the heat resistance temperature. 10 Measurement of thermal conductivity (cal/cm・sec・℃) Measured according to JIS-A-1412-1968. 11 Measurement of volume resistivity (Ωcm) Measurement was performed according to the method described in JIS K-6911-1979. Reference Example 1 (1) Put 1500 g of each mixed aqueous solution at 25°C consisting of various compositions of hydrochloric acid and formaldehyde (listed in Table 1) into 2 separable flasks, and
98% by weight phenol (the remaining 2% by weight is water),
125 g of a mixed aqueous solution (25° C.) containing 20% by weight of phenol, 20% by weight of urea and 14.6% by weight of formaldehyde prepared using urea and 37% by weight of formalin and water was added. After adding and stirring for 15 seconds, it was left to stand for 60 minutes. While standing for 60 minutes, some of the contents in each separable flask remained transparent (Run No. 1 and Table 1).
20), and some changed from transparent to cloudy and remained cloudy (Run Nos. 3, 9 and 9 in Table 1).
18), and some changed from transparent to cloudy and gave white sediment (Run Nos. 2, 4 to 4 in Table 1).
8, 10-17 and 19). This white precipitate contains
When observed under a microscope, spherical objects, aggregates of spherical objects, and a small amount of powder were already observed. Next, the contents of each separable flask were heated to 80°C for an additional 60 minutes with occasional stirring, and then
Incubate the reaction product at 40-45℃ for 15 minutes at a temperature of 80-82℃
Wash with warm water of 0.5% by weight ammonia and 50%
In a mixed aqueous solution consisting of 60% methanol by weight
℃ for 30 minutes, washed again with warm water at 40-45℃ and dried at 80℃ for 2 hours. Table 2 shows the properties of reaction products obtained from mixed aqueous solutions of hydrochloric acid and formaldehyde of various compositions. (2) On the other hand, the following experiment was conducted for comparison. 1
Distilled phenol in a separable flask.
Add 282g, 369g of 37% by weight formalin, and 150g of 26% by weight aqueous ammonia, raise the temperature from room temperature to 70℃ in 60 minutes while stirring, and then
Stir and heat for 90 minutes at a temperature of 70-72°C. Next, the mixture was allowed to cool, and dehydration was carried out by azeotropic distillation under a reduced pressure of 40 mmHg while adding 300 g of methanol little by little. 700 g of methanol was added as a solvent, and a transparent yellowish-brown resol resin solution was taken out. When a portion of the thus obtained resol resin was desolvated under reduced pressure, it foamed violently and turned into a gel. This gelled product is further heated at a temperature of 160℃ under nitrogen gas.
After heat curing for 60 minutes, the resulting cured foam was crushed to obtain a small amount of powder that passed through a 150 Tyler mesh sieve. In this case, the thermosetting resol resin is extremely hard, and it is extremely difficult to obtain a powder of 150 mesh passes even using various types of crushers, ball mills, or vibrating mills under fluorescent X-rays.
The thus obtained thermosetting resol resin powder was mixed with 0.5% by weight of ammonia under the same conditions as described above.
It was treated with a mixed aqueous solution consisting of 50% by weight methanol, washed with warm water and then dried. The properties of the sample thus obtained are listed in Table 2 as Run No. 21. Next, put 390 g of phenol, 370 g of 37% by weight formalin, 1.5 g of oxalic acid, and 390 g of water into a separable flask, and while stirring.
Raise the temperature to 90℃ in 60 minutes, and at a temperature of 90-92℃
Stir and heat for 60 minutes. Then 35% by weight hydrochloric acid
1.0 g was added, and the mixture was further stirred and heated at a temperature of 90 to 92°C for 60 minutes. Next, 500 g of water was added and cooled, the water was removed by a siphon, and the mixture was heated under reduced pressure of 30 mmHg and heated at a temperature of 100° C. for 3 hours.The temperature was further increased and the mixture was heated under reduced pressure at a temperature of 180° C. for 3 hours.
The resulting novolak resin was obtained as a tan solid upon cooling. This one has a softening temperature of 78
~80°C, and the free phenol content determined by liquid chromatography was 0.76% by weight. The above novolac resin was ground and mixed with 15% by weight of hexamethylenetetramine, the mixture was heat cured in nitrogen gas at a temperature of 160°C for 120 minutes, then ground in a ball mill and passed through a sieve of 150 Tyler mesh. I forced it. The powder thus obtained was treated with a mixed aqueous solution of 0.5% by weight ammonia and 50% by weight methanol under the same conditions as described above, washed with warm water and then dried. The properties of the sample thus obtained are listed in Table 2 as Run No. 22. Furthermore, the above novolac resin was made with a hole diameter of 0.25mmφ.
Melt spinning was carried out at a temperature of 136-138°C using a spinneret with 120 holes. Obtained average fineness 21
Denier spun yarn is mixed into an aqueous solution containing 18% by weight of hydrochloric acid and 18% by weight of formaldehyde.
It was immersed for 60 minutes at a temperature of 20-21°C, then raised to a temperature of 97°C over 5 hours, and held at a temperature of 97-98°C for 10 hours. The thus obtained cured novolak fibers were washed with warm water under the same conditions as described above, treated with a mixed aqueous solution consisting of 0.5% by weight ammonia and 50% by weight methanol, washed with warm water, and then dried. This material was ground with a ball mill. The properties of the material that passed through the 150 Tyler mesh sieve are listed in Table 2 as Run No. 23. (3) Table 1 shows the hydrochloric acid and formaldehyde used, the total concentration of hydrochloric acid and formaldehyde, the ratio of the weight of the hydrochloric acid-formaldehyde solution to the total weight of phenol and urea, and the ratio of formaldehyde (mol) to phenol (mol) and urea (mol). mol) and the total molar ratio is shown. Also,
Table 2 shows the results obtained by microscopic observation of the obtained samples.
Content of particles 0.1-50μ and 0.1-100μ,
The amount of passage through the sieve (150 mesh passes) when the obtained sample is passed through a 150-meter mesh sieve, and the infrared absorption spectroscopy of the obtained sample.
960~1020cm ^-1 , 1280~1360cm ^-1 and 1580~
The absorption wavelength intensity ratio (IR intensity ratio) of the absorption intensity at 1650 cm ^-1 to the absorption intensity between 1450 and 1500 cm ^-1 is shown.

【table】

【table】

[Table] Run No. 1, 2, 6, 17 and 20 in Table 1
In this experiment, many sticky resins and large hard lumps or plates were formed at the bottom of the separable flask. Also, in the experiments of Run Nos. 1, 2 and 20, less than 49 g of solid material was obtained from the 25 g of phenol and 25 g of urea used. The content (%) of 0.1-50μ and 0.1-100μ particles and 150 mesh pass (weight%) listed in Table 2 for Run No. 1, 2, 3, 6, 17 and 20 are based on adhesive resin, lumpy The value is for granular or powdery materials relative to the total solids including solids and plate-like materials. However, the content (%) of 0.1 to 50 μ and 0.1 to 100 μ particles in only granular or powdered solids produced in these experiments and the numerical values of 150 mesh pass (% by weight) are shown in Table 2. It was the value shown when closed with a cutlet. From the above experimental facts including the results listed in Table 2, Run Nos. 1, 2, 3, 6, 17 and 20 cannot be recommended as manufacturing methods. However, even with these manufacturing methods, if we limit ourselves to the granular or powdery products produced, these granular or powdery products are sufficiently suitable for use as the granular or powdery nitrogen-containing resin used in the present invention. It has the following characteristics. FIG. 1 of the accompanying drawings shows an infrared absorption spectrum diagram of the granular or powdery material obtained in Run No. 12. In addition, FIG. 1 also shows t, which is required when determining the absorption intensity D from the infrared absorption spectrum diagram.
The method for determining _p and t _b is illustrated. A baseline is drawn at a certain peak, and t _p and t _b at that wavelength are determined as illustrated. Reference Example 2 10 kg of a mixed aqueous solution consisting of 18% by weight hydrochloric acid and 11% by weight formaldehyde was placed in each of 20 6 reaction vessels in a room at a room temperature of 21 to 22°C. 3.34% of a mixed aqueous solution consisting of 30% by weight of phenol, 20% by weight of urea and 11% by weight of formaldehyde was added to each flask while stirring at a temperature of 23°C.
Kg, 2.66Kg, 1.60Kg, 1.06Kg, 0.74Kg and 0.45
Kg added. The bath ratios in this case are 7.0, 8.5, and
They were 13.5, 20.0, 28.0 and 45.0. In either case, when the mixed aqueous solution was continued to be stirred after being added, it rapidly became cloudy in 10 to 60 seconds. As soon as the mixture became cloudy, stirring was stopped and the mixture was allowed to stand for 3 hours. Thirty minutes after the internal temperature gradually rose and the mixture became cloudy, a white slurry or resin-like substance was observed 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 7.0, a large amount of resin-like cured material fused to the stirring rod, making stirring very difficult. Next, the contents were treated in a 0.3% by weight ammonia aqueous solution 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 is 0.5 in each case.
It was less than % by weight. The contents are Run No. 31, 32, 33, 34, 35 and 36 in descending order of reaction bath ratio.
shall be. 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 determined by microscopic observation, and the proportion of 150 tyers in the reaction product. The content of the mesh-passed product, the bulk density of the 150-mesh-passed product, the thermal fusibility of the reaction product at 100°C, the methanol solubility, 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, adhesive 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. Note that the presence or absence of spherical particles in Run No. 31 is small because the proportion of granular or powdery substances 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 have sufficient characteristics of the granules or powders preferably used in the present invention. In addition, almost all of the granular or powdery substances in Run No. 31 to 36 are 0.1 to
The particle size was 100μ. Reference Example 3 A mixture of 20% by weight hydrochloric acid and 8% by weight formaldehyde placed in the separable flask from 2 at 24°C.
While stirring 1250 g of a mixed aqueous solution, add a solution of phenols and nitrogen-containing compounds diluted to 20-80% by weight with 37% formalin so that the total amount of phenols and nitrogen-containing compounds is 50 g. Prepared and added to the bath. When the solution was added, it became cloudy,
The color instantly changed to white, pink, or brown, and stirring was stopped 10 seconds after the solution was added. After stopping the stirring, let it stand for 60 minutes, then raise the temperature to 75℃ for 30 minutes while stirring again, and then keep it at a temperature of 73 to 76℃.
Hold for 60 minutes. Each reaction product was washed with water, then treated in a mixed aqueous solution consisting of 0.3% by weight ammonia and 60% by weight methanol at a temperature of 45°C for 60 minutes, washed with water, and then 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 concentrations of the diluted solutions of the phenols and nitrogen-containing compounds used in formalin,
The color of the reaction product 60 minutes after addition of this diluted solution, the yield of the reaction product based on the total amount of phenols and nitrogen-containing compounds used, and the proportion of the reaction product in the reaction product.
The content of 0.1-50μ particles, the amount of reaction product over 150 mesh passes, and the infrared absorption spectrum intensity ratio are shown.

[Table] Reference example 4 18
1000 g of a mixed aqueous solution containing 9% by weight of hydrochloric acid and 9% by weight of formaldehyde at 18° C. was added. Room temperature is 15
It was warm at ℃. While stirring each of these, first dissolve 15 g of urea, then add 25 g of diluted mixture containing 80% by weight of phenol and 5% by weight of formaldehyde.
g was added to each at once. In both cases, stirring was stopped 10 seconds after the diluent was added and the mixture became stationary, but 18 to 19 seconds after the stirring was stopped, the mixture suddenly became cloudy and a milky white product was observed. The temperature of each liquid gradually rose from 18℃ and reached 31-32 within 5-7 minutes after adding the diluent.
It reached the °C peak and descended again. After adding the diluent, 0.5 hours (Run No. 61), 1 hour (Run No. 62), 3
After being left at room temperature for 6 hours (Run No. 63), 6 hours (Run No. 64), 24 hours (Run No. 65), and 72 hours (Run No. 66), the contents were washed with water and placed in 0.75% by weight ammonia water for 15 hours. After treatment at a temperature of ~17°C for 3 hours, it was washed with water, then dehydrated and dried at a temperature of 40°C for 6 hours. Table 5 shows the passing rate of the obtained dry sample through a 150-meter mesh sieve, the IR intensity ratio of 960 to 1020 cm ^-1 ,
The amount of methanol dissolved and the free phenol content are shown. In addition, all of the samples of Run No. 61 to Run No. 66 were fused in a heat fusion test at 100° C. for 5 minutes.

[Table] Reference Example 5 800 kg of a mixed aqueous solution at 22.5°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 rod, and the mixed aqueous solution was heated at 20°C while stirring. wt% phenol and 10
40 kg of a mixed aqueous solution consisting of hydroquinone (wt%) and urea (20wt%) was charged. After adding the entire amount of the mixed aqueous solution and stirring for 20 seconds, stirring was stopped and the mixture was left standing for 2 hours. In the reaction vessel, rapid cloudiness was observed 35 seconds after the entire amount of the mixed aqueous solution was added, white granules were gradually formed, and the internal temperature gradually rose to 35.5°C and then dropped 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, and then heated to 18°C.
After being immersed in a 0.5% by weight ammonia aqueous solution for a day and night, the product was washed again with water and dehydrated to obtain 29.9 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.
67). 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;
The amount passed through a 150-meter mesh sieve (150 mesh pass) and methanol solubility are shown.

[Table] Example 1 60 parts by weight of the product of Run No. 35 (as a matrix), various fillers as short glass fibers cut into 3 mm (Run No. 71), asbestos (Run No.
72), carbon black (Run No. 73), whitebait balloon (Run No. 74), wood flour (Run No. 75), kraft pulp (Run No. 76), 6-nylon short fiber cut into 3 mm (Run No. 77), and After mixing 40 parts by weight of each of Kevlar short fibers (Run No. 78) cut into 3 mm pieces, a certain amount of the various mixtures obtained was put into a mold preheated to 120℃ using a press machine. , 250 to 350 Kg/cm ² for 30 minutes to obtain 10 molded specimens of each mixture with dimensions of 12 mm in width, 100 mm in length, and 3.5 to 3.8 mm in thickness. similarly
60 parts by weight of the product of Run No. 63 (as a matrix), the above short glass fibers (Run No. 79), wood flour (Run No. 80) and 6-nylon short fibers (Run No.
81), 60 parts by weight of the product of Run No. 67 (as a matrix), the above short glass fibers (Run No. 82), wood flour (Run No. 83) and 6-nylon short fibers ( Using 40 parts by weight of each sample (Run No. 84), 10 molded test pieces were prepared using the same method and conditions as above. On the other hand, for comparison, the uncured resol resin (as a matrix) obtained in Run No. 21 was calculated in terms of solid content.
60 parts by weight and various fillers include short glass fibers cut to 3 mm (Run No. 85), asbestos (Run No. 86), carbon black (Run No. 87), whitebait balloons (Run No. 88), and wood powder (Run No. .89), kraft pulp (Run No. 90), 6- cut into 3mm pieces
Using 40 parts by weight each of nylon short fibers (Run No. 91) and Kevlar short fibers cut to 3 mm (Run No. 92), the resol resin solution and filler were first mixed, then air-dried at room temperature for 24 hours, and then further mixed. A product obtained by drying at a temperature of 80° C. for 30 minutes to remove the solvent was obtained. A certain amount of the thus obtained mixture is heated to 250 to 350℃ using a mold preheated to 150℃ using a press machine.
Treated for 30 minutes under pressure of Kg/cm ² , dimensions 12mm wide,
Ten molded specimens with a length of 100 mm and a thickness of 3.0 to 3.2 mm were obtained for each mixture. Table 7 shows the types of matrix and filler used, the average value of bending strength measured using each of the five molded test products obtained, and the heat resistance temperature measured using each of five molded test products.

【table】

[Table] Run Nos. 71 to 84 were easily molded without any problems, but in Run Nos. 85 to 92, the flow of the resin composition was poor, or the resol resin melted out of the mold. In addition, a lot of gas was generated and the moldability was not good. Example 2 30 parts by weight of the product of Run No. 40 (as filler) and 2 mm cut short glass fiber (as filler)
25 parts by weight and the uncured resol resin used in Run No. 21 as a matrix, novolac resin (mixed with 15 parts by weight of hexamine) used in Run No. 22, furan resin (Hitafuran-303; Hitachi Chemical Co., Ltd.), epoxy Example 1 was prepared using 45 parts by weight each of a resin (Epicote 815; Ciel Kagaku Co., Ltd.) and a melamine resin (Melmite; Toyo Koatsu Kogyo Co., Ltd.) (Run No. 93 to Run No. 97 in order of matrix). Various molding mixtures were obtained by powder mixing or solution mixing according to the method of . A fixed amount of each of the various molding mixtures obtained by the above method was heated at 150 to 170°C under a pressure of 200 to 400 kg/cm ² using a hot press machine and a mold according to Example 1.
Molding was carried out for 30 minutes at a temperature of 100 mm in width.
5 test pieces each with a length of 100 mm and a thickness of 4.7 to 5.1 mm (for thermal conductivity measurement), and a test piece with dimensions of 10 mm in width and 10 in length.
Five test pieces (for compressive strength measurement) each having a thickness of 3.3 to 3.7 mm were prepared. Similarly, test pieces were created using the same composition and method as above for the product of Run No. 47 (as a filler) and the product of Run No. 50 (as a filler) (Run No. 98 to
107). As control products, 55 parts by weight of glass fiber cut into 2 mm length, uncured resol resin used in Run No. 21, novolak resin (containing 15 parts by weight of hexamethylenetetramine) used in Run No. 22, and furan resin were used. , epoxy resin and melamine resin (Run No.
Test pieces were prepared in the same manner as above using 45 parts by weight of each of Run No. 108 to Run No. 112). Table 8 shows the type of filler used, the type of amount matrix used (45 parts by weight), and the average value of compressive strength and average value of thermal conductivity of the molded products.

【table】

[Table] In addition, Run No. 40, Run No. 47, or Run No. 50 products are not used, and Run No.
Similar to Nos. 108 to 112, an attempt was made to obtain a molded product using 25 parts by weight of glass fiber and 75 parts by weight of various resins forming the matrix, but the resin forming the matrix flowed out between the molds or foamed. However, it was not possible to obtain a satisfactory molded product. Example 3 The uncured resol resin solution used in Run No. 21 and the product of Run No. 12 as a filler were mixed in various proportions, air-dried at room temperature for 48 hours, and then treated at a temperature of 70°C for 60 minutes. . In addition, a molding mixture was obtained in the same manner from the resol resin solution and powders of Run No. 21 and Run No. 22 as fillers. Next, the above various molding mixtures were molded at a temperature of 150 to 180°C under a pressure of 200 kg/cm ² using the press machine and mold used in Example 1, and the dimensions were 12 mm in width and 12 mm in length. Fifteen test pieces each having a diameter of 100 mm and a thickness of 3.0 to 3.5 mm were prepared. Table 9 shows resol resin (solid content equivalent) and Run
The amounts of the powder used for the product No. 12, the powder of Run No. 21, and the powder of Run No. 22, the moldability, the heat resistance temperature of the obtained molded product, and the volume resistance before and after boiling are shown.

【table】

[Table] Note that foaming traces and surface roughness were observed in the test pieces of Run No. 113, Run No. 119, and Run No. 120. Example 4 40 parts by weight of the uncured novolac resin used in Run No. 22 (as a matrix) and as a filler
Run No. 13 product, Run No. 67 product, Run No. 21
, 60 parts by weight each of the powder of Run No. 22 and the powder of Run No. 23 were mixed together. Next, these mixtures were placed in a melter preheated to 160°C, extruded under a pressure of 5 kg/cm ² through a nozzle with a diameter of 1 mm, and received into a mold with dimensions of 50 mm square and 25 mm deep. The thus obtained plate-shaped product was cooled to room temperature and then taken out from the mold. Table 10 shows the above extrusion moldability, the apparent thickness and bulk density of the plate-like material taken out from the nozzle, and the heating rate of 25°C/hour when each plate-like material was placed in a dryer. The figure shows the shape when heat treated to a temperature of 200℃.

[Table] Note that the filler and matrix were uniformly mixed in the plate-like products of Run No. 121 and Run No. 122, but in Run No. 123 to 125, the matrix components were mixed as the extrusion time from the nozzle elapsed. The proportion was increasing.

[Brief explanation of the drawing]

FIG. 1 of the accompanying drawings is an infrared absorption spectrum diagram of an example of a granular or powdery 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.

Claims (1)

[Scope of Claims] 1 (a) A granular or powdery compound consisting of a phenol having the following properties (A) and (B), a nitrogen-containing compound having at least two active hydrogens, and a condensate with an aldehyde. Nitrogen resin (A) The condensate is (1) substantially composed of carbon, nitrogen, hydrogen, and oxygen atoms, and (2) at least two methylene groups, methylol groups, and the above nitrogen-containing compounds. residues from which active hydrogen has been removed and trifunctional phenol residues bonded to methylene groups at one position at the 2, 4 and 6-positions and to methylene groups and/or methylol groups at the other two positions. group as the main bonding unit,
(3) In the infrared absorption spectrum of the resin by the KBr tablet method, the largest absorption intensity in the range of 1450 to 1500 cm ^-1 (absorption peak attributed to aromatic double bonds) is D _{1450 to 1500} , and 960 to 1020 cm ^-1
_{( B} ) the granular _shape The particle size of nitrogen-containing resin or powdered nitrogen-containing resin is
(b) a curable resin other than the granular or powdery nitrogen-containing resin of (a) above, and/or (c) a filler material, containing spherical primary particles of 0.1 to 100 microns and secondary aggregates thereof; A thermosetting resin composition characterized by containing at least. 2. The resin composition according to claim 1, wherein the curable resin (b) is a thermosetting resin. 3. The resin composition according to claim 1 or 2, wherein the curable resin (b) is a resol resin, a novolak resin, an epoxy resin, a furan resin, a melamine resin, or a urea resin. 4. The resin composition according to any one of claims 1 to 3, wherein the filler material (c) is an inorganic material. 5. The resin composition according to any one of claims 1 to 4, wherein the filler material (c) is fibrous. 6. The resin composition according to any one of claims 1 to 5, wherein the filler material (c) is glass fiber, carbon fiber, or asbestos. 7. The resin composition according to any one of claims 1 to 4, wherein the filler material (c) is not granular or powdery. 8 The above filling material (c) is carbon, silica, alumina, silica alumina, diatomaceous earth, calcium carbonate,
Calcium silicate, magnesium oxide, clay,
The resin composition according to any one of claims 1 to 4 and 7, which is an antimony oxide or shirasu balloon. 9. The resin composition according to any one of claims 1 to 3, wherein the filler substance (c) is an organic substance. 10. The resin composition according to any one of claims 1 to 3 and 9, wherein the filler material (c) is wood flour, linter, pulp, or polyamide fiber. 11. According to any one of claims 1 to 10, the granular or powdery nitrogen-containing resin (a) comprises at least 30% of spherical primary particles with a particle size of 0.1 to 100 microns and secondary aggregates thereof. The resin composition described. 12 The granular or powdery nitrogen-containing resin (a) is
In the infrared absorption spectrum obtained by the KBr tablet method, the highest absorption intensity in the range of 1280 to 1360 cm ^-1 (absorption peak attributed to carbon-nitrogen bonds) is
The resin composition according to any one of claims 1 to 11, wherein when expressed as D _{1280 to 13600} , D _{1280 to} 1360 / D _{1450 to 1500} = 0.15 to 3.0. 13 The granular or powdery nitrogen-containing resin (a) is KBr
The resin composition according to any one of claims 1 to 12, which has _D960-1020 / _D1450-1500 =0.15-0.6 in an infrared absorption spectrum measured by a tablet method. 14 The granular or powdery nitrogen-containing resin (a) is KBr
The resin composition according to any one of claims 1 to 13, which has _D1280-1360 / _D1450-1500 =0.2-2.0 in an infrared absorption spectrum measured by a tablet method. 15 The granular or powdery nitrogen-containing resin (a) is KBr
The resin composition according to any one of claims 1 to 14, which has _D1280-1360 / _D1450-1500 =0.3-1.5 in an infrared absorption spectrum measured by a tablet method. 16 Claims 1 to 1, wherein the granular or powdery nitrogen-containing resin (a) has a size such that at least 50% by weight of the entire nitrogen-containing resin can pass through a sieve of 150 Tyler mesh.
The resin composition according to any one of Item 5. 17. The resin composition according to any one of claims 1 to 16, wherein the granular or powdery nitrogen-containing resin (a) has a free phenol content of 500 ppm or less as measured by liquid chromatography. 18 The granular or powdered nitrogen-containing resin (a) contains at least 1% by weight of nitrogen.
The resin composition according to any one of items 1 to 17. 19 Claims 1 to 18, wherein the granular or powdery nitrogen-containing resin (a) contains 2 to 30% by weight of nitrogen.
3. The resin composition according to any one of Items 1 to 9. 20 The granular or powdered nitrogen-containing resin (a) is one that at least partially fuses when held at a temperature of 100°C for 5 minutes according to the thermal fusion measurement method described in the text. The resin composition according to any one of claims 1 to 19. 21 10 g of the granular or powdery nitrogen-containing resin (a) is
When heated under reflux in 500 ml of substantially anhydrous methanol, the following formula S = W ₀ - _{W 1} /W ₀ ×100 where W ₀ is the weight (g) of the granular or powdered nitrogen-containing resin used. ), W ₁ is the weight (g) of the granular or powdered nitrogen-containing resin remaining after heating and refluxing, and S is the methanol solubility (wt%) of the granular or powdered nitrogen-containing resin. The resin composition according to any one of claims 1 to 20, which has a content of 20% by weight or more. 22 Claims that the granular or powdered nitrogen-containing resin (a) does not substantially melt or fuse when held at a temperature of 100°C for 5 minutes according to the thermal fusion measurement method described in the main text. The resin composition according to any one of Items 1 to 19. 23 The curable resin (b) is 10 to 90% by weight based on the total amount of the curable resin (b) and the granular or powdery nitrogen-containing resin (a) in the thermosetting resin composition. Claims 1 to 22 containing the amount of
3. The resin composition according to any one of Items 1 to 9. 24 The curable resin (b) is 16 to 80% by weight based on the total amount of the curable resin (b) and the granular or powdery nitrogen-containing resin (a) in the thermosetting resin composition. The resin composition according to claim 23, containing the resin composition in an amount of . 25 The curable resin (b) is weighed in an amount of 24 to 70% by weight based on the total amount of the curable resin (b) and the granular or powdery nitrogen-containing resin (a) in the thermosetting resin composition. % of the resin composition according to claim 24. 26 The filler (c) is added in an amount of 5 to 89% by weight based on the total amount of the filler (c) and the granular or powdery nitrogen-containing resin (a) in the thermosetting resin composition. The resin composition according to any one of claims 1 to 22, containing: 27 The filler (c) is added in an amount of 10 to 77% by weight based on the total amount of the filler (c) and the granular or powdery nitrogen-containing resin (a) in the thermosetting resin composition. The resin composition according to claim 26, which contains: 28 The filler (c) is added in an amount of 15 to 63% by weight based on the total amount of the filler (c) and the granular or powdery nitrogen-containing resin (a) in the thermosetting resin composition. The resin composition according to claim 27, which contains: