JPS639548B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention relates to a resin composition containing a novel granular or powdery nitrogen-containing phenol formaldehyde resin. More specifically, the present invention relates to a resin composition containing a novel granular or powdery nitrogen-containing phenolic aldehyde resin that has good storage stability and flow characteristics and is reactive, and is suitable as a molding material. 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. However, when a novolak resin and a thermoplastic resin are blended, the former novolac resin may cause foaming of the molded product due to ammonia generated by decomposition of hexamine, or undecomposed hexamine products and organic bases produced as by-products. It has disadvantages such as remaining in the molded product and deteriorating the physical properties of the molded product.
Furthermore, in the case of the latter novolak resin, the crosslinking reaction progresses excessively only in the parts that come into contact with paraformaldehyde and acid catalysts, making it difficult to form a uniform crosslinked structure as a whole, and the acid catalyst and paraformaldehyde remaining, resulting in the reaction progressing over time. Problems such as physical properties may change or foaming may occur due to decomposition during curing.
In addition, since novolac resins are obtained by a reaction with excess phenol, they contain a relatively large amount of free phenol (for example, about 0.5-2% by weight), and therefore compositions containing this resin generate phenol during heat molding. This causes problems during molding operations. In addition, in relatively recent years, novolak resins have been heated at high temperatures to obtain products with a fairly high degree of condensation, and this has been purified to separate and remove low condensates, resulting in phenol groups containing 7 to 10 methylene groups. A relatively high condensate bonded by groups is obtained, and this is heated and melt-spun to form a novolak resin fiber, which is immersed in a mixed aqueous solution of hydrochloric acid and formaldehyde, and then heated gradually from room temperature for a long period of time. A method of producing cured novolak resin fibers was proposed by proceeding the curing reaction from the outside of the fibers (Japanese Patent Publication No. 1983-1999).
No. 11284). However, cutting or pulverizing the cured novolac fibers produced as described above is not only expensive, but also cannot be made into granules or powders with good flow characteristics. Also, conventionally known resol resins are prepared in excess of formaldehyde, such as at a molar ratio of phenol to formaldehyde of 1 to 1 to 2 in the presence of a basic catalyst (about 0.2 to 2%) such as sodium hydroxide, ammonia, or an organic amine. It is produced by reacting under the following conditions. The resol resin obtained in this way is mainly composed of phenol mono- or trimers 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 a 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). Further, resol resins usually contain 1 to 10% by weight of free phenol based on the solid content. In addition, in recent years, a hydrophilic polymer compound is added to a condensate obtained by reacting phenols and formaldehyde in the presence of at least a nitrogen-containing compound, and the reaction is performed to produce granular or powdered resin. Although a method has been announced (Special Publication 1973-
42077), the non-gelled resin obtained by this method contains a large amount of free phenol, about 5-6% by weight (Examples 1 to 4), and the gelled product (Example 5) is extremely hard. Not only is it a non-reactive resin, but it also contains a hydrophilic polymer compound, which has the disadvantage of reducing the performance of molded products obtained using it. Furthermore, a method is known in which a prepolymer obtained by reacting phenol and formaldehyde in a basic aqueous solution is mixed with a protective colloid and coagulated into inert solid beads under acidic conditions (Japanese Patent Publication No. 51
-13491), which corresponds to the so-called cured resol resin, has no reactivity, and also contains salts, acids, and other protective colloids, which similarly impairs the performance of molded products obtained using it. There are drawbacks that reduce it. As mentioned above, attempts have been made to blend phenol/formaldehyde resin into thermoplastic resins, but when viewed as a filler for thermoplastic resins, phenol/formaldehyde resins have been obtained in a shape or form suitable for fillers. First of all, it is difficult to do so, and it also has the problem of containing substances that have an undesirable effect on the thermoplastic resin. 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 resin composition containing a novel granular or powdery nitrogen-containing resin and a thermoplastic resin. Another object of the present invention is to provide a resin composition with good moldability, which contains a granular or powdery nitrogen-containing resin that is granular or powdery and has good flow characteristics. Still another object of the present invention is to provide a resin composition that contains a granular or powdery nitrogen-containing resin with a small free phenol content of 500 ppm or less, and is therefore safe and easy to handle. Still another object of the present invention is to contain a granular or powdery nitrogen-containing resin which can undergo a crosslinking reaction by itself and which can also react with a thermoplastic resin; The object of the present invention is to provide a resin composition that can be bonded with other materials. Still another object of the present invention is to provide a resin containing a granular or powdered nitrogen-containing resin that exhibits excellent mechanical properties such as excellent strength, high hardness, low compressive strain, or excellent dimensional stability in a molded form. An object of the present invention is to provide a composition. Yet another object of the present invention is to provide excellent electrical insulation;
Another object of the present invention is to provide a resin composition that provides a molded article that exhibits chemical resistance and can be easily plated. Further objects and advantages of the invention will become apparent from the description below. 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, and (2) contains methylene groups, methylol groups, and the above-mentioned a residue from which at least two active hydrogens have been removed from a nitrogen compound and which is bonded to a methylene group at one position in the 2, 4 and 6-positions and to methylene and/or methylol groups at the other two positions Contains trifunctional phenolic 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 defined as D _{1450 to 1500} , and 960～
The highest absorption intensity in the range of 1020 cm ^-1 (absorption peak attributed to methylol group) is
When expressed as D _{960 ~ 1020} , D _{960 ~ 1020} / D _{1450 ~ 1500} = 0.1 ~ 2.0,
and (B) the granular or powdered nitrogen-containing resin has a particle size of
This is achieved by a resin composition characterized by containing spherical primary particles of 0.1 to 100 microns and secondary aggregates thereof, and (b) containing at least a thermoplastic resin. The resin composition of the present invention contains the granular or powdery nitrogen-containing phenol aldehyde resin specified in (A) and (B) above. 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. Cresol, bisphenol A, o-, m- or p-C ₂
~Includes condensates of mixtures with one or more known phenol derivatives such as _C4 alkylphenol, p-phenylphenol, xylenol, and resorcinol, and nitrogen-containing compounds and aldehydes having at least two active hydrogens. do. The granular or powdery nitrogen-containing resin in the resin composition of the present invention has the properties (A) and (B) described above. In the specification of (A) and (B) above, the particle size of the spherical primary particles and secondary aggregates thereof in (B) is 0.1 to 100
The specification that it is micron and the specification that D _{960 - 1020} / D _{1450 - 1500} = 0.1 - 2.0 in (A) are both 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 between 100 and 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%, especially at least 50%, especially at least 50% of the number of particles in the field of the optical micrograph according to the above definition (as the average value of 5 fields).
70 to substantially 100% consist of spherical primary particles and secondary agglomerates thereof ranging from 0.1 to 50 microns, more preferably from 0.1 to 20 microns. As mentioned above, the granular or powdery nitrogen-containing resin is formed mainly of the spherical primary granules and the microparticles of their secondary aggregates, so it is extremely small and the overall at least 50
% by weight, preferably 70% by weight, particularly preferably at least 80% by weight of the total passes through a 150 taylor mesh sieve. Such an indication that the granular or powdered nitrogen-containing resin product used in the present invention passes through the sieve may be indicated by gently kneading the granular or powdered product by hand or brushing it. A force that does not forcibly destroy the particles (including secondary aggregates) is applied, such as lightly pushing or smoothing the particles on the sieve with a sieve, or tapping them with your hand. This 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: D _960-1020 /D _1450-1500 = 0.1-2.0, and preferably, D _1280-1360 /D _1450-1500 = 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. A particularly preferred one has the following properties: D _960-1020 /D _1450-1500 = 0.2-0.4, and preferably D _1280-1360 /D _1450-1500 = 0.3-1.5. In addition, the granular or powdered nitrogen-containing resin used in the present invention further has a maximum absorption intensity in the range of 1580 to 1650 cm ^-1 expressed as D _{1580 to 1650} in an infrared absorption spectrum measured by the KBr tablet method. _1580-1650 /D _1450-1500 = 0.3-4.5 (preferably 0.75-2.0, particularly preferably 1.0-4.5
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 of D _1580-1650 /D _1450-1500 indicate values that can clearly distinguish the ratio in phenol-formaldehyde resins that do not contain nitrogen, and therefore are similarly characteristic values for specifying the resin of the present invention. It can be recognized as absorption. The ratio of the above absorption intensities in the infrared absorption spectrum, which is one parameter for specifying the nitrogen-containing resin used in the present invention, for example
The range of D _{960 to 1020} / D _{1450 to 1500} = 0.1 to 2.0 indicates that the nitrogen-containing resin used in the present invention contains a considerable amount of methylol groups, and the content of methylol groups is also within a certain range. It can be understood that it represents a characteristic value associated with a structure that can be adjusted. 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,
Further preferred products have a free phenol content of
300ppm or less, especially 100ppm or less. The granular or powdered resin obtained by the method disclosed in Japanese Patent Publication No. 53-42077 contains an extremely large amount of free phenol, from 0.3 to about 6% by weight, whereas the granular or powdered resin used in the present invention The free phenol content of 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 is 20% by weight or more, even 30% by weight or more, and even more than 40% by weight. Included are resins that exhibit methanol solubility of . 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 containing at least 50% of these, 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 thermoplastic resin in a relatively large amount. Furthermore, since at least many of the nitrogen-containing resins used in the present invention have extremely small spherical primary particles as their basic constituents, the resin composition of the present invention containing them has excellent mechanical properties. It has various characteristics. 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 shows reactivity when heated, and as shown in the examples below,
Forms a resin molded product that has extremely excellent not only physical and mechanical properties but also heat insulation, heat resistance, and other electrical properties. 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 when obtaining a molded article from the resin composition of the present invention, not only side reactions caused by phenols do not occur, but also physical properties of the resin molded product do not deteriorate due to free phenols. Become a reason. In addition, the granular or powdered nitrogen-containing resin used in the present invention 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 polymer compounds. For this reason, when the resin composition of the present invention is heat-molded, 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
It is extremely fine, has good storage stability and flow properties, contains some methylol groups, and usually has a very low free phenol content, so that when the resin composition of the present invention is molded and heated, Alternatively, it has the excellent feature of being reactive with certain types of thermoplastic resins. For example, in the granular or powdered resin used in the present invention, the methylol group causes a dehydration reaction with the hydrogen of the amide group of polyamide, which is a thermoplastic resin, and thereby chemically bonds with the polyamide resin and hardens. React as you would. Thus, among the granular or powdery nitrogen-containing resins used in the present invention, the resin of (a) above exhibits fusion properties at least in part when heated at 100°C for 5 minutes according to the thermal fusion measurement method. The resin composition of the present invention can be blended with a thermoplastic resin in a relatively large amount and provides a molded article particularly excellent in heat resistance, heat insulation, electrical insulation, or chemical resistance. The resin (b), which does not exhibit fusion properties by measurement, provides the fat composition of the present invention, which provides molded articles with particularly excellent heat resistance or compression resistance. The granular or powdery nitrogen-containing resin used in the present invention has (1) the following composition (a) a hydrochloric acid (HCl) concentration of 3 to 28% by weight, and (b) a formaldehyde (HCHO) concentration of 3 to 28% by weight.
25% by weight and the concentration of aldehydes other than formaldehyde is 0 to 10% by weight, and (c) the total concentration of hydrochloric acid and formaldehyde is 10 to 10% by weight.
(2) A phenol 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 (I): 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. In addition to the three conditions (a), (b), and (c) above, the composition of the hydrochloric acid-formaldehyde bath in (1) above is as follows: It is preferable that the total molar ratio of phenols (moles) and nitrogen-containing compounds (moles) that come into contact with the bath 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 is preferably 20 or less, particularly 15 or less. The above molar ratio is particularly from 4 to
15, particularly preferably 8 to 10. The feature of the above production method is that a bath of a hydrochloric acid-formaldehyde aqueous solution 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, the method is to contact the phenols and the nitrogen-containing compound at a large ratio, preferably 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 above method is carried out at a total concentration of hydrochloric acid and formaldehyde of 10% by weight or more, the total weight of hydrochloric acid and formaldehyde relative to the total weight of phenols and nitrogen-containing compounds is 80% 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 formula (I) 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 in such a way 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. Depending on the ratio of phenols and nitrogen-containing compounds and the reaction conditions, the bath (reaction liquid) may be subjected to mechanical shearing force such as stirring during the period from the time when cloudiness occurs until solid matter is formed. It is preferable not to give 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 diluted solutions thereof), 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. 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, 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 time or instantaneously within a few minutes, and granular or powdery solids are rapidly formed. Keep the temperature of the hydrochloric acid-formaldehyde bath below 40℃.
The temperature is preferably kept at 5° to 35°C, particularly preferably 10 to 30°C, and the phenols and nitrogen-containing compounds are added as they are or their diluted solutions, preferably a diluted solution of phenols and nitrogen-containing compounds in water are added to this bath. death,
Approximately below 50℃, preferably 45℃ after cloudiness occurs
In granular or powdered solids that have completed the desired reaction at a temperature below, the curing reaction has not progressed sufficiently, so they generally exhibit heat fusibility in the 100°C heat fusing test described below. 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 generated in a non-stirring state, and then a pale pink granular or powdery solid is generated without increasing the temperature, and this solid is heated at a temperature higher than 50°C.
Preferably, when the desired reaction is completed by heating to a temperature of 70° to 95°C, the curing reaction progresses more, so the heat fusion properties at 100°C are reduced or substantially eliminated, or even more so. The material exhibits heat fusibility at high temperatures, for example, 200°C, or has substantially no heat fusibility even at such high temperatures. 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 as long as it contains at least 50% by weight of phenol, especially at least 70% by weight, o-cresol, m-cresol, p-cresol, etc.
It may be a mixture with one or more of known phenol derivatives such as cresol, bis-phenol A, o-, m- or p- _C2 - _C4 alkylphenol, p-phenylphenol, xylenol, and resorcinol. 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 resin composition of the present invention contains a thermoplastic resin in addition to the granular or powdery nitrogen-containing phenol aldehyde resin. As the thermoplastic resin, thermoplastic resins known in the field of polymers are widely used. For example, general-purpose engineering plastics such as polyethylene resin, polypropylene resin, polystyrene resin, acrylic resin, vinyl resin, fluororesin, polyacetal resin, polyamide resin, polyester resin, polycarbonate resin, or polyurethane resin are preferably used. Among these, polyethylene resin, polypropylene resin,
Vinyl resins, polyamide resins or polyester resins are particularly preferably used. Such thermoplastic resins can be used alone or in combination of two or more. The thermoplastic resins include homopolymers and copolymers. Copolymers may be random, grafted or blocked. The polyethylene resin preferably contains ethylene units in the polymer chain in an amount of 50% by weight or more, more preferably 85% by weight or more.
The polypropylene resin contains propylene units in the polymer chain, preferably 50% by weight or more, more preferably
Contains 85% or more by weight. The polystyrene resin preferably contains styrene units in the polymer chain in an amount of 50% by weight or more, more preferably 85% by weight or more. The acrylic resin preferably contains units of methyl or ethyl ester of acrylic acid or methacrylic acid in the polymer chain, preferably 50% by weight or more, more preferably 85% by weight.
Contains at least % by weight. The vinyl resin preferably contains 50% by weight or more, more preferably 85% by weight or more of vinyl monomer units having ethylenically unsaturated bonds, such as vinyl chloride, vinylidene chloride, and vinyl acetate, in the polymer chain. do. As the vinyl resin, polyvinyl chloride is particularly preferably used. The fluororesin preferably contains 50% by weight or more, more preferably 85% by weight or more of units of fluorine-containing vinyl monomers such as tetrafluoroethylene, fluoroethylene, and hexafluoropropylene in the polymer chain. . Units other than the above-mentioned main units that form the above-mentioned polyethylene resin, polypropylene resin, polystyrene resin, acrylic resin, vinyl resin, or fluororesin are other units different from each main unit, such as ethylene, propylene, acrylic It can be a monomeric unit of acids, methacrylic acid, lower alkyl esters of these acids such as methyl or ethyl esters, styrene, alpha-methylstyrene, vinyl chloride, vinyl acetate, acrylonitrile, and the like. As the polyacetal resin, for example, polyoxymethylene and poly(oxymethylene-oxyethylene) copolymer are preferably used. The poly(oxymethylene-oxyethylene) copolymer may contain up to 15% by weight of oxyethylene units derived from ethylene oxide in the polymer chain. Examples of polyamide resins include polycaproamide (6-nylon), polyhexamethylene adipamide (6,6-nylon), polyhexamethylene sebaamide (6,10-nylon), and polyundecanamide (11-nylon). Nylon), polydodecanamide (12-nylon), polyundecamethylene terephthalamide (11,T-nylon), etc. are preferably used. As the polyester resin, a saturated polyester resin is preferable, and for example, polyethylene terephthalate, polytetramethylene terephthalate, polyhexamethylene terephthalate, etc. are preferably used. As the polycarbonate resin, for example, polycarbonate of bisphenols, particularly bisphenol A, is preferably used. The thermoplastic resins used in the present invention are all well known in the technical field. The appropriate blending ratio of the granular or powdery nitrogen-containing resin and the thermoplastic resin in the resin composition of the present invention is determined by the characteristics of the granular or powdery nitrogen-containing resin used, such as whether it is heat-fusible or not. Or, strictly speaking, it varies depending on the type of thermoplastic resin used. However, in the resin composition of the present invention, preferably 0.01 to 20 parts by weight, more preferably 0.02 to 3 parts by weight, particularly 0.03 to 0.9 parts by weight of the above granular or powdery nitrogen-containing resin per 1 part by weight of thermoplastic resin. is,
It contains a thermoplastic resin and a granular or powdery nitrogen-containing resin. The resin composition of the present invention is provided as a thermoplastic or thermosetting resin composition. According to the present invention, a thermoplastic resin composition in which the granular or powdery nitrogen-containing resin is used in an amount of 0.05 to 0.5 parts by weight per 1 part by weight of the thermoplastic resin is particularly preferably provided. The thermosetting resin composition of the present invention is generally obtained when the granular or powdery nitrogen-containing resin used is highly reactive and the amount of thermoplastic resin used is relatively small. Further, even when the amount of the thermoplastic resin used is relatively large, it can also be obtained when the thermoplastic resin has reactivity with the highly reactive granular or powdery nitrogen-containing resin used. The composition that provides such a resin composition of the present invention will become clear from the following description. As is clear from the above description, the resin composition of the present invention is a granular or powdered nitrogen-containing phenol aldehyde resin, and when pressed at a temperature of 100°C for 5 minutes according to the heat fusion measurement method described later. , (a) At least a part of it is fused to form a lump or plate, or (b) It is not substantially melted or fused and takes the form of granules or powder. All of these granular or powdered nitrogen-containing resins can be said to have thermosetting properties because the curing reaction is further advanced by heating. However, since the curing reaction of resins with property (a) above has not yet progressed sufficiently, they melt or fuse when heated, whereas resins with property (b) above do not have the properties described in (a) above. Since the curing reaction has progressed further than that of resin, it is different in that it does not melt or fuse when heated and maintains a granular or powdery form. Further, the resin composition of the present invention includes a thermoplastic resin as another component. Therefore, since the resin composition of the present invention contains a thermosetting resin and a thermoplastic resin, in general, when the content of the thermoplastic resin is large, there is a strong tendency to exhibit thermoplasticity. When there is a large amount of powdered nitrogen-containing resin, there is a strong tendency to exhibit thermosetting properties. However, as mentioned above, whether the resin composition of the present invention is thermoplastic or thermosetting is not determined simply by the blending amount of the granular or powdery nitrogen-containing resin and the thermoplastic resin. will be explained in more detail below. According to research by the present inventors, the resin composition of the present invention exhibiting thermoplasticity is advantageously provided by the following embodiments. (i) When using a resin having the fusibility described in (a) above as the granular or powdered nitrogen-containing resin, preferably 0.5 parts by weight or less per 1 part by weight of the thermoplastic resin is used as the granular or powdered nitrogen-containing resin. Advantageously, resins are used. (ii) When using the resin that does not melt or fuse as described in (b) above as the granular or powdered nitrogen-containing resin, preferably 2 parts by weight or less of the granular or powdered nitrogen-containing resin is added to 1 part by weight of the thermoplastic resin. Advantageously, resins are used. (iii) When using the resin in (a) above and the resin in (b) above as particulate or powdered nitrogen-containing resin, preferably the resin in (a) above is used in an amount of 0.5 parts by weight per 1 part by weight of the thermoplastic resin. parts by weight or less, and the total amount of the resin in (a) and the resin in (b) is 1.5 parts by weight or less,
It is preferable to use the granular or powdery nitrogen-containing resin. The thermoplastic resin composition of the present invention can be made into a molded article by a molding method generally used for molding thermoplastic resins, such as extrusion molding or mold molding. The resulting molded articles have superior mechanical properties, such as superior strength, high hardness, low compressive strain, superior dimensional stability, or superior electrical insulation properties, than those made from the thermoplastic resin used alone. Has chemical or heat resistance. According to research by the present inventors, the thermosetting resin composition of the present invention is advantageously provided by the following embodiments. (i) When using the resin of (a) above as a granular or powdered nitrogen-containing resin, the granular It is advantageous to use nitrogen-containing resins or powdered nitrogen-containing resins. (ii) When using the resin of (b) above as a granular or powdered nitrogen-containing resin, preferably more than 2 parts by weight and 6 parts by weight or less, more preferably 2 parts by weight, per 1 part by weight of the thermoplastic resin. It is advantageous to use the granular or powdery nitrogen-containing resin in an amount exceeding 3 parts by weight or less. As the thermoplastic resin, polyamide, polyvinyl chloride, polyacetal resin, etc., which are reactive with the granular or powdery nitrogen-containing resin, are preferably used. When using a granular or powdery nitrogen-containing resin in an amount exceeding the above upper limit, it becomes difficult to obtain a molded article. (iii) When using the resin in (a) above and the resin in (b) above as particulate or powdered nitrogen-containing resin, preferably the resin in (a) above and the resin in (b) are mixed with respect to 1 part by weight of the thermoplastic resin. The total amount of the resins in ) is more than 0.5 parts by weight and less than 20 parts by weight, and the ratio of the resins in (a) and (b) is expressed by the following formula: 6-0.3x>y>2-4x where: , x is the part by weight of the resin in (a), and y is
It is advantageous to use a granular or powdery nitrogen-containing resin so as to satisfy (b), which is the weight part of the resin. The thermosetting resin composition of the present invention can be made into a molded article by a molding method generally used for molding thermosetting resins, such as a mold molding method. The obtained molded product has superior toughness and strength to the molded product obtained from the granular or powdered nitrogen-containing resin used in the present invention alone.
High hardness, low compressive strain, dimensional stability,
It has excellent electrical insulation, chemical resistance, and heat resistance, and can be plated. The resin composition of the present invention may optionally contain fibrous materials such as glass fibers, carbon fibers, or asbestos; carbon, silica, alumina, silica alumina, diatomaceous earth, calcium carbonate, calcium silicate, magnesium oxide, and clay. , granular or powdered materials such as antimony oxide or shirasu balloons; or organic substances such as wood flour, linters, pulp or polyamide fibers. These fillers may normally be contained in an amount of up to 30% by weight, more preferably up to 20% by weight of the total composition containing them. The thermoplastic resin composition of the present invention is produced by solid-mixing a granular or powdered nitrogen-containing phenol aldehyde resin, a thermoplastic resin, and, if necessary, a filler using a mixer such as a V-type blender, or by mixing It can be produced by introducing the material as it is into, for example, a melt extruder and melt-mixing it therein. In this case, the resin composition of the present invention can be obtained in the form of chips or pellets, or it can be obtained directly as a molded product. The thermoplastic resin composition of the present invention can be prepared by charging a solid mixture of the above-mentioned components or the above-mentioned chips or pellets into a mold or an injection molding machine, and molding or injection molding, respectively, into a molded product. It can also be converted. The thermosetting resin composition of the present invention is usually solid-mixed using a mixer such as a V-type blender, and then charged into a mold and converted into a molded article by molding. Further, depending on the case, the heat history may be reduced and the mixture may be melt-mixed in a melt extruder to form chips or pellets, and then converted into molded products in a mold. The operating conditions of the mold are usually a temperature of 80-300°C, a time of 0.1-10 hours and optionally a pressure of 5-500 Kg/ ^cm2 . The molded article made from the resin composition of the present invention can be used for electrical and electronic parts such as printed circuit boards, switch boxes, and computer circuit boards; for example, molds for thermoplastic resins by utilizing the various excellent properties described above. ; Electrolytic cells; Gears, bearings, type; Insulating plates and structural materials for internal combustion engines; Interior materials and structural materials such as dash boards for automobiles and aircraft; Sealing materials such as packing gaskets for opening and closing parts of refrigerators, chemical tanks, etc. It is suitably used for. The present invention will be described in more detail below with reference to Examples. In addition, the abbreviations in the examples are as follows. 1. Method for measuring 0.1-100 μ particles Sample approximately 0.1 g of each sample. Such sampling is performed five times from different locations for one sample. 1 of each approximately 0.1g 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 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 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 were read under the microscope field N ₁ : Number 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). Measurement sample prepared by the normal KBr tablet method using an infrared spectrophotometer (Model 225) manufactured by Hitachi, Ltd. The infrared absorption spectrum was measured. The absorption intensity at a specific wavelength was determined as follows. In the measured infrared absorption spectrum diagram, draw a baseline at the peak whose absorption intensity is to be determined. The transmittance at the top of that peak is
When 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 by the ratio of the respective absorption intensities (D _960~1020 /D _1450~1500 ). 3. Amount passed through a 150-meter mesh sieve After massaging the dried sample thoroughly by hand if necessary, weigh approximately 10 g of it accurately, and shake it in small portions over a 5-minute period using a 150-meter mesh sieve shaker (size of the sieve). ;200mmφ, shaking conditions;200RPM)
After adding the sample, shake for another 10 minutes. The amount of passage through the 150 Tyler mesh is calculated using the following formula. Amount passed through the 150 Tyler mesh sieve (weight%) = ω ₀ − _{ω 1} / ω ₀ ×100 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 the 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-BondapakC 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), Range 0.01
(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℃ Approximately 5g of a sample passed through a 150 tile mesh was inserted between two 0.2mm thick stainless steel plates, and this was prepared using a heat press machine (manufactured by Co., Ltd.) preheated to 100℃. 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) Accurately weigh about 10 g of the sample (the exact weighed weight is _W0 ), and dissolve it in approximately 500 ml of substantially anhydrous methanol.
Heat under reflux for a minute. Pass through a glass filter (No. 3), and wash the filter residue sample on the filter with about 100 ml of methanol.
The filter residue sample was then dried at a temperature of 40° C. for 5 hours (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 Bulk density It reaches the end at the 100 ml 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) 8. Measurement of compressive strength This was carried out according to the method described in JIS K-6911-1970. 9 Measurement of heat distortion temperature Measured according to JIS K-6717. 10 Measurement of volume resistivity (Ω·cm) 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 each mixed aqueous solution (25°C) containing 20 wt% phenol, 20 wt% urea, and 14.6 wt% formaldehyde prepared using urea, 37 wt% 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 No. 3, 9 and 18 in Table 1),
In some cases, the state changed from transparent to cloudy and gave a white precipitate (Run Nos. 2, 4 to 8, 10 to 1 in Table 1).
17 and 19). When observed under a microscope, this white sediment already contained spherical objects, aggregates of spherical objects, and a small amount of powder. Next, add the contents of each separable flask, stirring occasionally.
The temperature was raised to 80°C for 60 minutes, and then the reaction product was washed with hot water at 40-45°C for 15 minutes at a temperature of 80-82°C, and a mixed aqueous solution consisting of 0.5% by weight ammonia and 50% by weight methanol was prepared. medium, at a temperature of 60℃
It was treated for 30 minutes, washed again with warm water at 40-45°C, and then dried at 80°C for 2 hours. Table 2 shows the properties of 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 282 g, 369 g of 37 wt% formalin, and 150 g of 26 wt% aqueous ammonia, 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. 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 for fluorescent X-rays.
The thus obtained thermosetting resol resin powder was mixed with 0.5% by weight of ammonia under the same conditions as described above.
It was treated with a mixed aqueous solution consisting of 50% by weight methanol, washed with warm water and then dried. The properties of the sample thus obtained are listed in Table 2 as Run No. 21. Next, put 390 g of phenol, 370 g of 37% by weight formalin, 1.5 g of oxalic acid, and 390 g of water into a separable flask, and add 60 g of water while stirring.
The temperature rises to 90℃ in minutes, and the temperature rises to 60℃ at a temperature of 90-92℃.
Stir and heat for minutes. Next, 1.0g of 35% by weight hydrochloric acid
was added and further stirred and heated at a temperature of 90 to 92°C for 60 minutes. Next, 500g of water was added and cooled, the water was removed using a siphon, the mixture was heated under a reduced pressure of 30mmHg, and the temperature was further raised to 100℃ for 3 hours.
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 material has a softening temperature of 78-80℃
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 novolac 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. Shattered. 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.
The content of particles of 0.1 to 50μ and 0.1 to 100μ, the amount passed through the sieve when the obtained sample is passed through a 150-meter mesh (150 mesh passes), and the infrared absorption spectroscopy of the obtained sample.
960~1020cm ^-1 , 1280~1360cm ^-1 and 1580~
Absorption wavelength intensity ratio of absorption intensity at 1650 cm ^-1 to absorption intensity between 1450 and 1500 cm ^-1 (1R intensity ratio)
showed that.

【table】

【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 solids were obtained from the 25 g of phenol and 25 g of urea used. Content (%) of 0.1-50μ and 0.1-100μ particles and 150 mesh pass (wt%) listed in Table 2 for Run No. 1, 2, 3, 6, 17 and 20
The numerical value is the value for granular or powdery materials relative to the total solids including adhesive resin, lumps, 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 _p
and how to find t _b is illustrated. Draw a baseline at a certain peak, and at that wavelength, t _p and t _b
can be obtained 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 0.45Kg
added. The bath ratios in this case are 7.0, 8.5, 13.5, respectively.
They were 20.0, 28.0 and 45.0. In either case, if the mixed aqueous solution is 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, 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 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 a diluted mixture containing 80% by weight of phenol and 5% by weight of formaldehyde.
25g was added to each at once. In either case,
Stirring was stopped 10 seconds after the diluent was added and the mixture was allowed to stand still, 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 a peak in °C and then dropped again. After adding the diluent, 0.5 hours (Run No. 61), 1 hour (Run No. 62),
After being left at room temperature for 3 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 dissolved in 0.75% by weight ammonia water. After treatment at a temperature of 15-17°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, 150
The amount passed through a Tyler mesh sieve (150 mesh passes) and methanol solubility are shown.

[Table] Example 1 6 nylon chip (manufactured by Ube Industries, trade name
1013B) For 1 part by weight, 0, 0.015, 0.025, 0.04,
0.07, 0.15, 0.4 and 0.8 parts by weight were mixed and cooled while kneading and extruding with an extruder (manufactured by Sumitomo Heavy Industries, Ltd., type: 3AGM) to make guts, and each of them was made into chips. Next, each of the eight types of chips obtained was extruded into a mold maintained at 80°C at a cylinder temperature of 250°C, and the width of Run No. 51 to 58 listed in Table 7 was 5.
Eight types of molded products measuring cm x length 20 cm x thickness 0.5 cm were obtained. Table 7 shows the flow of the mixed resin during extrusion molding, the dispersibility of the granular or powdered resin, the compressive strength of the obtained molded product, and the volume resistivity before and after boiling when boiled in water. .

[Table] In Table 7, the symbol ◎ indicates that the flow of the resin or the dispersibility of the granular or powdered resin was very good, and the symbol ○ indicates that each was excellent. show. Example 2 12 nylon powder (manufactured by Ube Industries, trade name 3035J)
For 1 part by weight, the product of Run No. 12, the product of Run No. 40, the product of Run No. 47, the product of Run No. 50,
Products (cured products) obtained in Run No. 21, Run No. 22, and Run No. 23 and short glass fibers (fiber diameter 10 μ, length 2
0.3 parts by weight of each of mm) was added according to Example 1.
Eight types of molded products with Run Nos. 79 to 86 were created. Table 8 shows the moldability, volume resistivity and compressive strength before and after boiling in water of the obtained molded product.

[Table] Example 3 Polyester resin (manufactured by Kanebo Gosen Co., Ltd., trade name: Velpet EFG-6), polycarbonate resin (manufactured by Bayer Corporation, trade name: Macrolon 3100), polyethylene resin (manufactured by Mitsui Chemicals, Ltd., Product name Hi-Zex
2000), nylon 66 (manufactured by Ube Industries, Ltd., trade name: Nylon 2020B) and vinyl chloride resin (manufactured by Tekkosha Co., Ltd., trade name: Reeuron 7001), for 1 part by weight each of the product of Run No. 64. Blend 0.45 parts by weight of each,
The mixture was melt-mixed at a temperature of 150-300°C, then cooled and cut. Approximately 100 g of each sample was divided into 10 equal parts and treated for 5 minutes under a pressure of 100 to 500 kg/cm ² in a mold that had been preheated to 100 to 250°C between a hot press machine.
Molded products of Run No. 87 to 91 listed in Table 9 (width 13
mm, thickness 5.2 to 6.8 mm, and length 100 mm), 10 pieces were obtained for each sample. Table 9 shows the average properties of each of the 10 samples, including the heat deformation temperature of the above molded product and the flame resistance of the pine.
The flammability (Matsuchi test) is shown when exposed for 10 seconds. In addition, as a comparative example, molded products were similarly created using only each of the resins used above, and the results were reported in Run No.
They are also listed in Table 9 as 92-96.

[Table] Example 4 12 nylon powder (manufactured by Ube Industries, Ltd., trade name 3035J)
For 1 part by weight, add 1 and 3 of the product of Run No. 67, respectively.
and 10 parts by weight and pre-mix between heated press machine.
300Kg/cm ² in a mold heated to 150-170℃
Run No. listed in Table 10.
97~99 molded plate (width 13mm, thickness 0.5~0.6mm, length
100mm) were made. For comparison, 10 was molded under the same conditions as above except that only 12 nylon powder was used and a mold heated to 120°C was used.
Two molded plates were obtained (Run No. 100). Table 10 shows the average properties of the 10 samples, including the residual rate of heat shrinkage when the obtained molded plate is left in the air for 30 minutes in a dryer at 200℃, and the residual rate of heat shrinkage when the plate is left in the air at 500℃ under a nitrogen gas atmosphere. The thermal meltability and compressive strength when held at temperature for 10 minutes are shown.

【table】

【table】 [Brief explanation of the drawing]

FIG. 1 of the accompanying drawings is an infrared absorption spectrum diagram of an example of a granular or powdery 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 of methylene groups, methylol groups, and the above nitrogen-containing compounds. Residues from which active hydrogen has been removed and trifunctional phenolic 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. contains 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 defined as D _{1450 to 1500} , and 960～
The highest absorption intensity in the range of 1020 cm ^-1 (absorption peak attributed to methylol group) is
When expressed as D _{960 ~ 1020} , D _{960 ~ 1020} / D _{1450 ~ 1500} = 0.1 ~ 2.0,
and (B) the granular or powdered nitrogen-containing resin has a particle size of
A resin composition containing at least spherical primary particles of 0.1 to 100 microns and secondary aggregates thereof, and (b) a thermoplastic resin. 2. Claim 1, wherein the thermoplastic resin (b) is polyethylene resin, polypropylene resin, polystyrene resin, acrylic resin, vinyl resin, fluorine resin, polyacetal resin, polyamide resin, polyester resin, polycarbonate resin, or polyurethane resin. The composition described in . 3. According to any one of claims 1 to 2, 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. Compositions as described. 4 The granular or powdered nitrogen-containing resin (a) has the highest absorption intensity in the range of 1280 to 1360 cm ^-1 in the infrared absorption spectrum measured by the KBr tablet method.
The composition according to any one of claims 1 to 3, wherein when expressed as D _{1280 to 1360} , D _{1280 to 1380} / D _{1450 to 1500} = 0.15 to 3.0. 5 The granular or powdery nitrogen-containing resin (a) is KBr
The composition according to any one of claims 1 to 4, wherein _D960-1020 / _D1450-1500 is 0.15-0.6 in an infrared absorption spectrum measured by a tablet method. 6 The granular or powdery nitrogen-containing resin (a) is KBr
The composition according to any one of claims 1 to 5, wherein _D1280-1360 / _D1450-1500 is 0.2 to 2.0 in an infrared absorption spectrum measured by a tablet method. 7 The granular or powdery nitrogen-containing resin (a) is KBr
The composition according to any one of claims 5 to 6, wherein _D1280-1360 / _D1450-1500 is 0.3 to 1.5 in an infrared absorption spectrum measured by a tablet method. 8. The granular or powdered 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. Composition. 9. The composition according to any one of claims 1 to 8, wherein the granular or powdery nitrogen-containing resin (a) has a free phenol content of 500 ppm or less as measured by liquid chromatography. 10 The granular or powdered nitrogen-containing resin (a) contains at least 1% by weight of nitrogen.
The composition according to any one of items 1 to 9. 11 Claims 1 to 10 wherein the granular or powdery nitrogen-containing resin (a) contains 2 to 30% by weight of nitrogen.
The composition according to any of paragraphs. 12 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. A composition according to any one of claims 1 to 11. 13 10g 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 powdery nitrogen-containing resin remaining after heating and refluxing, and S is the methanol solubility (% by weight) of the granular or powdery nitrogen-containing resin. The composition according to any one of claims 1 to 12, wherein the content is 20% by weight or more. 14 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 composition according to any one of items 1 to 11. 15. The composition according to any one of claims 1 to 14, wherein the granular or powdery nitrogen-containing resin (a) is used in an amount of 0.01 to 20 parts by weight per 1 part by weight of the thermoplastic resin (b). 16. The composition according to claim 15, wherein the granular or powdery nitrogen-containing resin (a) is used in an amount of 0.02 to 3 parts by weight per 1 part by weight of the thermoplastic resin (b). 17. The composition according to claim 16, wherein the granular or powdery nitrogen-containing resin (a) is used in an amount of 0.03 to 0.9 parts by weight per 1 part by weight of the thermoplastic resin (b). 18 The composition according to claim 17, wherein the thermoplastic resin (b) is contained in an amount of 0.05 to 0.5 parts by weight of the granular or powdery nitrogen-containing resin (a) per 1 part by weight, and the composition is thermoplastic. Composition.