JPS6340214B2 - - Google Patents

Description

[Detailed description of the invention]

The present invention provides novel granular or powdered phenol
The present invention relates to a rubber composition containing formaldehyde resin. More specifically, the present invention provides a novel granular or powdery phenol which has good storage stability and flow characteristics and is reactive, and which is suitable as a molding material.
The present invention relates to a rubber composition containing a formaldehyde resin. Conventionally, novolac resins and resol resins are known as typical phenol formaldehyde resins. Novolac resins usually have a molar ratio of phenol to formaldehyde of, for example, 1.
in the presence of an acid catalyst such as oxalic acid (usually
0.2-2%) by reacting phenol with formalin. The novolac resin obtained by such a method is mainly composed of trimers to pentamers of phenols bonded mainly through methylene groups, contains almost no free methylol groups, and therefore cannot self-react by itself. It has no crosslinking properties and is thermoplastic. Therefore, the novolac resin is reacted under heat with a crosslinking agent which is itself a formaldehyde generator and also an organic base (catalyst) generator, such as hexamethylenetetramine (hexamine), or with a solid acid catalyst and paraformaldehyde, etc. A cured resin can be obtained by mixing with the resin and subjecting it to a heating reaction. However, when novolak resin is used as a rubber filler, the rubber molded product may foam due to ammonia generated by the decomposition of hexamine, or undecomposed hexamine products and organic by-products may form. The base remains in the rubber molded product, which has disadvantages such as deteriorating the physical properties of the molded product and requiring a long time for the curing reaction.Furthermore, in the case of the latter novolak resin, parts that come into contact with paraformaldehyde and acid catalysts are disadvantageous. The crosslinking reaction progresses excessively, making it difficult to form a uniform crosslinked structure as a whole, and acid catalysts and paraformaldehyde may remain, resulting in changes in physical properties over time, or foaming due to their decomposition during curing. Other disadvantages may also occur. In addition, since novolak resin is obtained by a reaction with excess phenol, it contains a relatively large amount of free phenol (for example, about 0.5-2% by weight), so rubber compositions containing this as a filler do not contain phenol during curing. This can cause problems during curing 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 decompose and remove low condensates, resulting in 7 to 10 phenol groups and methylene 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 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, conventionally known resol resins are prepared in the presence of a basic catalyst (approximately 0.2 to 2%) such as sodium hydroxide, ammonia, or an organic amine in an excess of formaldehyde, such as at a molar ratio of phenol to formaldehyde of 1:1 to 2. It is produced by reacting under the following conditions. The resol resin thus obtained is mainly composed of mono- to trimer of phenol having a relatively large amount of free methylol groups, and has extremely high reactivity, so it is usually prepared as a water or methanol solution with a solid content of 60% or less. It is stored in 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. In addition to being a non-reactive resin, this resin also contains a nitrogen-containing compound used as a catalyst and a hydrophilic polymer compound, which reduces the performance of rubber molded products obtained by using it as a filler. There is. 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 contains salts, acids, and other protective colloids, so it can also be used as a filler for rubber molding. There are drawbacks that reduce product performance. As mentioned above, attempts have been made to use phenol-formaldehyde resin as a rubber filler, but when viewed as a rubber filler, it is difficult to obtain phenol-formaldehyde resin in a shape or form suitable for use as a filler. First of all, this is difficult in itself, and it also has the problem of containing substances that have an undesirable effect on the rubber. The present inventors have previously provided a new granular or powdery phenol formaldehyde resin that does not have the above-mentioned drawbacks and a method for producing the same. Therefore, an object of the present invention is to provide a rubber composition containing a novel granular or powdered resin. Another object of the present invention is to provide a rubber composition having good moldability and containing a granular or powdery resin having good flow properties. Still another object of the present invention is to provide a rubber composition that contains a granular or powdered resin with a small free phenol content of 500 ppm or less, and is therefore safe and easy to handle. Yet another object of the present invention is to provide a rubber composition containing a particulate or powdered resin that is reactive with rubber so that the resin can chemically bond with the rubber in the cured form. be. Yet another object of the invention is to contain a granular or powdered resin which is reactive with rubber and therefore exhibits good mechanical properties in the cured form, such as good strength, high hardness, low compressive strain or good An object of the present invention is to provide a rubber composition exhibiting dimensional stability. Still another object of the present invention is to provide a rubber composition that exhibits excellent electrical insulation or heat resistance in a cured form. Further objects and advantages of the present invention will become apparent from the following description. These objects and advantages of the present invention are as follows: (a) 100 parts by weight of a rubber-like elastic material; and (b) a condensate of phenols and formaldehyde having the following properties (A) and (B). 200 parts by weight or less of a granular or powdered resin consisting of (A) the condensate (1) consisting essentially of carbon, hydrogen and oxygen atoms; (2) containing methylene groups, methylol groups and phenols; Contains a trifunctional residue as the main bonding unit, (3) The trifunctional residue is a 2-,
It is bonded to a methylene group at one position at the 4 and 6 positions, and a methylol group and/or a methylene group at at least one other position, and (4) has an absorption peak of 1600 cm ^-1 (absorption peak attributed to benzene). Absorption intensity D ₁₆₀₀ , 990 ~ 1015 cm ^-1
When the largest absorption intensity in the range (absorption peak attributed to the methylol group) is expressed as D _{990 to 1015} , and the absorption intensity in the range 890 m ^-1 (absorption peak of the vertical hydrogen atom of the benzene nucleus) is expressed as D ₈₉₀ , , D _{990 ~ 1015} / D ₁₆₀₀ = 0.2 ~ 9.0D ₈₉₀ / D ₁₆₀₀ =
0.09 to 1.0, and (B) the granular or powdered resin has a particle size of 1 to 150
This is achieved in a rubber composition containing micron spherical primary particles and secondary aggregates. The rubber-like elastic material (a) in the present invention is a substance that exhibits so-called rubber elasticity in a cured (or crosslinked or vulcanized) state or in an as-is state. Such rubbery elastic materials are well known in the art and include, for example, natural rubber or e.g. polybutadiene,
Polyisoprene, copoly(butadiene-styrene), copoly(butadiene-acrylonitrile),
Synthetic rubbers such as copoly(ethylene-propylene), polyisobutylene, copoly(isobutylene-isoprene), polychloroprene, polyacrylate rubber, polysulfide, silicone rubber, chlorinated polyethylene, fluorocarbon rubber, chlorosulfonated polyethylene or polyurethane are mainly used. Suitably used in the invention. These rubber-like elastic materials are suitably used as uncured products (or uncrosslinked products or unvulcanized products). Among the above rubber-like elastic materials, copoly(butadiene-acrylonitrile), polyacrylate rubber,
Fluorine rubber, copoly(butadiene-styrene),
Polychloroprene, chlorinated polyethylene, chlorosulfonated polyethylene, copoly(ethylene-propylene) or silicone rubber are particularly preferably used in the present invention. The rubber composition of the present invention using these preferably used rubber-like elastic materials is compared with a conventional rubber composition mixed with a phenol formaldehyde resin in a cured state for use in the present invention described below. The granular or powdered resin used provides superior heat resistance, abrasion resistance, adhesion, compressive strength,
Provides hardness or tearability. Furthermore, in the rubber composition of the present invention, the granular or powdered resin has a better effect of curing or thickening the rubber than conventional phenol formaldehyde resins. The granular or powdered phenolic-formaldehyde resin used in the present invention is composed of phenol, or at least 50% by weight, especially at least 70% by weight.
of phenols and e.g. o-
Cresol, m-cresol, p-cresol,
Bis-phenol A, o-, m- or p-C ₂ ~
It includes a condensate of formaldehyde and a mixture with one or more of known phenol derivatives such as C ₄ alkylphenol, p-phenylphenol, xylenol, and resorcinol. The granular or powdery resin in the rubber 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 thereof in (B) is 0.1 to 150 microns, D ₉₉₀ to ₁₀₁₅ in (A)(4) /D ₁₆₀₀ = 0.2 to 9.0 D ₈₉₀ /D ₁₆₀₀ = 0.09 to 1.0 are all based on the measurement method described below. The first characteristic of the above-mentioned granular or powdered resin is that it is a cured product of a conventionally known novolak resin or a cured product of a resol resin, which is extremely difficult to crush, or a cured product of a conventionally known cured resin. Completely different from pulverized novolac resin fibers, these are spherical primary particles and their secondary aggregates as specified in (A) above, with a particle size of 0.1 to 150 microns, preferably 0.1 to 100 microns. Contain something. The above granular or powdered resin is usually at least 30%, preferably at least 50% in the form of granules of 0.1 to 150%.
It consists of spherical primary particles of microns, more preferably 0.1 to 100 microns, and secondary aggregates thereof. This indication of 30% or 50% means 30% of the total number of particles (including secondary aggregates) in one field of view of an optical microscope at a magnification of 100 to 1000 times, as defined in the particle size measurement method below. It means % or 50%. Particularly preferred is one in which 70 to substantially 100% of the granular or powdered resin consists of spherical primary particles and secondary aggregates thereof having a particle size of 0.1 to 150 microns. Particularly preferred is at least 30%, 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.
100% to substantially 100% consist of spherical primary particles and secondary aggregates thereof ranging from 0.1 to 100 microns, more preferably from 0.1 to 50 microns. As mentioned above, the above granular or powdered resin is formed mainly of microparticles of the above spherical primary particles and their secondary aggregates, so it is extremely small, and at least 50% of the total % by weight, preferably 70% by weight, particularly preferably at least 80% by weight of the total passes through a 100 taylor mesh sieve. This indication that the granular or powdered product of the present invention passes through the sieve means that the granular or powdered product of the present invention is lightly massaged by hand or passed through the sieve with a brush-like object. Avoid applying any force that does not forcefully destroy the particles (including secondary aggregates), such as lightly pressing or smoothing the particles on top, or tapping them with your hand. It's not a thing. The above granular or powdered resin further comprises the above (A)
As specified in (4), it has the characteristics of _D990-1015 / _D1600 =0.2-9.0 and _D890 / _D1600 =0.09-1.0 in the infrared absorption spectrum. Further, the resin used in the present invention preferably has a _D990-1015 / _D1600 of 0.3-7.0, particularly 0.4-5.0, and a _D890 / _D1600 of 0.1-0.9, particularly 0.12-0.8. have In the infrared absorption spectrum, the peak at D ₁₆₀₀ indicates absorption attributed to the benzene nucleus, and the peak at D _{990 to 1015}
The peak of shows the absorption attributed to the methylol group,
Furthermore, it is already known for phenol-formaldehyde resin that the D ₈₉₀ peak shows absorption attributed to isolated hydrogen atoms of benzene nuclei. The resin used in the present invention has D _{990 ~ 1015} / D ₁₆₀₀ =
The characteristic values of 0.2 to 9.0 indicate that the resins used in the present invention contain at least some amount of methylol groups, and that the methylol group content can vary quite widely. Especially D _990~1015
=0.3 to 7.0, especially 0.4 to 5.0, the resin preferably used in the present invention contains an appropriate concentration of methylol groups and is more stable. Furthermore, in the infrared absorption spectrum of the resin used in the present invention, D ₈₉₀ /D ₁₆₀₀ = 0.09 to 1.0, and a more suitable resin has D ₈₉₀ /D ₁₆₀₀ = 0.1 to 0.9, particularly 0.12.
The fact that the resin used in the present invention exhibits a characteristic of ˜0.8 indicates the fact that the reactive sites (ortho and para positions) of the phenolic skeleton of the resin used in the present invention are moderately blocked by methylene bonds or methylol groups. Cured products of conventionally known resol resins are generally
Both or one of D _{990 to 1015} /D ₁₆₀₀ and D ₈₉₀ /D ₁₆₀₀ is lower than the lower limit of the upper air characteristic value of the resin used in the present invention, and the novolac resin cured with hexamine also has D ₈₉₀ /DD ₁₆₀₀ is generally lower than the lower limit of 0.09 for the resins used in the present invention. The granular or powdered resin used in the present invention usually has a free phenol content of 500 ppm or less as measured by liquid chromatography, and more preferable products have a free phenol content of 500 ppm or less as measured by liquid chromatography.
400ppm or less, particularly 300ppm or less. The granular or powdered resin obtained by the method disclosed in Japanese Patent Publication No. 53-42077 contains an extremely large amount of free phenol, from 0.3 to about 6% by weight, whereas the granular or powdered resin used in the present invention The free phenol content of the resin is extremely low. This fact provides an important advantage in use for this type of granular or powdered resin. The granular or powdered resin used in the present invention is
According to elemental analysis, it consists essentially of carbon, hydrogen and oxygen, with the following composition: C: 70-80% by weight, H: 5-7% by weight and O: 17-21% by weight (total 100% by weight). It is also clear that there is. The granular or powdered resin used in the present invention is
According to the manufacturing method described later, it is possible to take either a state in which the curing reaction has not progressed sufficiently or a state in which the curing reaction has progressed relatively. As a result, the granular or powdered resin used in the present invention thermally exhibits (a) at least It includes both (b) those in which a part of them is fused to form a lump or plate, 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 . In addition, the granular or powdered resin used in the present invention has an acetylation weight increase rate of 23 to 40% by weight, more preferably 25 to 37% by weight, particularly 27 to 35% by weight, as measured by the method described later. % is also included. The resin in (b) above that does not substantially melt or fuse,
This usually corresponds to a resin that exhibits the above-mentioned acetylated weight increase rate. In addition, when the solubility of resins exhibiting such acetylation weight increase rate in methanol is measured according to the test method described later, the methanol solubility is 20% by weight or less, and 15% by weight or less for resins with a low solubility in methanol. Furthermore, it shows 5% by weight or less,
High resistance to methanol solubility. The granular or powdered resin used in the present invention is characterized by having the characteristics (A) and (B) described above. The granular or powdered resin used in the present invention has a particle size of 0.1 to 150 microns, preferably 0.1 to 150 microns.
Contains spherical primary particles of 100 microns and their secondary aggregates (condition (B) above), preferably contains at least 50% of these, and usually at least 50% of these.
% by weight, preferably at least 70% by weight, has a size that allows it to pass through a 100 Tyler mesh sieve, so it has very good fluidity and can be mixed easily and in relatively large amounts with elastomeric materials. Can be done. Furthermore, since at least many of the resins used in the present invention have extremely small spherical primary particles as their basic constituents, cured molded products obtained by curing the rubber composition of the present invention containing these particles are It exhibits excellent mechanical properties, especially strong resistance to compression. The granular or powdered resin used in the present invention is made by growing white cloudy microparticles, which are the initial reaction product of phenols, and reacting with formaldehyde, so it is extremely stable at room temperature, and it itself contains a considerable amount of methylol. Because it contains groups, it exhibits reactivity when heated, and as shown in the examples below, it forms rubber molded products that have extremely excellent not only physical and mechanical properties but also heat insulation, heat resistance, and other electrical properties. . The granular or powdered resin used in the present invention further has a free phenol content of usually 500 ppm or less,
It is preferably as low as 400 ppm or less, especially 300 ppm or less. Since the phenol content is extremely low, the granular or powdered resin used in the present invention is extremely easy to handle and safe. This also means that when obtaining a molded article from the rubber composition of the present invention, not only side reactions caused by phenols do not occur, but also physical properties of the rubber molded product do not deteriorate due to free phenols. Become a reason. Furthermore, as is clear from the production method described below, the granular or powdered resin used in the present invention is produced by a production method that does not substantially contain a nitrogen-containing basic compound or a hydrophilic polymer compound in the reaction system. Therefore, it usually does not substantially contain nitrogen-containing basic compounds or hydrophilic polymer compounds.
For this reason, when the rubber 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 phenol-formaldehyde resin used in the present invention is extremely fine, has good storage stability and flow characteristics, contains a certain amount of methylol groups, and usually has a low free phenol content. Since the amount is extremely small, the rubber composition of the present invention has an excellent feature of being reactive when molded and heated. Thus, among the granular or powdered resins used in the present invention, at least a portion of the resin exhibits fusion properties when heated at 100°C for 5 minutes according to the heat fusion measurement method.
The resin (a) provides the rubber composition of the present invention that provides a particularly heat-resistant or heat-insulating rubber molded product, and the resin (b), which does not show fusion properties by the above measurement method, has a particularly heat-resistant or heat-insulating rubber molded product. , the rubber composition of the present invention provides a heat-insulating or impact-resistant rubber molded article. The granular or powdered resin used in the present invention has the following composition: (1) The following composition Hydrochloric acid (HCL) concentration: 5 to 28% by weight, (preferably 10 to 25% by weight, especially 15 to 22% by weight), Formaldehyde ( HCHO) concentration is 3-25
% by weight (preferably 5-20% by weight, especially 7-15% by weight)
weight%), and the total concentration of hydrochloric acid and formaldehyde is 15 to 40
% by weight (preferably 20-35% by weight, especially 25-32% by weight)
(wt%), (2) The following formula A, bath ratio = weight of the above hydrochloric acid-formaldehyde bath/weight of phenols...... (A) The bath ratio expressed by the following formula is at least 8 or more ( (3) Bringing the phenols into contact with the hydrochloric acid-formaldehyde bath, and continuing this contact until the phenols become cloudy after coming into contact with the bath. (preferably by forming a clear solution before forming a cloudy state) and thereafter forming at least a pink granular or powdery solid. As for the composition of the hydrochloric acid-formaldehyde bath in (1) above, in addition to the three conditions (a), (b), and (c) above, the further condition (d) is: formaldehyde in the bath/contact with the bath. It is preferable that the molar ratio of the phenols used is at least 2 or more, especially 2.5 or more, particularly 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 having a considerably high concentration of hydrochloric acid (HCL) and containing an excess of formaldehyde relative to phenols is used at a bath ratio of 8 or more, preferably 10. The purpose is to bring it into contact with phenols at such a large ratio. As mentioned above, such phenol-formaldehyde reaction conditions are fundamentally different from the reaction conditions for the production of hitherto known novolac resins and resol resins. Before adding phenols to a hydrochloric acid-formaldehyde bath to form a white cloud, the bath is stirred so that the added phenols form a transparent solution as uniform as possible with the bath, and the white cloud is prevented. It is preferable not to apply mechanical shearing force, such as stirring, to the bath (reaction liquid) during the period from the time of generation until the pale pink solid is formed. The phenol to be added may be the phenol itself, but the phenol may be diluted with formalin, and the aqueous hydrochloric acid solution may be diluted with water. Furthermore, the temperature of the hydrochloric acid-formaldehyde bath when adding phenols (or their diluted solutions) is 90°C.
Temperatures below 0.degree. C., especially below 70.degree. C. are preferred. If the temperature of the bath is higher than 40℃, especially higher than 50℃,
Since the reaction rate between phenols and formaldehyde is high, it is preferable to add the phenols to the bath as a diluted solution, especially diluted with the formalin solution. In this case, since the reaction rate is high, it is preferable to bring the phenol, especially a dilute solution thereof, into contact with the solution in the form of a trickle or as small as possible droplets. When the bath temperature is 40°C or higher, especially 50°C or higher, when phenols or diluted solutions thereof are brought into contact with this bath, the higher the bath temperature, the faster the reaction rate between the phenols and formaldehyde. After the contact, white turbidity occurs within a short period of time or instantaneously, and a pink granular or powdery solid is rapidly formed. Keep the temperature of the hydrochloric acid-formaldehyde bath below 40℃.
The temperature is preferably kept at 5° to 35°C, particularly preferably 10 to 30°C, and phenols or the above-mentioned diluted solution thereof, preferably a water diluted solution of phenol, is added to this bath, and after white turbidity is formed, the temperature is approximately 50°C or lower, Preferably
For granular or powdered solids that have completed the desired reaction at a temperature of 45°C or lower, the curing reaction has not progressed sufficiently, so they generally do not exhibit thermal adhesive properties in the 100°C thermal adhesion test described below. Become. On the other hand, the temperature of the hydrochloric acid-formaldehyde bath was set to 40
℃ or below, preferably 15° to 35°C, substantially the entire amount of the phenol or its diluted solution to be added to this bath is added under stirring to form a clear solution, and then cloudy without stirring. is produced, and then a light pink granular or powdery solid is produced without raising the temperature, and this solid is heated to 50%
If the desired reaction is completed by heating to a temperature higher than 70°C, preferably 70°C to 95°C, the curing reaction will proceed more, so the heat fusion properties at 100°C will be reduced or substantially reduced. Or, it becomes one that exhibits heat fusibility at a higher temperature, for example, 200°C, or one that has substantially no heat fusibility even at such a high temperature. As the phenol used in the above method, phenol is most suitable, but as long as it contains at least 50% by weight of phenol, especially at least 70% by weight, o-cresol, m-cresol, p-cresol, etc.
It may be a mixture with one or more of known phenol derivatives such as cresol, bis-phenol A, o-, m- or p- _C2 - _C4 alkylphenol, p-phenylphenol, xylenol, resorcinol, etc. . The granular or powdery phenol-formaldehyde resin solids produced in the bath as described above and on which the desired reaction has been completed are separated from the hydrochloric acid-formaldehyde bath, washed with water, and preferably adhered. A desired product can be obtained by neutralizing hydrochloric acid with an alkaline aqueous solution such as ammonia water or methanolic ammonia water and washing with water. In this case, 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 rubber composition of the present invention contains the above-mentioned rubber-like elastic material and the above-mentioned granular or powdery resin. The blending ratio of the above elastic material and resin in the rubber composition of the present invention varies depending on the type of elastic material or the characteristics of the resin, such as the amount of methylol group content and its use, but in general, 100% of the weight of the rubber-like elastic material is The amount of the above-mentioned resin per part is 200 parts by weight or less, preferably 3 to 200 parts by weight, particularly preferably 5 to 150 parts by weight. Among these, 10 to 100 parts by weight is preferred. In addition to the rubber-like elastic material and granular or powdered resin, the rubber composition of the present invention contains various additives commonly used in rubber compounds, such as a vulcanizing agent, a vulcanization aid, a vulcanization accelerator, and a rubber compound. It may contain a protective agent, a rubber processing agent, a reinforcing agent, an extender, a coloring agent, etc. Examples of vulcanizing agents include sulfur, selenium,
Sulfur-based or oxime-based vulcanizing agents such as tellurium, sulfur chloride, p,p'-dibenzoylquinone dioxime, and p-quinone dioxime; and, for example, 1,1-bis(t-butyl)peroxy 3,
3,5-trimethylcyclohexane, benzoyl peroxide, t-butylperoxyisopropyl carbonate, dicumyl peroxide, t
-Organic peroxides such as butylcumyl peroxide, methyl ethyl ketone peroxide, and cumene hydroperoxide can be mentioned. Examples of vulcanization aids include zinc oxide, white lead,
Calcium hydroxide, litharge, stearic acid, oleic acid, lauric acid, linseed oil, cottonseed oil fatty acid, zinc stearate, lead oleate, dibenzylamine, diphenylguanidine phthalate, dibutylammonium oleate, diethanolamine, monoethanolamine, etc. can be given. Examples of vulcanization accelerators include guanidines such as diphenylguanidine, triphenylguanidine, and diphenylguanidine phthalate; aldehydes and ammonias such as hexamethylenetetramine, acetaldehyde, and ammonia; acetaldehyde, aniline, anhydrous formaldehyde, p-
Amines or nitrosos such as toluidine, mixtures of butyraldehyde and ethylene polyamine, condensates of acrolein and aromatic amines; such as 2-mercaptobenzothiazole, dibenzothiazyl disulfide, cyclohexylbenzothiazyl sulfenamide Thiazoles; Thioureas such as thiocarvanilide and trialkylthiourea; Zn-butyl xanthate, Zn-isopropyl xanthate, Zn-dimethyldithiocarbamate, Na-diethyldithiocarbamate, Pd
- thioates or dithioates such as dimethyldithiocarbamate, Cu-dimethyldithiocarbamate, Pb-pentamethylenedithiocarbamate; tetramethylthiuram monosulfide,
Examples include thiurams such as tetramethylthiuram disulfide and dipentamethylenethiuram tetrasulfide; or mixtures of two or more of the above-mentioned species. The above-mentioned vulcanizing agent, vulcanizing aid, or vulcanizing accelerator can be contained preferably in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the rubbery elastic material in the rubber composition of the present invention. Examples of rubber protectants include antioxidants such as N-phenyl-1 naphthylamine, p-(p-trisulfonylamide) diphenylamine, phenyl isopropyl p-phenylenediamine, and p-phenylphenol; For example, antiozonants such as p-phenylenediamine, 6-amino-2,2,4-trimethyl-2,2-dihydroquinoline, nickel dibutyl dithiocarbamate; for example, N-phenyl-2-naphthylamine, N , N'-diphenylethylenediamine; or, for example, copper damage inhibitors such as diβ-naphthylparaphenylenediamine and calgon. Examples of rubber processing agents include plasticizers or softeners such as various esters, ketones, aromatic hydrocarbons, alcohol mineral vegetable oils, and coal tar products;
For example, carbolic acid resin, coumaron indene resin,
Binder such as turpentine styrene resin; for example,
Examples include dispersants such as fatty acids and their soaps and amines; for example, combustion inhibitors such as tricylenyl phosphate and tricresyl phosphate. Examples of reinforcing agents include carbon black, zinc white, clay, magnesium carbonate, various silicas,
Inorganic reinforcing agents such as silicate calcium carbonate;
Examples include organic reinforcing agents such as asphalt-based materials, phenolic resins, terpene resins, coumaron/indene resins, various natural fibers, various artificial fibers, and various synthetic fibers. As the filler, for example, clay, talc, chiyolk, barite, lithopone, magnesia carbonate, zinc white, white glaze, etc. are used. Examples of colorants include inorganic pigments such as various carbon blacks, titanium whites, zinc whites, red iron oxides, iron blues, cobalt blues, yellow ocher, chrome greens, and chrome oranges; for example, phthalocyanine blues, parallets, Hansa yellows, and oranges. Organic pigments such as lakes can be used. The above-mentioned rubber protective agent, rubber processing agent, reinforcing agent, thickener, or coloring agent may be contained in the rubber composition of the present invention in an amount of up to 100 parts by weight based on 100 parts by weight of the rubber-like elastic material. You can force it. The rubber composition of the present invention is prepared by mixing a rubber-like elastic material, a granular or powdered resin, and various additives such as those mentioned above, using an open roll or the like.
After melt mixing at a temperature of 150°C or mixing with a solvent suitable for the rubbery elastic material used, such as toluene, xylene, perchlorethylene, trichlorethylene, ketones, ethers, alcohols, ethyl acetate, gasoline or light oil. It can be prepared by removing solvent. The rubber composition of the present invention is cured (crosslinked or vulcanized) during melt mixing or solvent mixing or desolvation, and the rubber composition of the present invention also includes such compositions. For example, an oil seal obtained by heat-treating the rubber composition of the present invention at a temperature of 100 to 200°C,
Gaskets, gaskets, oil-resistant hoses, conveyor belts, rubber rolls, window frame rubber, tires, diaphragms, electrical parts, soles and heels of shoes, etc. have excellent mechanical properties such as excellent strength, high hardness, small compressive strain, and excellent Indicates the desired properties required for the product, such as dimensional stability, electrical insulation, and heat resistance. The present invention will be described in more detail below with reference to Examples. In addition, the abbreviations in the examples are as follows. Accelerator TT: Tetramethylthiuram disulfide DM: Dibenzothiazyl sulfide M: 2-Mercaptobenzothiazole 22: Above mixture M + TT Aritax: Benzothiazyl disulfide Lissage: Pbo; Acid acceptor pine tar; Pine resin light process oil: A type of oil DDM: Dodecyl mercapton GMF: Paradinitrosobenzene-containing accelerator TAIC: Allyl isocyanurate DOP: Dioctyl phthalate TET: Tetraethyltetramine 1 Method for measuring 0.1-150 μ particles Approximately 0.1 g of sample is sampled from one sample. Such sampling is performed five times from different locations for one sample. One portion of each approximately 0.1 g sample was placed on a microscope slide glass. To facilitate observation of the sample placed on a slide glass, spread it out so that the particles do not overlap as much as possible. Microscopic observation shows that granular or powdery substances and/or their secondary aggregates are observed in the visual field under an optical microscope.
Do this for about 50 locations. It is usually desirable to observe at a magnification of 10 ² to ^{10 3} times. The sizes of all particles present in the field of view under the light microscope are read and recorded by a measurer in the field of view under the light microscope. The content (%) of particles with a size of 0.1 to 150μ is determined by the following formula. Content rate (%) of 0.1 to 150 μ particles = N ₁ / N ₀ × 100 N ₀ : Total number of particles whose dimensions were read under the microscope N ₁ : Number of particles with dimensions of 0.1 to 150 μ out of N ₀ Number: The content of particles of 0.1 to 150μ is expressed as the average value of the results of five samples for one sample. 2. 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 tp and the baseline transmittance at that wavelength is expressed as tb, the absorption intensity D at that specific wavelength is given by the following formula. D=logtb/tp Therefore, for example, the ratio between the absorption intensity of the peak at 890 cm ^-1 and the absorption intensity of the peak at 1600 cm ^-1 is the ratio of the respective absorption intensities calculated using the above formula (D ₈₉₀ /
D ₁₆₀₀ ). 3. Amount passing through a 100-meter mesh sieve After thoroughly kneading the dry sample with your hands if necessary, accurately weigh about 10 g of it, and shake it through a 100-meter mesh sieve in small portions over 5 minutes. ;200mmφ, shaking conditions;200RPM)
After adding the sample, shake for another 10 minutes. The amount of passage through a 100 tiler mesh is calculated using the following formula. Amount passing through the 100 Tyler mesh sieve (weight%) = ω ₀ − _{ω 1} / ω ₀ ×100 ω ₀ : Input amount (g) ω ₁ : Amount remaining on the sieve without passing through the 100 Tyler mesh sieve (g ) 4 Determination of free phenol content Approximately 10 g of a sample passed through a 100-meter mesh is accurately weighed and heated under reflux for 30 minutes in 190 g of 100% methanol. Glass filter (No.3)
The filtrated solution was subjected to high performance liquid chromatography (6000A, manufactured by Waters, USA) to quantify the phenol content in the solution, and the free phenol content in the sample was determined from a separately prepared calibration curve. The operating conditions for high performance liquid chromatography are as follows. Equipment: 6000A manufactured by Waters Co., USA Column carrier: μ-Bondapak C ₁₈ column: 1/4 inch diameter x 1 foot length Column temperature: Room temperature Eluent: Methanol/water (3/7, volume ratio) Flow rate: 0.5 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°C Approximately 5 g of sample passed through 100 tyler mesh was
A heat press machine (manufactured by Shinto Metal Industry Co., Ltd., single-acting compression molding machine) was prepared by inserting the material between two 0.2 mm thick stainless steel plates and preheated it to 100℃.
Pressed for 5 minutes at an initial pressure of 50 kg. After releasing the press, the hot-pressed sample was taken out from between the two stainless steel plates. If the sample taken out is clearly fixed to form a flat plate due to melting or fusion, it is determined that the sample has fusible properties, and if there is almost no difference between before and after hot pressing, the sample is judged to be It was judged to be infusible. 6 Methanol solubility (S) Accurately weigh approximately 10 g of the sample (the accurately weighed weight is defined as W ₀ ), and dissolve it in approximately 500 ml of substantially anhydrous methanol.
Heat under reflux for 30 minutes. Pass through a glass filter (No. 3), and wash the remaining 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 Acetylation weight increase rate Approximately 10 g of the dry sample was accurately weighed, and this accurately weighed sample was mixed with 78% by weight of acetic anhydride and 20% by weight of acetic acid. and 2% by weight of orthophosphoric acid.
Add to g. Then 45 degrees from room temperature to 115℃
Heat gradually to 115°C for 1 minute or more.
Hold for 15 minutes. Thereafter, it is allowed to cool, and carefully filtered through a No. 3 glass filter while suctioning with an aspirator, and then thoroughly washed with hot water on the glass filter, and finally washed with a small amount of cold methanol. Next, the glass filter and the residue on the glass filter are dried in a dryer at 70° C. for 2 hours, and then left overnight in a desiccator using silica gel as a desiccant. Accurately weigh the dry weight of the residue on the filter. The acetylation weight increase rate (I) is determined by the following formula. I=W ₁ −W ₀ /W ₀ ×100 W ₀ : Accurately weighed weight of dry sample before acetylation (g) W ₁ : Accurately weighed weight of dry sample after acetylation (g) 8 OH group value Hydroxyl group value Measure according to the measurement method (Cosmetic Raw Materials Standard Commentary, 1st edition, Yakuji Nipposha, 1975, General Test Method 377). 9. Bulk density: It is cut off at the 100ml mark.
Pour the sample that has passed through the 100 ml mesh into a 100 ml graduated cylinder from 2 cm above the rim of the graduated cylinder. The bulk density is determined by the following formula. Bulk density (g/ml) = W (g) / 100 (ml) W: Weight per 100ml (g) 10 Measurement of hardness and tensile strength and elongation Performed according to the method described in JIS K-6301-1975 Ivy. 11 Measurement of compressive strain Measurement was performed according to the method described in JIS K-6301-1975. However, the measurement was performed under the conditions of 25% compression and 70°C for 22 hours. 12 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 of phenol (the remaining 2% by weight is water) and
A mixed aqueous solution (25°C) containing 80 wt% phenol and 5 wt% formaldehyde prepared using 37 wt% formalin and water was prepared, respectively.
62.5g was added. After adding and stirring for 20 seconds,
It was left to stand for 60 minutes. While standing still for 60 minutes,
Some of the contents in each separable flask remain transparent (Run
Nos. 1 and 20), some changed from transparent to cloudy (Run Nos. 3, 9 and 18 in Table 1), and some changed from transparent to cloudy and then turned pale pink (Run No. 3, 9 and 18 in Table 1). Run No. 2, 4 to 8 in Table 1
10-17 and 19). When observed under a microscope, this pink colored material already contained spherical objects, aggregates of spherical objects, and a small amount of powdery material. Next, while stirring the contents in each separable flask from time to time, the temperature was further increased to 80°C over 60 minutes, and then maintained at a temperature of 80 to 82°C for 15 minutes to obtain a reaction product. The reaction product thus obtained was
Washed with warm water at ~45 °C, treated in a mixed aqueous solution consisting of 0.5 wt% ammonia and 50 wt% methanol at a temperature of 60 °C for 30 min, and then washed again at 40-45 °C.
It was washed with warm water and dried at 80°C for 2 hours. Table 2 shows the properties of the reaction products obtained from the mixed aqueous solutions of hydrochloric acid and formaldehyde of various compositions thus obtained. (2) On the other hand, the following experiment was conducted for comparison. 282g of distilled phenol, 369g of 37% by weight formalin, and 150g of 26% by weight ammonia water were placed in a separable flask from Step 1, and the temperature was raised from room temperature to 70°C in 60 minutes while stirring.
The mixture was further stirred and heated at a temperature of 70 to 72°C for 90 minutes. Then, it was left to cool, and 300 g of methanol was added little by little to remove water by azeotropic distillation under a reduced pressure of 40 mmHg, using methanol as a solvent.
700g was added and a yellowish brown transparent resol resin solution was taken out. When a portion of the thus obtained resol resin was desolvated under reduced pressure, it foamed violently and turned into a gel. This gelled product is further heated at a temperature of 160℃ under nitrogen gas.
After heat curing for 60 minutes, the resulting cured foam was crushed to obtain a small amount of powder that passed through a 100-meter mesh sieve. In this case, the thermosetting resol resin is extremely hard, and it is extremely difficult to obtain a powder of 100 mesh passes even using various types of crushers, ball mills, or vibrating mills for fluorescent X-rays.
The thus obtained thermosetting resol resin powder was mixed with 0.5% by weight of ammonia under the same conditions as described above.
It was treated with a mixed aqueous solution consisting of 50% by weight methanol, washed with warm water and then dried. The properties of the sample thus obtained are listed in Table 2 as Run No. 21. Next, put 390 g of phenol, 370 g of 37% by weight formalin, 1.5 g of oxalic acid, and 390 g of water into a separable flask, and while stirring.
Raise the temperature to 90℃ in 60 minutes, and at a temperature of 90-92℃
Stir and heat for 60 minutes. Then 35% by weight hydrochloric acid
1.0 g was added, and the mixture was further stirred and heated at a temperature of 90 to 92°C for 60 minutes. Next, 500 g of water was added and cooled, the water was removed with a siphon, and the mixture was heated under reduced pressure of 30 mmHg, heated at 100°C for 3 hours, and further heated to 180°C for 3 hours under reduced pressure and heated. did.
The resulting novolak resin was obtained as a tan solid upon cooling. This one has a softening temperature of 78
~80°C, and the free phenol content determined by liquid chromatography was 0.76% by weight. The above novolac resin was ground and mixed with 15% by weight of hexamethylenetetramine, the mixture was heat cured in nitrogen gas at a temperature of 160°C for 120 minutes, then ground in a ball mill and passed through a sieve of 100 Tyler mesh. I forced it. The powder thus obtained was treated with a mixed aqueous solution of 0.5% by weight ammonia and 50% by weight methanol under the same conditions as described above, washed with warm water and then dried. The properties of the sample thus obtained are listed in Table 2 as Run No. 22. Furthermore, the above novolac resin was made with a hole diameter of 0.25mmφ.
Melt spinning was carried out at a temperature of 136-138°C using a spinneret with 120 holes. average fiber obtained
A spun yarn of 2.1 denier was immersed in a mixed aqueous solution containing 18% by weight of hydrochloric acid and 18% by weight of formaldehyde at a temperature of 20 to 21°C for 60 minutes, and then immersed at 97°C.
It took 5 hours to raise the temperature to 97-98℃.
The temperature was kept at ℃ for 10 hours. The thus obtained cured novolak fibers were washed with hot 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 100-meter mesh sieve are listed in Table 2 as Run No. 23. (3) Table 1 shows the hydrochloric acid and formaldehyde used, the total concentration of hydrochloric acid and formaldehyde, and the molar ratio of formaldehyde to phenol. Table 2 also shows 1-50 μ, 1-100 μ, and 1-1 μ by microscopic observation of the obtained samples.
Content of 150μ particles, amount of sieve passing through a 100-meter mesh sieve (100 mesh passes), 990 to 1015 cm ^-1 and 890 cm ^-1 of the obtained sample by infrared absorption spectroscopy of
Absorption wavelength intensity ratio (IR intensity ratio) to 1600cm ^-1
and the weight increase rate due to acetylation.

【table】

[Table] In the experiments of Run Nos. 1, 2, 3, 6, 17, and 20 in Table 1, many sticky resins and hard large lumps or plate-like materials were formed at the bottom of the separable flask. Also, in the experiments of Run Nos. 1, 2 and 20, only less than 49 g of solids were obtained from the 50 g of phenol used. 1-50μ, 1-100μ and 1 listed in Table 2 for Run No. 1, 2, 3, 6, 17 and 20.
The values for the content (%) of ~150μ particles and 100 mesh pass (% by weight) are for granules or powders based on the total solids including adhesive resin, lumps and platelets. However, among the solid materials produced in these experiments, only granular or powdery materials of 1 to 50μ, 1
The content (%) of ~100μ and 1-150μ particles and 100 mesh pass (% by weight) were the values shown in Table 2, respectively, enclosed in a box. From the above experimental facts including the results listed in Table 2, Run Nos. 1, 2, 3, 6, 17 and 20 cannot be recommended as manufacturing methods. However, even if these manufacturing methods are used, as far as the granules or powders produced are concerned, these granules or powders have characteristics that are fully included in the granules or powders of the present invention. There is. Reference Example 2 10.2 to 11.7 kg of a mixed aqueous solution consisting of 20% by weight hydrochloric acid and 11% by weight formaldehyde was put into each of 6 20 reaction vessels as shown in the bath ratio shown in Table 3. In each flask, add phenol 90% by weight and formaldehyde while stirring at a temperature of 23 °C.
1.8Kg and 1.5Kg of mixed aqueous solution consisting of 3.7% by weight, respectively.
Kg, 0.9Kg, 0.7Kg, 0.4Kg and 0.25Kg added. The bath ratios in this case were 7.3, 8.5, 13.5, 17.0, 28.9 and 45.6, respectively. In either case, if you continue stirring after adding the phenol mixed aqueous solution, the
It rapidly became cloudy in 120 seconds. As soon as the mixture became cloudy, stirring was stopped and the mixture was allowed to stand still. As the internal temperature gradually rose, the contents gradually changed color to pale pink, and 30 minutes after the contents became cloudy, a slurry-like or resin-like substance was observed to be formed in each case. Next, each content was heated to 75° C. over 2 hours while stirring, and then stirred and heated at a temperature of 75 to 76° C. for 30 minutes. In this case, in the system with a bath ratio of 7.3, a large amount of cured resin material adhered to the stirring rod, making stirring extremely difficult. In both cases, the color of the contents changed from pale pink to pink and then red as the temperature rose. Next, the contents were washed with water, treated in a mixed aqueous solution of 0.1% by weight ammonia and 55% by weight methanol at a temperature of 50°C for 60 minutes, and further washed with warm water at 80°C for 60 minutes. The resulting granules, powders, or lumps were lightly massaged by hand and dried at a temperature of 100° C. for 2 hours. The moisture content after drying is
It was 0.2% by weight or less. The contents are Samples 31, 32, 33, 34, 35, and 36 in descending order of reaction bath ratio. Table 3 shows the maximum temperature reached in the reaction system from the start of the reaction until 30 minutes after it becomes cloudy, the yield of the reaction product, the presence or absence of spherical primary particles as determined by microscopic observation, and the proportion of 100 tyers in the reaction product. The content of the mesh-passed material, the heat fusion property of the reaction product at 100°C, the elemental analysis value of the reaction product, the OH group value of the reaction product, and the light reflectance at 500 mμ of the acetylated product are shown.

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

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

[Table] Example 1 (1) 100 parts by weight of Neoprene W (manufactured by Showa Neoprene Co., Ltd.), 5 parts by weight of zinc white, 4 parts by weight of highly active magnesia, 3 parts by weight of light process oil, 1 part by weight of stearic acid, promotion Agent 22 3 parts by weight and SRF
To 30 parts by weight of black, (2) 0, 1, 3, 5, 10, 50, 100, 150, 200 and 250 parts by weight of the granular or powdered resin obtained in Run No. 12 were mixed, Ten different mixtures were prepared. Twice the amount of trichlorethylene was added to each of these 10 mixtures to dissolve them. Next, after thoroughly stirring each solution, the solvent was removed under reduced pressure of 30 mmHg. Cut this into pieces of 1 to 3 mm and preheat to 170℃. Dimensions: 120 mm x 150.
Place it in a mm mold, pressurize it while degassing,
Finally, the rubber sheets of Run Nos. 51 to 60 listed in Table 6 were obtained by hot pressing for 30 minutes under a pressure of 100 Kg/cm ² . Table 6 shows the mixing amount of the above resin; the thickness, hardness, compressive strain, tensile strength, tensile elongation, and volume resistivity of the obtained molded products; and the temperature of each molded product at 170°C.
hardness, tensile strength and tensile elongation after heat treatment at a temperature of 24 hours.

[Table] Example 2 Nitrile rubber (Hiker OR25; Nippon Zeon)
100 parts by weight, 5 parts by weight of zinc white, 1.5 parts by weight of stearic acid, 1.5 parts by weight of Aritax, 3 parts by weight of pine tar
Parts by weight of accelerator DM, 2 parts by weight of sulfur, and 40 parts by weight of carbon black were kneaded in an open roll at 95°C, and Run No. 1 of Reference Example 1 was added to the mixture.
12, 40 parts by weight of wood flour and the sample produced in Run No. 44, Run No. 47, Run No. 21, Run No. 22, or Run No. 23 were added, thoroughly mixed, and extruded into a sheet. Next, the rubber sheet obtained by the above method was heat treated at a temperature of 170° C. for 3 hours under a pressure of 1 to 2 kg/cm ² . All of these heat-treated sheets have a thickness of 1.0 to 1.1
mm, and Run No. 61 to Run in the order of the filler used.
It was named No.68. Table 7 shows the type and blendability of the filler; the tensile strength and elongation of the obtained sheet; and the shrinkage rate and tensile strength retention of the heat-treated sheet heat-treated at a temperature of 180° C. for 24 hours.

[Table] Example 3 For 100 parts by weight of the various rubbers listed in Table 8,
50 to 110 parts by weight of carbon black and various compounding agents listed in Table 8 using an open roll.
Kneaded at a temperature of °C. After extruding this kneaded material into a sheet form, it was heat-treated at a temperature of 160°C for 5 hours (16 hours in the case of fluoro rubber) under a pressure of 0 to 2 kg/cm ² to form various sheets with a thickness of 0.9 to 1.1 mm. A rubber sheet was obtained. Table 8 shows the type of rubber; the type and amount of compounding agents; the hardness and tensile strength of the rubber sheets obtained; and the heat-treated sheets obtained by heat-treating each sheet at a temperature of 150°C for 24 hours. Hardness, strength retention and shrinkage were shown. The granular resin in the table is that obtained in Run No. 35 of Reference Example 2.

【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 phenol formaldehyde resin used in the present invention. 1st
The figure also illustrates a method for determining the absorption intensity at a specific wavelength of the peak.

Claims (1)

[Scope of Claims] 1. (a) 100 parts by weight of a rubber-like elastic material, and (b) 200 parts by weight of a granular or powdery resin comprising a condensate of phenols and formaldehyde having the following properties (A) and (B). Below parts by weight, (A) the condensate is (1) substantially composed of carbon, hydrogen, and oxygen atoms; (2) mainly composed of trifunctional residues of methylene groups, methylol groups, and phenols; (3) The trifunctional residue is the 2,
It is bonded to a methylene group at one position at the 4 and 6 positions, and a methylol group and/or a methylene group at at least one other position, and (4) has an absorption peak of 1600 cm ^-1 (absorption peak attributed to benzene). Absorption intensity D ₁₆₀₀ , 990 ~ 1015 cm ^-1
When the largest absorption intensity in the range (absorption peak attributed to the methylol group) is expressed as D _{990 to 1015} , and the absorption intensity in the range 890 m ^-1 (absorption peak of the isolated hydrogen atom of the benzene nucleus) is expressed as D ₈₉₀ , D _990-1015 /D ₁₆₀₀ =0.2-9.0D ₈₉₀ /D ₁₆₀₀ =
0.09 to 1.0, and (B) the granular or powdered resin has a particle size of 1 to 150
A rubber composition comprising micron spherical primary particles and secondary aggregates. 2. The rubber composition according to claim 1, wherein the rubbery elastic material is uncured natural rubber or synthetic rubber. 3 Uncured synthetic rubber is polybutadiene, polyisoprene, copoly(butadiene-styrene), copoly(butadiene-acrylonitrile), copoly(butadiene-propylene), polyisobutylene,
The composition according to claim 2, which is copoly(isobutylene-isoprene), polychloroprene, polyacrylate rubber, polysulfide, silicone rubber, chlorinated polyethylene, fluororubber, chlorosulfonated polyethylene or polyurethane. 4 The granular or powdered resin is at least 30% of the
The composition according to any one of claims 1 to 3, comprising spherical primary particles having a particle size of 0.1 to 150 microns and secondary aggregates thereof. 5. The composition according to any one of claims 1 to 4, wherein the granular or powdered resin has a _D990-1015 / _D1600 of 0.3-7.0 in an infrared absorption spectrum determined by a KBr tablet method. 6. The composition according to any one of claims 1 to 5, wherein the granular or powdered resin has a D ₈₉₀ /D ₁₆₀₀ of 0.1 to 0.9 in an infrared absorption spectrum determined by the KBr tablet method. 7. The granular or powdered resin is at least 50% of the total
7. The composition according to any one of claims 1 to 6, wherein the weight percent is such that it can pass through a 100-meter mesh sieve. 8. The composition according to any one of claims 1 to 7, wherein the granular or powdered resin has a free phenol content of 500 ppm or less as measured by liquid chromatography. 9 The granular or powdered resin essentially consists of carbon, hydrogen and oxygen as determined by elemental analysis, and has the following composition: C: 70 to 80% by weight, H: 5 to 7% by weight, and O: 17 to 21% by weight. (Total 100% by weight) The composition according to any one of claims 1 to 8. 10 The granular or powdered resin is at least partially fused when held at a temperature of 100°C for 5 minutes according to the thermal fusion measurement method described in the main text. The composition according to any one of items 1 to 9. 11 When 10 g of the granular or powdered resin is heated under reflux in 500 ml of substantially anhydrous methanol, the following formula S = W ₀ - _{W 1} /W ₀ ×100 W ₀ is the granular or powdered resin used. The weight of the resin (g), _W1 is the weight (g) of the granular or powdered resin remaining after heating and refluxing, and S is the methanol solubility (% by weight) of the granular or powdered resin. The composition according to any one of claims 1 to 10, wherein the amount is 20% by weight or more. 12 10 g of the granular or powdered resin was heated at 45°C from room temperature to 115°C in 300 g of an acetylation bath with the following composition: 78% by weight of acetic anhydride, 20% by weight of acetic acid, and 2% by weight of orthophosphoric acid.
When acetylation treatment is performed by gradually heating for 15 minutes and holding at 115℃ for 15 minutes, the following formula: I=W ₁ −W ₀ /W ₀ ×100 (%) W ₀ is the value before acetylation. The weight (g) of the granular or powdered resin, W ₁ is the weight (g) of the granular or powdered resin after acetylation, and I is the acetylation weight increase rate (% by weight) of the granular or powdered resin. 10. The composition according to any one of claims 1 to 9, wherein the acetylation weight increase rate expressed by is 23 to 40% by weight. 13 The granular or powdered resin 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, or Claims 1 to 9 13. The composition according to any one of Item 12. 14. The composition according to any one of claims 1 to 13, wherein the granular or powdered resin is contained in an amount of 3 to 200 parts by weight based on 100 parts by weight of the rubber-like elastic material. 15. The composition according to any one of claims 1 to 14, wherein the granular or powdered resin is contained in an amount of 5 to 150 parts by weight based on 100 parts by weight of the rubber-like elastic material. 16. The composition according to any one of claims 1 to 15, wherein the rubber composition is in a cured form.