JP2009013224A - Non-thermomeltable granular phenolic resin, method for producing the same, thermosetting resin composition, semiconductor sealing material, and semiconductor adhesive - Google Patents

Abstract

Non-thermomelt with high heat resistance, small average particle diameter, low viscosity when used as a sealing material or adhesive, and reduced ionic impurity content A granular phenolic resin, a method for producing the same, a resin composition containing the granular phenolic resin, a semiconductor sealing material and an adhesive using the resin composition are provided.
A non-heat-meltable granular phenol resin having an average particle size of 20 μm or less, a single particle ratio of 0.7 or more, and a chlorine content of 500 ppm or less and a method for producing the same are provided. Preferably, the average particle size is 10 μm or less, and the chlorine content is 100 ppm or less. Moreover, the thermosetting resin composition containing the said granular phenol resin, the sealing material for semiconductors using the said resin composition, and the adhesive agent for semiconductors are provided.
[Selection] Figure 1

Description

  The present invention relates to a non-heat-meltable granular phenol resin and a method for producing the same. The present invention also relates to a thermosetting resin composition containing the non-thermomeltable granular phenol resin, and a semiconductor sealing material and a semiconductor adhesive using the thermosetting resin composition.

  In general, an integrated circuit device such as an IC (Integrated Circuit) and a memory includes a semiconductor element, an insulating support substrate, a lead frame, a lead, and the like. In order to seal and bond them, a sealing material or an adhesive is used. Is used. Conventionally, it has been the mainstream to use a resin composition containing an inorganic filler such as spherical silica, an epoxy resin, and a curing agent for such a sealing material or adhesive.

  However, in recent years, sealing materials and adhesives are applicable to 1) increase in soldering temperature due to the transition to lead-free solder and application to electronic components that require high-temperature operation guarantee such as in-vehicle electronic components. Therefore, in order to cope with further miniaturization of the internal wiring of the integrated circuit, the miniaturization of the filler in the sealing material and the adhesive, the sealing material and the adhesive However, it has been difficult to satisfy both of these new required characteristics with the conventional blending.

  That is, the epoxy resin that is an organic substance and the spherical silica that is an inorganic substance (fused silica) differ greatly in the linear expansion coefficient. Deterioration such as stress is generated at the interface and cracks are a problem.

  Patent Document 1 describes that an amino-based silane coupling agent that acts on the silica surface is blended in the semiconductor sealing composition in order to improve the mechanical properties of the cured product. However, since the heat resistance of the silane coupling agent itself is low, the heat resistance of the sealing material is also relatively low depending on the heat resistance of the silane coupling agent.

  As one means for eliminating the occurrence of stress at the interface between the epoxy resin and the spherical silica, it is conceivable to use an organic filler that is an organic substance instead of an inorganic filler such as spherical silica. This is because the difference in the linear expansion coefficient with the epoxy resin is reduced by using the organic filler. For example, Patent Documents 2 to 4 describe that an organic filler can be used for a semiconductor sealing material or a semiconductor adhesive. However, no specific organic filler having the required characteristics has been proposed.

  By the way, a phenol resin is a material excellent in heat resistance, mechanical performance, and electrical characteristics, and is used as various industrial materials such as for electronic materials. If the hardened | cured material of a phenol resin can be used as an organic filler, the favorable characteristic which the said phenol resin has can be provided to the sealing material for semiconductors and an adhesive agent.

  However, a phenolic resin cured product that has high heat resistance and realizes fine resin particles and low viscosity when used as a sealing material or an adhesive has not been proposed so far. In addition, as an organic filler used for a semiconductor sealing material and a semiconductor adhesive, it is desired that the ionic impurity content, particularly the halogen ion content, is small. In the first place, a phenol resin is an ionic catalyst in an aqueous medium. Since it is usually polymerized, it is difficult to obtain a cured phenol resin in which the ionic impurity content is reduced to a level applicable to semiconductor applications.

Patent Documents 5 and 6 describe a phenol resin in which ionic impurities are reduced by a specific cleaning treatment, and it is stated that the phenol resin is useful for applications such as a semiconductor sealing material. . However, the phenol resins described in these documents are uncured and are not used as organic fillers. Moreover, the washing | cleaning method described in these literature cannot be used for the removal of the ionic impurity in phenol resin hardened | cured material.
Japanese Patent Laid-Open No. 11-172077 JP 2000-269247 A JP 2002-226824 A JP 2004-168848 A Japanese Patent Laid-Open No. 10-60068 Japanese Patent Laid-Open No. 2-245011

  The present invention has been made in view of such a situation, and the object thereof is to have high heat resistance and a small average particle diameter, and a low viscosity when used as a sealing material or an adhesive. It is an object of the present invention to provide a non-heat-meltable granular phenol resin having a reduced ionic impurity content and a method for producing the same. Another object of the present invention is to use a resin composition containing a non-heat-meltable granular phenol resin having high heat resistance and low viscosity and having a reduced ionic impurity content, and the resin composition. The present invention provides a semiconductor sealing material and a semiconductor adhesive.

  As a result of diligent research, the present inventors have found that the phenol resin composition containing a granular phenol resin has a sufficiently small average particle diameter of the granular phenol resin and agglomeration of the particles in order to achieve low viscosity. It has been found that the secondary agglomerate content by is required to be small. Further, it has been found that the granular phenol resin cured product may be washed with alcohols and / or an alkaline aqueous solution in order to reduce the ionic impurities, particularly the halogen ion content, of the granular phenol resin cured product. That is, the present invention is as follows.

  The non-heat-meltable granular phenol resin of the present invention is characterized by an average particle size of 20 μm or less, a single particle ratio of 0.7 or more, and a chlorine content of 500 ppm or less. The average particle size is preferably 10 μm or less. Moreover, it is preferable that chlorine content is 100 ppm or less. The definitions of the terms “non-thermal meltability”, “average particle diameter” and “single particle ratio” will be described later.

  In the non-heat-meltable granular phenol resin of the present invention, the variation coefficient of the particle size distribution represented by the following formula [1] is preferably 0.65 or less.

Coefficient of variation of particle size distribution = (d _84% −d _16% ) / (2 × average particle size) [1]
Here, d _84% and d _16% are particle diameters showing cumulative frequencies of 84% and 16%, respectively, in the frequency distribution obtained by the laser diffraction / scattering method.

  Moreover, in the non-heat-meltable granular phenol resin of this invention, it is preferable that the sphericity of particle | grains is 0.5 or more. Furthermore, the free phenol content is preferably 500 ppm or less. The definitions of the terms “sphericity” and “free phenol content” will be described later.

  In the present invention, (1) aldehydes and phenols are reacted in an aqueous medium in the presence of hydrochloric acid and a protective colloid agent as an acidic catalyst having a molar concentration of 2.0 mol / L or more in the reaction solution. A granular phenol resin forming step for forming a granular phenol resin, and (2) a non-thermal melting step for heating the reaction solution containing the granular phenol resin to form a non-heat-meltable granular phenol resin. (3) separating the non-heat-meltable granular phenol resin from the reaction solution; and (4) one or more kinds selected from alcohols and alkaline aqueous solutions. And a washing step of washing with a liquid medium. A method for producing a non-heat-meltable granular phenol resin is provided.

  The washing using alcohol in the washing step is preferably performed at a temperature equal to or higher than the glass transition temperature of the non-heat-meltable granular phenol resin.

  The aldehydes are preferably formaldehyde, paraformaldehyde or a mixture thereof.

  The molar ratio of the phenols to the aldehydes is preferably 0.9 or less. The protective colloid agent is preferably a water-soluble polysaccharide derivative.

  Furthermore, this invention provides the non-heat-meltable granular phenol resin obtained using any one of the above methods.

  Here, the average particle diameter of the non-heat-meltable granular phenol resin obtained by using any of the above methods is 20 μm or less, the single particle ratio is 0.7 or more, and the chlorine content is 500 ppm or less. It is preferable. More preferably, the average particle size is 10 μm or less. The chlorine content is more preferably 100 ppm or less.

  In the non-heat-meltable granular phenol resin obtained by any of the above methods, the coefficient of variation of the particle size distribution represented by the above formula [1] is preferably 0.65 or less. The sphericity of the particles is preferably 0.5 or more. The free phenol content is preferably 500 ppm or less.

  Furthermore, this invention provides the thermosetting resin composition characterized by containing the non-heat-meltable granular phenol resin in any one of the said, an epoxy resin, and a hardening | curing agent. The thermosetting resin composition of the present invention may further contain an inorganic filler.

  Furthermore, this invention provides the sealing material for semiconductors which consists of the said thermosetting resin composition, and the adhesive agent for semiconductors.

  According to the present invention, the average particle diameter is 20 μm or less, the particle diameter is very small, and there are hardly any secondary aggregates due to the aggregation of the minute primary particles, and the chloride ion content is greatly increased. A non-heat-meltable granular phenolic resin is provided. Such a non-heat-meltable granular phenol resin of the present invention can be suitably used as an additive for materials in various industrial fields such as molding materials, paints, refractories, papermaking, friction materials, grindstones, and adhesives. . In particular, a thermosetting resin composition using the non-heat-meltable granular phenol resin as an organic filler is extremely useful as a semiconductor sealing material and a semiconductor adhesive.

  Moreover, this invention provides the manufacturing method suitable for manufacturing the non-heat-meltable granular phenol resin which has the above outstanding characteristics especially as a semiconductor use. According to the method for producing a non-heat-meltable granular phenol resin of the present invention, it is possible to produce a non-heat-meltable granular phenol resin having a reduced chloride ion content by a relatively simple method. The non-heat-meltable granular phenol resin obtained by the method can be suitably used as an organic filler for semiconductor sealing materials and semiconductor adhesives.

<Non-heat-melting granular phenolic resin>
The non-heat-meltable granular phenol resin of the present invention is a non-heat-meltable phenol resin comprising a reaction product of phenols and aldehydes, and is a particle (as a term for secondary aggregates, both primary particles and The average particle size is 20 μm or less, and the single particle ratio serving as an index for the content of secondary aggregates is 0.7 or more. Thus, when the average particle diameter of the phenol resin particles is 20 μm or less, preferably 10 μm or less, and the single particle ratio is 0.7 or more, for example, when the granular phenol resin is used as an organic filler, a higher filling rate In addition, the filling material such as a resin composition filled with the granular phenolic resin has a lower viscosity than the conventional one, and thus is easy to handle. Such a reduction in viscosity of the resin composition is in line with the required characteristics of a sealing material and an adhesive that are recently required in the semiconductor field. Such a non-heat-meltable granular phenolic resin of the present invention can be applied not only for the above-mentioned use but also for a wide range of industrial fields such as molding materials, paints, refractories, papermaking, friction materials, and grindstones. In addition, although the method of grind | pulverizing the hardened phenol resin can be mentioned as a method of obtaining the fine powder of a non-heat-meltable phenol resin, In this method, the shape is indefinite and a granular material with sufficient filling property is obtained. It is not possible.

  The non-heat-meltable granular phenol resin of the present invention will be described in more detail. The non-heat-meltable granular phenol resin of the present invention is a non-heat-meltable phenol resin made of a reaction product of phenols and aldehydes. Here, the reaction product of phenols and aldehydes is basically a product obtained by an addition reaction and a condensation reaction, but also includes a product that has undergone only an addition reaction. . Although it does not specifically limit as phenols, For example, phenol, naphthol, hydroquinone, resorcin, xylenol, pyrogallol etc. can be mentioned. One type of phenol may be used, or two or more types may be used in combination. Especially, when the balance of the performance and cost of the phenol resin obtained is considered, it is preferable that phenols are phenol. The aldehydes are not particularly limited, and examples thereof include formaldehyde, paraformaldehyde, glyoxal, and benzaldehyde. The aldehydes may be used alone or in combination of two or more. Especially, it is preferable that aldehydes are formaldehyde, paraformaldehyde, or these mixtures.

  Here, in the present specification, “non-heat-meltable” means that the granular phenol resin does not fuse under a specific high-temperature pressurization condition. When 5 g is inserted between two 0.2 mm thick stainless steel plates and pre-heated to 100 ° C. and pressed with a total load of 50 kg for 2 minutes, granular phenol is melted and / or fused. It is defined as the property that the resin forms a flat plate, the phenol resin particles are deformed, or the phenol resin particles do not adhere to each other. Such properties can be imparted in the production of a granular phenol resin by synthesizing a phenol resin by a reaction between phenols and aldehydes, and then crosslinking and curing the phenol resin. Crosslinking / curing can be performed, for example, by heating a reaction solution obtained by reacting phenols with aldehydes.

  The boiling methanol solubility of the non-heat-meltable granular phenolic resin of the present invention is preferably less than 30%, more preferably less than 20%. In the present specification, “boiling methanol solubility” means the content of the boiling methanol-soluble component in the granular phenol resin, and is specifically defined as a value calculated by the following test. Specifically, about 10 g of a phenol resin sample was precisely weighed and heated under reflux in about 500 mL of substantially anhydrous methanol for 30 minutes. Filter through 3 glass filter and wash the residue on the glass filter with about 100 mL of anhydrous methanol. Next, the residue on the glass filter after washing is dried at 40 ° C. for 5 hours, and then the residue is precisely weighed. The value calculated by the following formula [2] is defined as “boiling methanol solubility”.

Boiling methanol solubility (% by weight) = (difference between phenol resin sample weight and residue weight after drying) / (phenol resin sample weight) × 100 [2]
“Boiled methanol solubility” is not a direct criterion for determining whether or not the phenol resin has “non-heat meltability”, but can be an index for knowing the degree of heat meltability of the phenol resin. Is. That is, the lower the “solubility of boiling methanol”, the lower the heat melting property. When the boiling methanol solubility is 30% or more, there are cases where the particles exhibit deformation or fusion due to heat melting due to heating or pressurization during use.

  As described above, the average particle diameter of the particles (primary particles) constituting the non-heat-meltable granular phenol resin of the present invention is 20 μm or less, preferably 10 μm or less. By setting the average particle size to 10 μm or less, it is possible to further improve the filling property and low viscosity when the granular phenol resin of the present invention is applied to an organic filler or the like. Here, in this specification, the “average particle diameter” means a measurement method using a laser diffraction particle size measuring machine, that is, a cumulative frequency of 50% obtained by a laser diffraction / scattering method (microtrack method). Mean value. As a laser diffraction particle size measuring instrument, Microtrac X100 manufactured by Nikkiso Co., Ltd. can be suitably used.

  When the average particle size of the non-heat-meltable phenol resin particles exceeds 20 μm, the chlorine content may not be sufficiently reduced depending on the method for producing the non-heat-meltable granular phenol resin of the present invention described later. Also in this sense, the average particle size of the non-heat-meltable phenol resin particles is preferably 20 μm or less, and more preferably 10 μm or less.

  Moreover, the single particle ratio of the non-heat-meltable granular phenol resin of the present invention is 0.7 or more, preferably 0.8 or more. When the single particle ratio is less than 0.7, the filling property and the low viscosity property when applied as an organic filler such as a semiconductor sealing material and a semiconductor adhesive tend to be insufficient. Here, in this specification, “single particles” means primary particles that do not form secondary aggregates due to aggregation, and “single particle ratio” means that granular phenol resin is dispersed in water droplets. The ratio of the total number of primary particles and the number of single particles in a randomly selected visual field including about 300 primary particles is counted, that is, the number of single particles / 1. It means the total number of secondary particles.

The chlorine content of the non-heat-meltable granular phenol resin of the present invention is 500 ppm or less. In the semiconductor field, non-halogenated electronic materials are required from the viewpoint of safety for the environment and health, and a lower chlorine content is preferable. If the chlorine content exceeds 500 ppm, it will affect the dielectric constant of the resin composition containing the non-heat-meltable granular phenolic resin, or lead to corrosion of lead wires, etc. It will not meet the required characteristics. The chlorine content is preferably 100 ppm or less. With such a content, the chlorine content can be suitably used for a semiconductor sealing material and a semiconductor adhesive. Here, “chlorine content” in the present specification is a chlorine content calculated from the following measurement method.
Measuring device: X-ray fluorescence analyzer ZSX100E manufactured by Rigaku Corporation
Measurement method: After pressurizing a measurement sample (non-thermomeltable phenol resin particles) and a measurement binder powder into a measurement pellet, fluorescent X-ray analysis is performed in the EZ scan mode using the above measurement apparatus. The measured value of the diffraction intensity of the chlorine Kα ray is normalized by the estimated molecular formula (C ₇ H ₆ O ₁ ) of the cured phenol resin to obtain the chlorine content (wt / wt). Note that the measurement target of the fluorescent X-ray measurement includes not only chlorine ions but also chlorine atoms such as organic chlorine compounds. For example, when a non-heat-meltable phenol resin is produced using the method of the present invention described later, Since there is no intentional addition of an organic chlorine compound, it can be said that the chlorine content obtained by fluorescent X-ray measurement is substantially equal to the chlorine ion content.

  Moreover, it is preferable that the non-heat-meltable granular phenol resin of this invention has a narrow particle size distribution. Specifically, it is preferable that the variation coefficient of the particle size distribution of the particles (primary particles) constituting the non-heat-meltable granular phenol resin of the present invention is 0.65 or less. The variation coefficient of the particle size distribution is more preferably 0.6 or less. In the present specification, the “coefficient of variation in particle size distribution” is a value calculated by the following equation [1].

Coefficient of variation of particle size distribution = (d _84% −d _16% ) / (2 × average particle size) [1]
Here, in the above formula [1], d _84% and d _16% are particle diameters showing cumulative frequencies of 84% and 16% in the frequency distribution obtained by the laser diffraction / scattering method, respectively. Is the average particle size defined above. By making the coefficient of variation of the particle size distribution 0.65 or less, for example, it is possible to further improve the filling property and low viscosity when used as an organic filler for a semiconductor sealing material or a semiconductor adhesive, Provided is a granular phenolic resin applicable to a wide range of industrial fields such as molding materials, paints, refractories, papermaking, friction materials, and grindstones. As a laser diffraction particle size measuring instrument, Microtrac X100 manufactured by Nikkiso Co., Ltd. can be suitably used.

  In order to improve the performance of a semiconductor sealing material or the like, it is preferable to improve the filling rate of the filler filled in the binder resin. Examples of a method for increasing the filling rate of the spherical filler include a method of blending fillers having different particle sizes. That is, it is a method of blending and designing so that the smaller filler just enters the closest packing gap of the larger filler. For example, conventionally, fused silica is usually used as a filler for sealants, but in order to increase the filling rate, it is performed to use fused silica having different average particle diameters. . In applying such a method, a filler having a desired average particle size and a narrow particle size distribution is required. According to this invention, the organic filler for semiconductor sealing materials applicable also to such a compounding design can be provided. Furthermore, in a specific field such as an adhesive used for adhering an IC chip to a substrate, for example, a small amount of filler having a large particle size exists even if the average particle size is small (that is, the particle size distribution is wide). However, there are fields in which the thickness of the adhesive layer is adversely affected and is difficult to use. According to the present invention, it is possible to provide a non-heat-meltable granular phenol resin that can be suitably applied in such fields.

  Furthermore, the particle shape of the non-heat-meltable granular phenol resin of the present invention is preferably as close to a true sphere as possible. Specifically, the sphericity is preferably 0.5 or more, more preferably 0.7 or more, and particularly preferably 0.9 or more. The closer the particle shape is to a true sphere, that is, the closer the sphericity is to 1.0, the further improvement in filling properties and low viscosity when used as an organic filler for semiconductor sealing materials and semiconductor adhesives, for example. A granular phenol resin that can be applied to a wide range of industrial fields such as molding materials, paints, refractories, papermaking, friction materials, and grindstones is provided. In this specification, “sphericity” means a field of view containing about 300 primary particles in an optical microscope observation, and an aspect ratio (that is, a ratio of minor axis / major axis) is determined. It means the average value of these 10 aspect ratios when 10 lowest primary particles are selected and the aspect ratio in the projected cross section is measured for each of these 10 primary particles.

  Furthermore, it is preferable that the free phenol content of the non-heat-meltable granular phenol resin of the present invention is 500 ppm or less. The free phenol content is more preferably 300 ppm or less, still more preferably 200 ppm or less. By setting the free phenol content to 500 ppm or less, the safety when handling the phenol resin and the safety of the product when the phenol resin is applied to various products (for example, sealing materials, adhesives) can be improved. . Here, in this specification, “free phenol content” is defined as a value calculated by the following test. That is, about 10 g of a phenol resin sample is precisely weighed, extracted in 190 mL of methanol under reflux for 30 minutes, and filtered through a glass filter. The concentration of phenols in the filtrate is quantified by liquid chromatography, and the weight of phenols in the filtrate is calculated. The ratio between the phenol weight and the sample weight, that is, the phenol weight / phenol resin sample weight is defined as “free phenol content”.

  Although the method for manufacturing the non-heat-meltable granular phenol resin having the above excellent characteristics is not particularly limited, the following method can be preferably used. The manufacturing method of the non-heat-meltable granular phenol resin shown below is also included in the present invention.

<Method for producing non-heat-meltable granular phenolic resin>
The manufacturing method of the non-heat-meltable granular phenol resin of this invention is characterized by including process (1)-(4) shown next. Hereinafter, each step will be described in detail.
(1) A granular phenol resin is formed by reacting an aldehyde and a phenol in an aqueous medium in the presence of an acidic catalyst and a protective colloid agent having a molar concentration of 2.0 mol / L or more in the reaction solution. Granular phenol resin formation process,
(2) A non-thermal melting step of heating the reaction solution containing the granular phenol resin to form a non-heat-meltable granular phenol resin,
(3) a separation step of separating the non-heat-meltable granular phenol resin from the reaction solution; and
(4) A cleaning step of cleaning the non-heat-meltable granular phenol resin using one or more liquid media selected from alcohols and alkaline aqueous solutions.

(1) Granular phenol resin formation process In this process, granular phenol resin is formed by making aldehydes and phenols react in an aqueous medium in presence of an acidic catalyst and a protective colloid agent. The aldehydes are not particularly limited, and examples thereof include formaldehyde, paraformaldehyde, glyoxal, and benzaldehyde. The aldehydes may be used alone or in combination of two or more. Especially, it is preferable that aldehydes are formaldehyde, paraformaldehyde, or these mixtures. As will be described later, one of the features of the method of the present invention is that a high concentration acidic catalyst is used. However, when paraformaldehyde, which is a polymer of formaldehyde, is used as the aldehyde, such a condition is used. Underneath, paraaldehyde is depolymerized, so it is believed that formaldehyde contributes substantially to the reaction. The type of aldehydes used and the amount used are preferably selected so as to dissolve in an aqueous medium during the reaction.

  Although it does not specifically limit as phenols, For example, phenol, naphthol, hydroquinone, resorcin, xylenol, pyrogallol etc. can be mentioned. One type of phenol may be used, or two or more types may be used in combination. Among these, considering the solubility in water and the balance between the performance and cost of the resulting phenol resin, the phenol is preferably phenol. The type of phenols to be used and the amount used are preferably selected so as to dissolve in an aqueous medium during the reaction.

  Specifically, for example, when phenol or the like is used as the phenol, the amount of phenol used (amount charged) is such that the concentration (weight ratio) of the phenol with respect to the total weight of the reaction solution is 10% by weight or less. Preferably it is selected. When phenols with lower water solubility (for example, naphthol) are used, they are guaranteed to dissolve in an aqueous medium during the reaction and have excellent characteristics (fine average particle size and high single particle) It is desirable to employ a lower concentration in order to express the rate). Here, the “total weight of the reaction solution” is the total weight of phenols, aldehydes, acidic catalyst, protective colloid agent and aqueous medium. By setting the concentration of phenols to 10% by weight or less based on the total weight of the reaction solution, temperature control from the reaction start stage to the granular phenol resin formation stage can be easily performed. For example, in the case of starting the reaction at around room temperature, if the concentration of phenols is 10% by weight or less, there is no excessive heat generation due to a runaway reaction or the like particularly in the initial stage of the reaction. A granular phenol resin having a small average particle size and suppressed secondary aggregation can be formed. In addition, although it is possible to make the density | concentration (weight ratio) of phenols with respect to the reaction liquid total weight higher than 10 weight%, in that case, it is often necessary to perform temperature management at the time of reaction appropriately.

  Moreover, it is preferable that the usage-amount (preparation amount) of the said aldehydes is selected so that the molar ratio of the phenols with respect to aldehydes may be 0.9 or less. The charging molar ratio of phenols to aldehydes is more preferably 0.75 or less, and further preferably 0.5 or less. By setting the molar ratio of phenols to aldehydes to 0.9 or less, the average particle size is small, secondary agglomeration is suppressed, and closer to a true sphere, the particle size distribution is narrow, and the free phenol content is reduced. A small amount of granular phenol resin can be formed. Moreover, secondary aggregation can be further suppressed by setting the charged molar ratio of phenols to aldehydes to 0.75 or less. In order to further improve the characteristics relating to these granular phenol resins, it is particularly preferable to set the molar ratio of phenols to aldehydes to 0.5 or less. There is no particular limitation on the lower limit of the molar charge ratio of phenols to aldehydes. For example, the molar charge ratio of phenols to aldehydes can be reduced by increasing the aldehydes within a range that dissolves in an aqueous medium. However, considering the use efficiency of the raw material, the molar ratio of the phenols to the aldehydes is preferably 0.1 or more.

  In this step, the aldehydes and phenols as described above are reacted in an aqueous medium. One of the characteristics of the production method of the present invention is that the reaction is performed using a high concentration acidic catalyst. . In the present invention, hydrochloric acid is used as the acidic catalyst. In the condensation reaction between aldehydes and phenols, for example, other strongly acidic catalysts such as phosphoric acid and sulfuric acid can be used. However, hydrochloric acid is easier to remove than phosphoric acid, sulfuric acid, etc. There is little worry about side reactions. In the present invention, the term “high concentration” specifically means that the molar concentration of hydrochloric acid in the reaction solution is 2.0 mol / L or more when the reaction is started near room temperature, and is more preferable. Is 3 mol / L or more. “Molar concentration of hydrochloric acid in the reaction solution” means the concentration of hydrogen chloride in the reaction solution. In order to obtain a granular phenol resin having a small average particle size and reduced secondary agglomeration, and a granular phenol resin having a particle size distribution close to that of a spherical shape and a small free phenol content. When starting near normal temperature, it is necessary to make the molar concentration of hydrochloric acid in the reaction solution 2.0 mol / L or more. Moreover, from the viewpoint of the reaction rate suitable for industrial production and the acid resistance of incidental equipment, the molar concentration of hydrochloric acid is preferably 6 mol / L or less. In addition, by raising the reaction start temperature from room temperature, the molar concentration of hydrochloric acid necessary to achieve the same reaction rate is slightly lower than when the reaction start temperature is near room temperature.

  Another feature of the production method of the present invention is that the reaction between aldehydes and phenols is carried out in the presence of a protective colloid agent. Here, the protective colloid agent contributes to the formation of a granular phenol resin. In order to form a granular phenol resin having a small average particle size and reduced secondary agglomeration, and also a granular phenol resin that is closer to a true sphere, has a narrow particle size distribution, and has a low free phenol content. It is necessary to use such protective colloid agents. In the present invention, it is preferable to use a water-soluble protective colloid agent as the protective colloid agent. As the water-soluble protective colloid agent, for example, a water-soluble polysaccharide derivative can be preferably used. Specific examples of water-soluble polysaccharide derivatives that can be suitably used include alkali metal salts or ammonium salts of carboxymethyl cellulose; water-soluble polysaccharide derivatives such as gum arabic, acacia, guar gum, locust bean gum and the like as main components. Natural glue. When the alkali metal salt or ammonium salt of carboxymethyl cellulose is used, the degree of carboxymethylation of cellulose is not particularly limited, but those having a degree of carboxymethylation of about 75% are commercially available. Can be used. When the protective colloid agent is obtained as a dry powder, it may be directly added to and dissolved in the reaction solution, or an aqueous solution of the protective colloid agent may be prepared in advance and added to the reaction solution. Good.

  Although the usage-amount of the said protective colloid agent is not restrict | limited in particular, It is preferable that it is 0.01 to 1 weight% of the usage-amount of the said phenols by solid content weight. When the amount of the protective colloid agent used is less than 0.01% by weight, it is insufficient to make the average particle size of the phenol resin particles 20 μm or less. For example, other parameters such as the amount of phenols used and the stirring speed Grain size control is required. In order to make the average particle size of the phenol resin particles 10 μm or less, the amount of the protective colloid agent used is preferably 0.04% by weight or more of the amount of phenols used. In addition, when the amount of the protective colloid agent used is more than 1% by weight of the amount of the phenols used, phenol resin particles having an average particle size of 10 μm or less can be obtained. Even if it is added, there is a tendency that an effect commensurate with it cannot be obtained. On the other hand, due to the increase in viscosity of the reaction solution, the separation rate tends to decrease in the separation step described later. Here, it should be noted that when the amount of the protective colloid agent used is within the above range, that is, 0.02 to 1% by weight of the amount of phenols used, the average particle size of the phenol resin particles is determined as the protective colloid agent. It can be controlled by adjusting the amount of use.

  Examples of the aqueous medium include water or a mixed solvent of water and a water-soluble organic solvent. In the present invention, an aqueous solvent is preferably used. The amount of the aqueous medium used is selected so that the concentration of hydrochloric acid is within the above range, and preferably the concentration of phenols is further within the above preferable range.

  Next, a specific method for carrying out the reaction using the aldehydes, phenols, acidic catalyst and protective colloid agent will be described. Specific examples of the reaction include the following two methods. (I) a method in which hydrochloric acid, a protective colloid agent and aldehydes are mixed in an aqueous medium to prepare a mixed solution, and then a phenol is added while stirring the mixed solution; (ii) a protective colloid agent in the aqueous medium A method of preparing a mixed solution by mixing aldehydes and phenols and then adding hydrochloric acid while stirring the mixed solution.

  Here, in any of the methods (i) and (ii), the mixed solution is preferably a substantially uniform solution. That is, it is preferable that the solute mixed in the aqueous medium is completely dissolved or at least almost completely dissolved. In the preparation of the mixed solution, the order of mixing is not particularly limited. The temperature at the start of the reaction of the mixed solution is not particularly limited, but is preferably about 10 to 50 ° C, more preferably about 20 to 40 ° C.

  In the method (i), the reaction between the aldehyde and the phenol is carried out by adding the phenol while stirring the mixed solution. The phenols may be added by adding the phenols directly to the mixed solution, or the phenols may be dissolved in water in advance and the aqueous solution added to the mixed solution. The reaction is preferably controlled so that the reaction temperature is about 10 to 60 ° C, preferably about 20 to 50 ° C. When the reaction temperature is less than about 10 ° C., the reaction rate tends to be low, and when the reaction temperature exceeds 60 ° C., there is a possibility that the particle size becomes coarse and secondary aggregates increase. The temperature at the start of the reaction of the mixed solution is about 20 to 30 ° C. and the concentration of phenols is 10% by weight or less with respect to the total weight of the reaction solution. The reaction can be carried out in the preferred temperature range with little management.

  In the method (ii), the reaction between the aldehyde and the phenol is performed by adding hydrochloric acid while stirring the mixed solution. The addition of hydrochloric acid may be performed at once, or may be performed dropwise over a certain period of time. Further, hydrochloric acid may be added by adding concentrated hydrochloric acid directly to the mixed solution, or concentrated hydrochloric acid may be diluted with water and the diluted solution may be added to the mixed solution. The reaction temperature is preferably controlled to be about 10 to 60 ° C., preferably about 20 to 50 ° C., as in the case of (i) above.

  In any of the above methods (i) and (ii), as the reaction proceeds, the reaction solution gradually becomes clouded (suspended) and a granular phenol resin is formed. Typically, this occurs several tens of seconds to several minutes after the addition of phenols or hydrochloric acid. The time required for whitening, that is, precipitation of phenol resin particles, tends to be shorter in the method (ii) than in the method (i). Further, after the white turbidity, the reaction solution typically exhibits a light pink color to a deep pink color. In the present invention, it is preferable to continue the reaction until such coloring is observed. The time until coloring after clouding is generally several tens of minutes to several hours. For example, in the method described in Japanese Patent Application Laid-Open No. 57-177011, it was necessary to stop the stirring after the precipitation of the phenol resin particles in order to prevent the particles from collecting and forming a bowl-like shape. According to the production method of the present invention using a colloid agent, stirring can be continued as it is even after precipitation of phenol resin particles. Therefore, according to the production method of the present invention, the temperature of the reaction solution can be controlled more strictly, and therefore, the polymerization degree and the crosslinking degree of the phenol resin are uniform, and the next non-thermal melting step is provided. Is possible. This can contribute to the homogeneity of the finally obtained granular phenolic resin.

(2) Non-thermal melting step In this step, the granular phenol resin is made non-heat-meltable by heating the reaction liquid containing the granular phenol resin. Such non-heat melting property is brought about by crosslinking and curing of the resin by heating. The heating temperature of the reaction liquid in this step is preferably 60 ° C. or higher, more preferably 70 ° C. or higher. Moreover, the heating temperature of the reaction solution is preferably 100 ° C. or lower, more preferably 90 ° C. or lower. When the heating temperature is less than 60 ° C., there is a possibility that sufficient non-thermal meltability cannot be obtained. In addition, sufficient non-thermal meltability here means having "non-heat meltability" defined above. Moreover, when heating temperature exceeds 100 degreeC, there exists a possibility that the reactor which has a capacitor | condenser may be required, or acid resistance, such as incidental equipment, may become a problem. Even when the heating temperature is as relatively low as about 60 ° C., it is possible to impart sufficient non-thermal meltability by providing a sufficient holding time. By adjusting the heating temperature and the heating time within the above preferred ranges, the degree of polymerization and the degree of crosslinking can be adjusted according to the intended use.

  The heating time is not particularly limited as long as sufficient non-thermal meltability can be imparted to the granular phenol resin, and is typically about several minutes to several hours although it depends on the heating temperature. In addition, after proceeding to the next step after the completion of the heat treatment, the reaction solution may be cooled to an appropriate temperature, or may proceed directly to the next step without cooling the reaction solution.

(3) Separation step In this step, the obtained non-heat-meltable granular phenol resin is separated from the reaction solution. As the separation method, for example, filtration or pressing can be suitably used. As a device for such a separation operation, for example, a filtration device, a centrifugal dehydrator, a belt press, a filter press, or the like can be used. Separation methods using evaporation such as distillation under reduced pressure or spray drying are not preferred because the reaction solution contains high-concentration hydrochloric acid, which may damage the equipment. When performing the separation operation by filtration, various filter aids such as diatomaceous earth and flocculants may be used. Note that the granular phenol resin of the present invention has a specific gravity of about 1.2 to 1.3 and settles upon standing, so that a preliminary operation such as decantation may be performed prior to the separation operation.

(4) Washing step Next, the separated granular phenol resin is washed with alcohols and / or an alkaline aqueous solution. By this washing operation, chlorine ions that have permeated into the phenol resin by the reaction can be extracted and separated. In order to perform this operation efficiently, washing with water for washing away the reaction solution on the surface of the phenol resin or an operation of neutralizing chlorine ions on the surface of the phenol resin with an alkaline aqueous solution may be used in combination. In the present invention, the cleaning solvent (cleaning liquid medium) used in the cleaning step may be either an alcohol or an alkaline solution, or both. Washing with alcohols and / or an alkaline aqueous solution can effectively reduce the chloride ion content in the non-heat-meltable granular phenol resin. According to the cleaning method of the present invention, the chlorine content in the non-heat-meltable granular phenol resin can be 500 ppm or less, 100 ppm or less, or even lower.

  Here, it should be noted that the chlorine ion content in the non-heat-meltable granular phenol resin can be reduced by washing with the alcohol and / or alkaline aqueous solution. This is because the particle size is sufficiently small and the single particle ratio is high. That is, when the non-heat-meltable granular phenol resin has a large average particle size or a low single particle ratio, it is difficult to reduce the chlorine content even by washing with alcohols and / or an alkaline aqueous solution. is there. Therefore, also in this respect, the present invention requires that the non-heat-meltable granular phenol resin has an average particle diameter of 20 μm or less and a single particle ratio of 0.7 or more.

  Next, a specific method of cleaning will be described. As a suitable example of the washing method, there can be mentioned a method in which the non-heat-meltable granular phenol resin separated from the reaction liquid is dispersed in a washing solvent (washing liquid medium) and stirred for a certain time. Prior to washing with an alcohol and / or an alkaline aqueous solution, the non-heat-meltable granular phenol resin separated from the reaction solution may be pre-washed with water or the like in advance. Examples of the preliminary washing method include a method in which the non-heat-meltable granular phenol resin separated from the reaction solution is dispersed in a liquid medium such as water and stirred at a temperature of room temperature to less than 100 ° C. More preferably, heated water is used for the preliminary cleaning. However, although the chlorine content can be reduced to some extent by this preliminary cleaning, it is impossible to reduce it to 500 ppm or less only by the preliminary cleaning, or it takes a very long time to achieve 500 ppm or less. Therefore, in order to sufficiently reduce the chlorine content, cleaning with the alcohol and / or alkaline aqueous solution according to the present invention is required.

  Alcohols are not particularly limited. For example, methanol, ethanol, n-propyl alcohol, isopropyl alcohol, n-butyl alcohol, isobutyl alcohol, s-butyl alcohol, t-butyl alcohol, ethylene glycol, diethylene glycol, triethylene glycol And propylene glycol. As will be described later, the glass transition temperature of the non-heat-meltable granular phenol resin according to the present invention is about 80 to 200 ° C., and when an extraction operation with alcohols is performed in a region exceeding this temperature, the extraction speed is remarkably increased. Rise. When extracting the chlorine content in such a preferable temperature range using low boiling alcohols, it is necessary to use an autoclave or the like. When alcohols with a high boiling point are used, it is possible to carry out the extraction operation in the above preferred temperature range at normal pressure, but the drying operation after washing (extraction) can be complicated. Considering such points, among the exemplified alcohols, ethylene glycol has a good balance of boiling points with respect to the glass transition temperature of the non-heat-meltable phenol resin, and the washing (extraction) operation and the drying operation are simple, It can be preferably used. In addition, only 1 type may be used for alcohols and it may use 2 or more types together.

  The amount of alcohol used is not particularly limited, and can be, for example, 200 parts by weight or more with respect to 100 parts by weight of the solid content of the non-heat-meltable granular phenol resin separated from the reaction solution.

  The washing temperature in the washing treatment using alcohols is preferably equal to or higher than the glass transition temperature of the non-heat-meltable granular phenol resin, and more preferably exceeds the glass transition temperature. By washing at a temperature equal to or higher than the glass transition temperature, the non-heat-meltable granular phenol resin becomes a rubbery state, so that the chlorine content (particularly chlorine ions) contained in the granular phenol resin is effectively reduced to alcohols. Can be extracted. The upper limit of the washing temperature is not particularly limited, but is preferably 250 ° C. or lower in order to avoid thermal decomposition of the non-heat-meltable granular phenol resin and alcohols. In addition, the glass transition temperature of the non-heat-meltable granular phenol resin according to the present invention is usually about 80 to 200 ° C.

  The pressure conditions during the cleaning with alcohol are not particularly limited, and the cleaning can be performed under normal pressure or under pressure. For example, when a relatively low boiling alcohol is used, the washing can be performed under pressure so that the washing temperature is equal to or higher than the glass transition temperature of the non-heat-meltable granular phenol resin. Moreover, the washing time, that is, the stirring time of the non-heat-meltable granular phenol resin dispersion is not particularly limited, and can be, for example, several minutes to several tens of hours.

  Cleaning with the alcohols may be performed only once, or may be repeated multiple times to achieve the desired chlorine content.

  Although it does not restrict | limit especially as alkaline aqueous solution in washing | cleaning using alkaline aqueous solution, It is preferable that it is weak alkaline aqueous solution. If a strong alkaline strong aqueous solution is used, the phenol resin particles may be discolored or dissolved. Further, in addition to the above, an aqueous solution of an alkali metal or alkaline earth metal hydroxide has a non-volatile ionic component and may remain even after a drying operation after washing. As the weak alkaline aqueous solution, for example, an aqueous ammonia solution, an aqueous pyridine solution, an aqueous dimethylamine solution, or the like can be preferably used. In particular, an aqueous ammonia solution is more preferable because of its high ability to remove chlorine ions. The ammonia concentration of the aqueous ammonia solution is not particularly limited, but is preferably from a concentration exceeding 0.5% by weight to 30% by weight, and more preferably from 1 to 25% by weight. When the ammonia concentration is 0.5% by weight or less, chlorine ions in the granular phenol resin cannot be effectively extracted into the aqueous ammonia solution. If the ammonia concentration exceeds 30% by weight, the phenol resin particles may be discolored or dissolved. Further, since the vapor pressure is high, a condenser is required or an autoclave is required depending on the washing temperature (extraction temperature).

  The amount of the alkaline aqueous solution used is not particularly limited and depends on the concentration of the alkaline substance contained. For example, it is 200 with respect to 100 parts by weight of the solid content of the non-heat-meltable granular phenol resin separated from the reaction solution. It can be more than parts by weight.

  The washing temperature in the washing treatment using an alkaline aqueous solution is not particularly limited, and chlorine ions are efficiently removed from the non-heat-meltable granular phenol resin even at a temperature lower than the glass transition temperature of the non-heat-meltable granular phenol resin. can do. Of course, you may wash | clean at the temperature more than the glass transition temperature of a non-heat-meltable granular phenol resin. In many cases, the chlorine content can be extracted more efficiently and in a short time by washing at a temperature equal to or higher than the glass transition temperature. When washing with an aqueous ammonia solution at a high temperature, it is preferable to use an autoclave or the like. The upper limit of the washing temperature is not particularly limited, but is preferably 250 ° C. or lower in order to avoid thermal decomposition of the non-heat-meltable granular phenol resin. More preferably, it is 100 degrees C or less.

  The pressure condition during washing with an alkaline aqueous solution is not particularly limited, and washing can be performed under normal pressure or under pressure. Moreover, the washing time, that is, the stirring time of the non-heat-meltable granular phenol resin dispersion is not particularly limited, and can be, for example, several minutes to several tens of hours.

  The washing using the alkaline aqueous solution may be performed only once, or may be repeated a plurality of times in order to obtain a desired chlorine content.

  In the present invention, in order to sufficiently reduce the chlorine content, it is also preferable to wash the non-heat-meltable granular phenol resin using both alcohols and an alkaline aqueous solution. Here, “use both alcohol and alkaline aqueous solution” means i) using a mixed solution of alcohol and alkaline aqueous solution as a washing solvent, ii) using an aqueous alkaline solution after washing with alcohol. And iii) washing with an aqueous alkali solution followed by washing with alcohols. Among these, the methods ii) and iii) are preferable, and the chlorine content can be sufficiently reduced, and the alkaline substance derived from the alkaline aqueous solution used can also be removed. The method is more preferred.

  In this invention, it is preferable to provide the process (post-cleaning process) which wash | cleans using the liquid medium different from alcohol and alkaline aqueous solution after washing | cleaning by the said alcohols and / or alkaline aqueous solution. The liquid medium is preferably substantially free of ionic impurities, and examples of such a liquid medium include pure water and ion-exchanged water. By the post-cleaning, alcohols adhering to the non-heat-meltable granular phenol resin, an alkaline aqueous solution, a salt generated by a neutralization reaction between the alkaline aqueous solution and the acidic catalyst, and the like are removed. In addition, the solid-liquid separation of the granular phenol resin and the cleaning liquid after the cleaning process or the post-cleaning process can be performed in the same manner as the above-described separation process.

  The washed granular phenol resin can be used in a state containing a liquid medium without drying, and such a non-heat-meltable granular phenol resin containing water is also within the scope of the present invention. However, when used as an organic filler, it is preferably dried. Although it does not specifically limit as a drying method, For example, the method using a shelf-type stationary dryer, an airflow dryer, a fluidized bed dryer etc. can be mentioned. By performing drying, a non-heat-meltable granular phenol resin powder exhibiting good fluidity with a liquid medium content of about 5% or less can be obtained. According to the method of the present invention, it is possible to obtain a granular phenol resin having a high single particle ratio by performing mild crushing as necessary, but using a crusher or the like during or after the drying step. Furthermore, the single particle ratio may be improved.

  According to the method for producing a non-heat-meltable granular phenol resin of the present invention as described above, the average particle diameter is 20 μm or less, particularly 10 μm or less, the single particle ratio is 0.7 or more, and the chlorine ion content is 500 ppm. The following non-heat-meltable granular phenol resin can be produced by a relatively simple method and a method suitable for mass production. In addition, according to the production method of the present invention, it is possible to produce a non-heat-meltable granular phenol resin having these characteristics, having a narrow particle size distribution, a spherical shape, and a very low free phenol content. In addition, the chlorine ion content can be 100 ppm or less. Such a non-heat-meltable granular phenol resin of the present invention can be suitably used for semiconductor applications.

<Thermosetting resin composition>
The thermosetting resin composition of the present invention includes the non-heat-meltable granular phenol resin of the present invention, an epoxy resin, and a curing agent. Since the thermosetting resin composition contains the non-heat-meltable granular phenol resin in which the chlorine content of the present invention, particularly the amount of chlorine ions, is reduced, the high heat resistance, mechanical performance, etc. of the phenol resin Can be suitably used as a semiconductor sealing material and a semiconductor adhesive. Here, the high heat resistance of the thermosetting resin composition is not only due to the high heat resistance of the non-heat-meltable granular phenol resin itself, but also a composite of non-heat-meltable granular phenol resin and epoxy resin. It is also caused by forming. That is, the non-heat-meltable granular phenol resin and the epoxy resin form a tough composite by the reaction between the hydroxyl group of the phenol skeleton of the non-heat-meltable granular phenol resin and the glycidyl group of the epoxy resin. The formation of such a composite increases the strength at the interface between the non-heat-meltable granular phenol resin and the epoxy resin, and therefore the thermosetting resin composition of the present invention has extremely good heat resistance. In addition, a small difference in linear expansion coefficient between the non-heat-meltable granular phenol resin and the epoxy resin is also a cause of high heat resistance.

  In the thermosetting resin composition of the present invention, the blending amount of the non-heat-meltable granular phenol resin that is an organic filler is not particularly limited. For example, when an epoxy resin is used as a binder resin, the epoxy resin and its curing agent are used. The total amount can be 20 to 900 parts by weight with respect to 100 parts by weight. When used as a semiconductor sealing material or a semiconductor adhesive, it is preferably 60 to 500 parts by weight, and 300 to 400 parts by weight with respect to 100 parts by weight of the total amount of the epoxy resin and its curing agent. More preferably. When the blending amount is less than 20 parts by weight with respect to 100 parts by weight of the total amount of the epoxy resin and its curing agent, the effect of imparting heat resistance tends to be difficult to obtain. On the other hand, when the blending amount exceeds 900 parts by weight, the phenol resin powder is non-heat-meltable, so that it is difficult to obtain a dense structure and is often limited to applications that do not require denseness. Moreover, when a non-heat-meltable granular phenol resin in an amount exceeding 500 parts by weight is added to 100 parts by weight of the total amount of the epoxy resin and its curing agent, it is excellent as a semiconductor sealing material or a semiconductor adhesive. Fluidity may not be obtained.

  A conventionally well-known thing can be used as an epoxy resin, For example, the glycidyl ether type epoxy resin of a phenol can be used suitably. Specific examples include, for example, bisphenol A type (or AD type, S type, F type) glycidyl ether, water added bisphenol A type glycidyl ether, ethylene oxide adduct bisphenol A type glycidyl ether, propylene oxide adduct bisphenol. A type glycidyl ether, glycidyl ether of phenol novolac resin, glycidyl ether of cresol novolac resin, glycidyl ether of bisphenol A novolac resin, glycidyl ether of naphthalene resin, trifunctional (or tetrafunctional type) glycidyl ether, dicyclopentadiene In glycidyl ether of phenol resin, glycidyl ester of dimer acid, trifunctional (or tetrafunctional) glycidylamine, glycidylamine of naphthalene resin, etc. That. These can be used alone or in combination of two or more.

  The curing agent is added for curing the epoxy resin. It does not specifically limit as a hardening | curing agent for epoxy resins, A conventionally well-known thing can be used. Specific examples include, for example, phenolic compounds, aliphatic amines, alicyclic amines, aromatic polyamines, polyamides, aliphatic acid anhydrides, alicyclic acid anhydrides, aromatic acid anhydrides, dicyandiamide, organic acids And dihydrazide, boron trifluoride amine complex, imidazoles, and tertiary amines.

  The compounding quantity of a hardening | curing agent is not restrict | limited in particular, It can be set as the range normally used in the said field | area, for example, can be 5-200 weight part with respect to 100 weight part of epoxy resins. However, the compounding amount of the curing agent is usually added in a weight corresponding to the epoxy equivalent of the epoxy resin, but in the present invention, it may be added slightly less than the weight corresponding to the epoxy equivalent. preferable. As described above, the non-heat-meltable granular phenol resin of the present invention reacts with the glycidyl group of the epoxy group at the surface or in the vicinity of the surface. Therefore, when the epoxy equivalent amount of the curing agent is added, the curing agent becomes excessive. Because. An excessive curing agent can cause adverse effects such as deterioration of thermal properties and bleeding. The amount to be reduced depends on the type of epoxy resin, the amount of non-heat-meltable granular phenol resin, the type of curing agent, etc. About 5 to 10%.

  The thermosetting resin composition of the present invention may further contain a curing accelerator. As the curing accelerator, conventionally known ones can be used. For example, imidazoles, dicyandiamide derivatives, dicarboxylic acid dihydrazide, triphenylphosphine, tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazole-tetra Examples thereof include phenyl borate and 1,8-diazabicyclo [5.4.0] undecene-7-tetraphenyl borate. Although the compounding quantity of a hardening accelerator is not restrict | limited in particular, For example, it can be 0-30 weight part with respect to 100 weight part of epoxy resins.

  The thermosetting resin composition of the present invention may contain additives other than those described above. Examples of other additives include antifoaming agents, leveling agents, colorants, diluents (organic solvents, etc.), viscosity modifiers, surfactants, light stabilizers, antioxidants, flame retardant aids, thermoplastic resins. And thermosetting resins other than epoxy resins. Moreover, the thermosetting resin composition of this invention may further contain other organic fillers and inorganic fillers other than the non-heat-meltable granular phenol resin of this invention. Examples of other organic fillers include carbon and rubber fillers (acrylonitrile butadiene rubber filler, silicone rubber filler, etc.). Inorganic fillers include metal fillers such as silver powder, gold powder, copper powder and nickel powder; silica (fused silica, crushed silica, fumed silica, etc.), alumina, boron nitride, titania, glass, iron oxide, ceramic, silica Calcium acid, mica and the like can be mentioned.

  The thermosetting resin composition of the present invention is mixed with a non-heat-meltable granular phenol resin, an epoxy resin, a curing agent, and other additives that are added as necessary, using a three-roll, ball mill or the like. It can be obtained by kneading.

  In addition, when using the thermosetting resin composition of this invention as a semiconductor adhesive, it is also preferable to shape | mold a thermosetting resin composition in the shape of a film for the purpose of workability | operativity improvement at the time of semiconductor manufacture. Examples of the method for producing the adhesive film include a method in which a thermosetting resin composition is applied on a substrate to form a layer of the resin composition, dried, and then the substrate is removed. . The drying temperature is not particularly limited, but can be, for example, about 50 to 200 ° C.

  EXAMPLES Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not limited to these.

[Preparation of non-heat-meltable granular phenolic resin and evaluation of properties]
<Example 1>
After preparing 10 kg of a mixed solution having a formaldehyde concentration of 8 wt% and a hydrochloric acid concentration of 17 wt% using 35 wt% hydrochloric acid and a 36 wt% aqueous formaldehyde solution, 20 g of a 2 wt% aqueous solution of carboxymethyl cellulose sodium salt was added to the mixed solution. And stirred to make a homogeneous solution. Next, after adjusting the temperature of the homogeneous solution to 20 ° C., 400 g of 95 wt% phenol at 40 ° C. was added with stirring. The concentration of phenols with respect to the total weight of the reaction solution is 3.65% by weight, the molar ratio of phenol to formaldehyde is 0.15, and the molar concentration of hydrochloric acid in the reaction solution is 5.0 mol / L. About 70 seconds after the addition of phenol, the reaction solution became cloudy. After the white turbidity, the reaction was continued at a reduced stirring speed. As a result, the reaction solution colored light pink about 30 minutes after the addition of phenol. At this time, the temperature of the reaction solution had reached 30 ° C. After coloring the reaction solution, the reaction solution was heated to 80 ° C. by external heating and kept at this temperature for 30 minutes. Subsequently, this reaction liquid was filtered, and the obtained granular phenol resin cake was washed with 1 kg of water to obtain about 700 g of wet granular phenol resin 1A. A portion of this was dried with a dryer at 50 ° C. for 10 hours and then subjected to fluorescent X-ray measurement. As a result, the chlorine content of the granular phenol resin was about 6500 ppm. The average particle diameter of the granular phenol resin 1A was 3.5 μm.

  Next, 500 g of the wet granular phenol resin 1A was dispersed in 5 L of ion-exchanged water, heated to 95 ° C. with stirring, and maintained at this temperature for 24 hours. Subsequently, the dispersion was filtered, and the granular phenol resin on the filter paper was washed with 500 g of ion-exchanged water to obtain a granular phenol resin 1B (corresponding to a dry weight of 320 g). When a part of the obtained granular phenol resin was dried at 105 ° C. for 10 hours and subjected to fluorescent X-ray measurement, the chlorine content was 1100 ppm.

  Next, wet granular phenol resin 1B (corresponding to a dry weight of 300 g) was dispersed in 900 g of ethylene glycol, heated to 180 ° C. with stirring, and held at this temperature for 3 hours. Next, after cooling to room temperature, the dispersion was filtered, and the granular phenol resin on the filter paper was washed with 500 g of ion-exchanged water. The obtained granular phenol resin was dried in a nitrogen stream at 180 ° C. for 5 hours to obtain 280 g of granular phenol resin 1C. The chlorine content of the granular phenol resin 1C was 70 ppm.

<Example 2>
280 g of granular phenolic resin 2A was obtained in the same manner as in Example 1 except that washing with ethylene glycol was performed twice in total (the same conditions as in Example 1 for both times). The chlorine content of the granular phenol resin 2A was 10 ppm. In addition, the drying process was not provided between the 1st washing | cleaning and the 2nd washing | cleaning.

<Example 3>
After preparing 10 kg of a mixed solution having a formaldehyde concentration of 8 wt% and a hydrochloric acid concentration of 18 wt% using 35 wt% hydrochloric acid and a 36 wt% aqueous formaldehyde solution, 30 g of a 2 wt% aqueous solution of carboxymethylcellulose sodium salt was added to the mixed solution. And stirred to make a homogeneous solution. Next, after adjusting the temperature of the homogeneous solution to 20 ° C., 400 g of 95 wt% phenol at 40 ° C. was added with stirring. The concentration of phenols with respect to the total weight of the reaction solution is 3.64% by weight, the molar ratio of phenol to formaldehyde is 0.15, and the molar concentration of hydrochloric acid in the reaction solution is 5.3 mol / L. About 60 seconds after the addition of phenol, the reaction solution became cloudy. After the white turbidity, the reaction was continued at a reduced stirring speed. As a result, the reaction solution colored light pink about 30 minutes after the addition of phenol. At this time, the temperature of the reaction solution had reached 30 ° C. After coloring the reaction solution, the reaction solution was heated to 80 ° C. by external heating and kept at this temperature for 30 minutes. Subsequently, this reaction liquid was filtered, and the obtained granular phenol resin cake was washed with 1 kg of water to obtain about 700 g of wet granular phenol resin 3A. A portion of this was dried with a dryer at 50 ° C. for 10 hours and then subjected to fluorescent X-ray measurement. As a result, the chlorine content of the granular phenol resin was about 6500 ppm. The average particle diameter of the granular phenol resin 3A was 5.8 μm.

  Next, 500 g of the wet granular phenol resin 3A was dispersed in 5 L of ion-exchanged water, heated to 95 ° C. with stirring, and maintained at this temperature for 24 hours. Next, the dispersion was filtered, and the granular phenol resin on the filter paper was washed with 500 g of ion-exchanged water to obtain a granular phenol resin 3B (corresponding to a dry weight of 320 g). A part of the granular phenol resin obtained was dried at 105 ° C. for 10 hours and subjected to fluorescent X-ray measurement. As a result, the chlorine content was 1700 ppm.

  Next, wet granular phenol resin 3B (corresponding to a dry weight of 300 g) was dispersed in 900 g of ethylene glycol, heated to 180 ° C. with stirring, and held at this temperature for 3 hours. Next, after cooling to room temperature, the dispersion was filtered, and the granular phenol resin on the filter paper was washed with 500 g of ion-exchanged water. The obtained granular phenol resin was dried in a nitrogen stream at 180 ° C. for 5 hours to obtain 280 g of granular phenol resin 3C. The chlorine content of the granular phenol resin 3C was 90 ppm.

<Example 4>
280 g of granular phenolic resin 4A was obtained in the same manner as in Example 3, except that washing with ethylene glycol was performed twice in total (the same conditions as in Example 3 for both times). The chlorine content of the granular phenol resin 4A was 30 ppm. In addition, the drying process was not provided between the 1st washing | cleaning and the 2nd washing | cleaning.

<Example 5>
500 g of the granular phenol resin 1A obtained in Example 1 was dispersed in 1.5 L (1350 g) of a 25 wt% aqueous ammonia solution, heated to 37 ° C. with stirring, and maintained at this temperature for 24 hours. Subsequently, the dispersion was filtered, and the granular phenol resin on the filter paper was washed with 500 g of ion exchange water. The obtained granular phenol resin was dried at 105 ° C. for 10 hours to obtain 320 g of granular phenol resin 5A. The chlorine content of the granular phenol resin 5A was 300 ppm.

<Example 6>
320 g of granular phenolic resin 6A was obtained in the same manner as in Example 5 except that washing with a 25 wt% aqueous ammonia solution was performed twice in total (the same conditions as in Example 5). The chlorine content of the granular phenol resin 6A was 50 ppm. In addition, the drying process was not provided between the 1st washing | cleaning and the 2nd washing | cleaning.

<Example 7>
The wet granular phenolic resin 1B obtained in Example 1 (corresponding to a dry weight of 300 g) was dispersed in 900 g of a 25 wt% aqueous ammonia solution and stirred at 80 ° C. for 2 hours using an autoclave. Subsequently, the dispersion was filtered, and the granular phenol resin on the filter paper was washed with 500 g of ion exchange water. The obtained granular phenol resin was dried at 105 ° C. for 10 hours to obtain 280 g of granular phenol resin 7A. The chlorine content of the granular phenol resin 7A was below the detection limit (10 ppm).

<Example 8>
The wet granular phenol resin 1A obtained in Example 1 (corresponding to a dry weight of 300 g) was dispersed in 900 g of ethylene glycol, heated to 180 ° C. with stirring, and held at this temperature for 3 hours. Next, after cooling to room temperature, the dispersion was filtered, and the granular phenol resin on the filter paper was washed with 500 g of ion-exchanged water. The obtained granular phenol resin was dried in a nitrogen stream at 180 ° C. for 5 hours to obtain 280 g of a granular phenol resin 8A. The chlorine content of the granular phenol resin 8A was 300 ppm.

<Example 9>
280 g of a granular phenol resin 9A was obtained in the same manner as in Example 8, except that washing with ethylene glycol was performed twice in total (the same conditions as in Example 8). The chlorine content of the granular phenol resin 9A was 60 ppm. In addition, the drying process was not provided between the 1st washing | cleaning and the 2nd washing | cleaning.

<Comparative Example 1>
After preparing 2000 g of a mixed solution having a formaldehyde concentration of 10 wt% and a hydrochloric acid concentration of 16 wt% using 35 wt% hydrochloric acid and a 36 wt% formaldehyde aqueous solution, 8 g of water was added to the mixed solution and stirred to make it uniform It was set as the solution. Next, after adjusting the temperature of the homogeneous solution to 20 ° C., 70 g of 95 wt% phenol at 30 ° C. was added with stirring. The concentration of phenols relative to the total weight of the reaction solution is 3.2% by weight, the molar ratio of phenol to formaldehyde is 0.11, and the molar concentration of hydrochloric acid in the reaction solution is 4.7 mol / L. About 95 seconds after the addition of phenol, the reaction solution became cloudy. After the white turbidity, the reaction was continued at a reduced stirring speed. As a result, the reaction solution colored light pink about 30 minutes after the addition of phenol. At this time, the temperature of the reaction solution had reached 30 ° C. After coloring the reaction solution, the reaction solution was heated to 80 ° C. by external heating and kept at this temperature for 30 minutes. Next, this reaction solution was filtered, and the resulting cake was washed with 500 g of water, then suspended in 500 g of 0.5 wt% aqueous ammonia solution, and neutralized at 40 ° C. for 1 hour. After the neutralization reaction, the suspension was subjected to suction filtration using an aspirator, washed with 500 g of water, and dried with a dryer at 50 ° C. for 10 hours to obtain 80 g of pale yellow granular phenol resin H1A. FIG. 3 shows an optical micrograph of the granular phenol resin H1A obtained in this comparative example. As shown in FIG. 3, it can be seen that the granular phenol resin H1A has a relatively large amount of aggregation of primary particles. The single particle ratio of the granular phenol resin H1A is 0.60.

<Comparative Example 2>
After preparing 2000 g of a mixed solution having a formaldehyde concentration of 10 wt% and a hydrochloric acid concentration of 5 wt% using 35 wt% hydrochloric acid and a 36 wt% formaldehyde aqueous solution, 8 g of a 2 wt% aqueous solution of carboxymethyl cellulose sodium salt was added to the mixed solution. And stirred to make a homogeneous solution. Next, after adjusting the temperature of the homogeneous solution to 20 ° C., 70 g of 95 wt% phenol at 30 ° C. was added with stirring. The concentration of phenols with respect to the total weight of the reaction solution is 3.2% by weight, the molar ratio of phenol to formaldehyde is 0.11, and the molar concentration of hydrochloric acid in the reaction solution is 1.5 mol / L. Even if the reaction was continued, no cloudiness was observed in the reaction solution, and no granular phenol resin was obtained.

<Comparative Example 3>
After mixing 140 g of 36 wt% formaldehyde aqueous solution, 204 g of 95 wt% phenol and 940 g of water to prepare 1284 g of mixed solution, 8 g of 2 wt% aqueous solution of carboxymethylcellulose sodium salt was added to the mixed solution and stirred. A homogeneous solution. Next, after adjusting the temperature of the homogeneous solution to 20 ° C., 914 g of 35 wt% hydrochloric acid at 30 ° C. was added with stirring. The concentration of phenols with respect to the total weight of the reaction solution is 8.8% by weight, the molar ratio of phenol to formaldehyde is 1.23, and the molar concentration of hydrochloric acid in the reaction solution is 4.5 mol / L. When the heating of the reaction solution was started, the resin adhered to the reaction vessel wall. The powder which was in a suspended state at the completion of heating was filtered off, washed, neutralized and dried to obtain about 50 g of granular phenol resin H3A. When the particles were observed with a microscope, many irregular particles were present, and the sphericity and the single particle ratio could not be obtained.

<Comparative example 4>
500 g of granular phenol resin 3B obtained in Example 3 above (chlorine ion content 1700 ppm) was dispersed in 5 L of ion-exchanged water, heated to 95 ° C. with stirring, and maintained at this temperature for 24 hours. Subsequently, the dispersion was filtered, and the granular phenol resin on the filter paper was washed with 500 g of ion exchange water. The obtained granular phenol resin was dried at 105 ° C. for 10 hours to obtain a granular phenol resin H4A. The chlorine content of the granular phenol resin H4A was 700 ppm.

<Comparative Example 5>
The same operation as in Comparative Example 4 was performed on the granular phenol resin H4A to obtain a granular phenol resin H5A. The chlorine content of the granular phenol resin H5A was 600 ppm.

<Comparative Example 6>
The same operation as in Comparative Example 4 was performed on the granular phenol resin H5A to obtain a granular phenol resin H6A. The chlorine content of the granular phenol resin H6A was 550 ppm.

<Comparative Example 7>
100 parts by weight of phenol, 39 parts by weight of 92% by weight paraformaldehyde, 9 parts by weight of hexamethylenetetramine, and 1 part by weight of gum arabic were dissolved in 100 parts by weight of water. 7 parts by weight of Bell Pearl R800 (manufactured by Air Water Co., Ltd.) was added as a core substance, and the temperature was raised to 85 ° C. over 60 minutes with gentle stirring, and further reacted for 60 minutes while maintaining a temperature of 85 ° C. The obtained reaction liquid was cooled and solid-liquid separated to obtain a spherical resol resin having an average particle diameter of about 500 μm. 100 parts by weight of this spherical resol resin was dispersed in a solution containing 1000 parts by weight of 17% by weight hydrochloric acid and 9% by weight formaldehyde, heated to 80 ° C. and held for 1 hour. The reaction solution was separated into solid and liquid by filtration, washed with water, and dried at 85 ° C. for 5 hours. The obtained resin exhibited substantially non-hot meltability while maintaining the spherical shape and particle size. The sphericity was 1.0, the single particle ratio was 1.0, the average particle size was about 500 μm, the boiling methanol solubility was 6%, and the chlorine content was 4500 ppm. In addition, the average particle diameter was directly read from the particle size distribution of the optical microscope image.

  The non-heat-meltable phenol resin particles having an average particle diameter of about 500 μm were washed twice with ethylene glycol according to the method described in Example 2 to obtain a granular phenol resin H7A. The chlorine content of the granular phenol resin H7A was 1200 ppm. In addition, the drying process was not provided between 1st washing | cleaning and 2nd washing | cleaning.

About the granular phenol resin of the said Example and comparative example, the characteristic hung up below was measured. The measurement method and measurement conditions are as follows. The measurement results are shown in Table 1 together with the reaction conditions.
(1) Non-thermal meltability: About 5 g of granular phenol resin sample was inserted between two 0.2 mm thick stainless steel plates and pressed for 2 minutes with a total load of 50 kg with a press machine preheated to 100 ° C. Sometimes, when melting and / or fusing, the granular phenolic resin forms a flat plate, the phenolic resin particles are deformed, or the phenolic resin particles do not adhere to each other, it is determined as having “non-thermomeltability” did.
(2) Boiling methanol solubility: About 10 g of phenol resin sample was precisely weighed and heated under reflux in about 500 mL of substantially anhydrous methanol for 30 minutes. Filter through 3 glass filter and wash the residue on the glass filter with about 100 mL of anhydrous methanol. Next, the residue on the glass filter after washing is dried at 40 ° C. for 5 hours, and then the residue is precisely weighed. Based on the obtained residue weight after drying and phenol resin sample weight, boiling methanol solubility is calculated based on the following formula.

Boiling methanol solubility (% by weight) = (Difference between phenol resin sample weight and residue weight after drying) / (phenol resin sample weight) × 100
(3) Average particle diameter: It is a 50% cumulative frequency value of the frequency distribution measured by a laser diffraction particle size analyzer (Microtrac X100 manufactured by Nikkiso Co., Ltd.).
(4) Single particle ratio: The granular phenol resin is dispersed in water droplets and observed with an optical microscope. In a randomly selected field of view containing about 300 primary particles, the total number of primary particles and single particles The ratio when the number of particles is counted, that is, the number of single particles / the total number of primary particles.
(5) Coefficient of variation of particle size distribution: An aqueous dispersion was prepared using a granular phenol resin, and the following formula [1] was obtained from the frequency distribution measured by a laser diffraction particle size measuring instrument (Microtrac X100 manufactured by Nikkiso Co., Ltd.). Calculated by

Coefficient of variation of particle size distribution = (d _84% −d _16% ) / (2 × average particle size) [1]
Here, in the above formula [1], d _84% and d _16% are particle diameters indicating the cumulative frequencies of 84% and 16%, respectively, in the obtained frequency distribution. When the coefficient of variation was 0.65 or less, it was determined to have a narrow particle size distribution.
(6) Sphericity: A field of view containing about 300 primary particles is randomly determined in observation with an optical microscope, and 10 primary particles having the lowest aspect ratio (ie, ratio of minor axis / major axis). It is the average value of these 10 aspect ratios when the aspect ratio in the projected cross section is measured for each of these 10 primary particles.
(7) Free phenol content: Defined as a value calculated by the following test. That is, about 10 g of a phenol resin sample is precisely weighed, extracted in 190 mL of methanol under reflux for 30 minutes, and filtered through a glass filter. The concentration of phenols in the filtrate is quantified by liquid chromatography, and the weight of phenols in the filtrate is calculated. The ratio between the phenol weight and the sample weight, that is, the phenol weight / phenol resin sample weight is defined as “free phenol content”.
(8) Chlorine content: After pressing the measurement sample (non-heat-meltable phenol resin particles) and the measurement binder powder into a measurement pellet, EZ scan using a fluorescent X-ray analyzer ZSX100E manufactured by Rigaku Corporation X-ray fluorescence analysis is performed in the mode. The measured value of the diffraction intensity of the chlorine Kα ray is normalized by the estimated molecular formula (C ₇ H ₆ O ₁ ) of the cured phenol resin to obtain the chlorine content (wt / wt).

  From the above examples, a granular phenol resin having a chlorine content of 100 ppm or less could be efficiently obtained by washing with ethylene glycol and / or washing with an aqueous ammonia solution. Alcohols such as ethylene glycol have chemical properties that are easy to diffuse into the interior of the phenolic resin particles, and improve the diffusion rate of chlorine ions in the phenolic resin. It is done. Further, it is considered preferable to perform the washing in a high temperature region where the mobility of the phenol resin molecule is increased. The same applies when an aqueous ammonia solution is used, and the aqueous ammonia solution diffuses into the interior of the phenolic resin particles, thereby improving the diffusion rate of chlorine ions in the phenolic resin. Conceivable.

  On the other hand, when Comparative Examples 4 to 6 are viewed, the phenol resin particles in the first washing with hot water (granular phenol resin 3B: chlorine content 1700 ppm) and the second time (granular phenol resin H4A: chlorine content is 700 ppm). Since chlorine ions on the surface are removed, there is a decrease in chlorine content, but there are still many chlorine ions trapped inside the phenolic resin, and diffusion of chlorine ions existing inside the particles to the particle surface As a result, the cleaning effect is significantly reduced in the third and fourth cleaning with hot water. When hot water is used, even if washing is performed four times, the chlorine content does not become 500 ppm or less, which is very inefficient. Furthermore, as shown in Comparative Example 7, it was found that a phenol resin having a relatively large average particle size did not sufficiently reduce the chlorine content even by washing with alcohol.

  1 is a scanning electron micrograph (SEM photograph, 500 times) of the granular phenol resin 1C obtained in Example 1. FIG. FIG. 2 is a further enlarged SEM photograph (3500 times) of the granular phenol resin 1C. As can be seen from FIG. 1, FIG. 2 and Table 1, even with ethylene glycol cleaning and / or aqueous ammonia cleaning, there is almost no change in the average particle size, single particle ratio, sphericity, surface state of phenol resin particles, etc. It was confirmed that washing with ethylene glycol or an aqueous ammonia solution did not adversely affect the phenol resin particles.

[Thermosetting resin composition]
<Example 10>
6 parts by weight of the granular phenol resin 2A obtained in Example 2 above and 4 parts by weight of an epoxy resin (“Epototo YD-128” manufactured by Tohto Kasei) were kneaded on a hot roll while being heated to 70 ° C., and then cured. As an agent, 0.2 part by weight of 2-ethyl-4-methylimidazole was further added and kneaded, the kneaded product was removed from the hot roll, and pulverized after cooling to obtain a powder that was a thermosetting resin composition. The thermosetting resin composition exhibited good melt fluidity, and had a 150 ° C. gel time of 33 seconds and a 200 ° C. gel time of 18 seconds.

Next, the thermosetting resin composition was set in a mold heated to 180 ° C. and held at a pressure of 20 kgf / cm ² for 3 minutes to obtain a cured product. The obtained cured product had a specific gravity of 1.24 and was lightweight.

<Example 11>
6 parts by weight of the granular phenol resin 2A obtained in Example 2 above and 4 parts by weight of an epoxy resin (“Epototo YD-8125” manufactured by Tohto Kasei) were kneaded on a hot roll while being heated to 70 ° C., and then cured. As an agent, 0.2 part by weight of 2-ethyl-4-methylimidazole was further added and kneaded, the kneaded product was removed from the hot roll, and pulverized after cooling to obtain a powder that was a thermosetting resin composition. The thermosetting resin composition exhibited good melt fluidity, and had a 150 ° C. gel time of 25 seconds and a 200 ° C. gel time of 14 seconds.

Next, the thermosetting resin composition was set in a mold heated to 180 ° C. and held at a pressure of 20 kgf / cm ² for 3 minutes to obtain a cured product. The obtained cured product had a specific gravity of 1.24 and was lightweight. The obtained cured product had a chlorine content of 70 ppm and could be used favorably as a semiconductor sealing material or semiconductor adhesive.

<Example 12>
15 parts by weight of the granular phenol resin 2A obtained in Example 2 above, 60 parts by weight of an epoxy resin (“Epototo YD-8125” manufactured by Tohto Kasei), and a phenol novolac resin (TD-manufactured by Nippon Ink Chemical Co., Ltd.) 2093) 6 parts by weight and 4 parts by weight of dicyandiamide were kneaded to obtain a semi-liquid thermosetting resin composition.

<Example 13>
60 parts by weight of the granular phenol resin 4A obtained in Example 4 above, 40 parts by weight of an epoxy resin (“Epototo YD-8125” manufactured by Toto Kasei), and 2 parts by weight of 2-ethyl-4-methylimidazole as a curing agent Kneaded to obtain a thermosetting resin composition 11 A. On the other hand, instead of the granular phenol resin 4 A, 106 parts by weight of fused silica (FB-301 manufactured by Denki Kagaku Kogyo) and 2-ethyl-4 as a curing agent were used. -2 parts by weight of methylimidazole were kneaded to obtain a thermosetting resin composition 11B, the volume ratio of the granular phenol resin 4A in the thermosetting resin composition 11A and the fused silica in the thermosetting resin composition 11B. Next, the thermosetting resin composition 11A and the thermosetting resin composition 11B were each heat-cured under a temperature condition of 150 ° C. to obtain a cured product. The cured products A and B were respectively measured for the cured products A and B using an orientec curast meter VPS, and the 150 ° C. torque value of the cured product A was measured. It was 1.34 times of hardened | cured material B. From this, the toughness at the time of a heat | fever is improving the hardened | cured material of the thermosetting resin composition using the non-heat-meltable granular phenol resin of this invention. It was confirmed.

  It should be understood that the embodiments and examples disclosed herein are illustrative and non-restrictive in every respect. The scope of the present invention is defined by the terms of the claims, rather than the description above, and is intended to include any modifications within the scope and meaning equivalent to the terms of the claims.

It is a scanning electron micrograph of granular phenol resin 1C obtained in Example 1 (500 times). It is the SEM photograph further expanded of granular phenol resin 1C (3500 times). 2 is an optical micrograph of granular phenol resin H1A obtained in Comparative Example 1.

Claims (22)

  A non-heat-meltable granular phenol resin having an average particle size of 20 μm or less, a single particle ratio of 0.7 or more, and a chlorine content of 500 ppm or less.   2. The non-heat-meltable granular phenol resin according to claim 1, wherein the average particle size is 10 μm or less.   The non-heat-meltable granular phenol resin according to claim 1 or 2, wherein the chlorine content is 100 ppm or less. The non-heat-meltable granular phenol resin according to any one of claims 1 to 3, wherein the coefficient of variation of the particle size distribution represented by the following formula [1] is 0.65 or less.
Coefficient of variation of particle size distribution = (d _84% −d _16% ) / (2 × average particle size) [1]
Here, d _84% and d _16% are particle diameters showing cumulative frequencies of 84% and 16%, respectively, in the frequency distribution obtained by the laser diffraction / scattering method.   The non-heat-meltable granular phenol resin according to any one of claims 1 to 4, wherein the sphericity is 0.5 or more.   The non-heat-meltable granular phenol resin according to any one of claims 1 to 5, wherein a free phenol content is 500 ppm or less. (1) A granular phenol resin is obtained by reacting an aldehyde with a phenol in an aqueous medium in the presence of hydrochloric acid as an acidic catalyst having a molar concentration of 2.0 mol / L or more in the reaction solution and a protective colloid agent. Forming a granular phenol resin forming step;
(2) a non-thermal melting step of heating the reaction solution containing the granular phenol resin to form a non-heat-meltable granular phenol resin;
(3) a separation step of separating the non-heat-meltable granular phenol resin from the reaction solution;
(4) a washing step of washing the non-heat-meltable granular phenol resin using one or more liquid media selected from alcohols and alkaline aqueous solutions;
The manufacturing method of the non-heat-meltable granular phenol resin characterized by including.   The method for producing a non-heat-meltable granular phenol resin according to claim 7, wherein the washing using the alcohol in the washing step is performed at a temperature equal to or higher than the glass transition temperature of the non-heat-meltable granular phenol resin.   The method for producing a non-heat-meltable granular phenol resin according to claim 7 or 8, wherein the aldehyde is formaldehyde, paraformaldehyde or a mixture thereof.   The method for producing a non-heat-meltable granular phenolic resin according to any one of claims 7 to 9, wherein a molar ratio of the phenols to the aldehydes is 0.9 or less.   The method for producing a non-heat-meltable granular phenol resin according to any one of claims 7 to 10, wherein the protective colloid agent is a water-soluble polysaccharide derivative.   The non-heat-meltable granular phenol resin obtained using the method in any one of Claims 7-11.   The non-heat-meltable granular phenol resin according to claim 12, wherein the average particle size is 20 µm or less, the single particle ratio is 0.7 or more, and the chlorine content is 500 ppm or less.   The non-heat-meltable granular phenol resin according to claim 13, wherein the average particle size is 10 μm or less.   The non-heat-meltable granular phenol resin according to claim 13 or 14, wherein the chlorine content is 100 ppm or less.   The non-heat-meltable granular phenol resin according to any one of claims 13 to 15, wherein the coefficient of variation of the particle size distribution represented by the above formula [1] is 0.65 or less.   The non-heat-meltable granular phenol resin according to any one of claims 13 to 16, wherein the sphericity is 0.5 or more.   The non-thermomeltable granular phenol resin according to any one of claims 13 to 17, wherein a free phenol content is 500 ppm or less.   A thermosetting resin composition comprising the non-heat-meltable granular phenol resin according to any one of claims 1 to 6 and 12 to 18, an epoxy resin, and a curing agent.   The thermosetting resin composition according to claim 19, further comprising an inorganic filler.   The semiconductor sealing material which consists of a thermosetting resin composition of Claim 19 or 20.   The adhesive for semiconductors which consists of a thermosetting resin composition of Claim 19 or 20.