JP2003137975A - Method for producing phenol resin and epoxy resin - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for efficiently producing a phenol resin and an epoxy resin by using phenols and an unsaturated cyclic hydrocarbon compound having two or more carbon-carbon double bonds as raw materials. SOLUTION: This method for producing the phenol resin comprises a step (I) for reacting phenols with unsaturated cyclic hydrocarbons by using a continuous reactor in the presence of an acid catalyst, a step (II) for stopping the reaction and a step (III) for removing and recovering the unreacted raw material from the reaction solution. The phenol resin having excellent properties can efficiently be produced by using a reactor having a multistage agitating structure as the continuous reactor in the step (I). The method enables further effective production by continuously carrying out these steps (II) and (III).

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing a phenol resin and an epoxy resin having excellent heat resistance, moisture resistance and crack resistance, which are useful as an electrical insulating material, particularly a resin for semiconductor encapsulating materials and a resin for laminated boards. Regarding

[0002]

2. Description of the Related Art In recent years, semiconductor-related technologies have been rapidly advancing, and the miniaturization of wiring and the shift from through-hole mounting to surface mounting have been progressing with the improvement in integration. However, in an automated surface mounting line, there is a problem that a semiconductor package undergoes a rapid temperature change during soldering of a lead wire, and a crack occurs in a resin molding portion for a semiconductor sealing material. In addition, there is a concern that the mounting environment will become hot due to lead-free solder, and it is expected that the required characteristics of the resin for the encapsulant will become more severe.

Conventionally, as a resin for semiconductor encapsulating materials, phenolic resins such as phenol novolac resin and cresol novolac resin have been used as a curing agent, and epoxy resins derived from these phenolic resins have been used as a main agent. There is. However, when these resins are used, the moisture resistance of the semiconductor package is poor, and as a result, there is a problem in that the occurrence of cracks during immersion in the solder bath as described above cannot be avoided.

Therefore, recently, a phenol resin or an epoxy resin modified with dicyclopentadiene (hereinafter sometimes referred to as DCPD) or the like has been proposed as a resin for semiconductor encapsulating material, and has moisture resistance, heat resistance, etc. Is being improved. Examples of methods for producing these resins include, for example, JP-A-5-214051, WO-66645,
JP-A-63-99224 and JP-A-11-1996
57, JP 61-123618, JP 5-
No. 5022 and Japanese Patent Laid-Open No. 7-157538. That is, a method is known in which unsaturated cyclic hydrocarbons such as dicyclopentadiene are sequentially added to a reactor charged with phenols and an acid catalyst to carry out the reaction. However, in the above-mentioned conventional method, since the reaction is carried out in a batch system, it is necessary to add an apparatus or increase the size in order to increase the production amount, and there is a limit in improving the production efficiency.

Further, Japanese Patent Laid-Open No. 5-214051, W
In O-66645, JP-A-63-99224, and JP-A-11-199657, the reaction solution was treated with a quenching agent such as hydrotalcites and inorganic alkalis to stop the reaction. After that, a method is known in which the deactivator and the catalyst residue are removed, and unreacted phenols and the like are removed by distillation. In those methods, a filling operation of a new deactivator is required at each reaction, and a work such as a filtration process and a water washing process for removing the deactivator and the catalyst residue from the reaction solution is required. There is a problem that not only the number increases but also the manufacturing process becomes complicated.

Further, Japanese Patent Application Laid-Open No. 61-123618 discloses a method of distilling a reaction solution under reduced pressure without performing deactivation treatment to remove the catalyst together with unreacted phenols. Similarly, JP-A-5-5022 discloses a method of removing a catalyst using a super strong acid such as trifluoromethanesulfonic acid as a catalyst without performing deactivation treatment. In those methods, the deactivation treatment is omitted, so that the manufacturing process is simplified, but the catalyst removal efficiency is extremely poor, and the catalyst residue remains in the resin, which adversely affects the resin properties, and There was a problem such as marked deterioration. Further, there is a problem that the production efficiency is rather lowered, for example, it is necessary to dissolve the obtained resin again in the solvent and wash it with water.

Further, Japanese Patent Laid-Open No. 7-157538 discloses a reaction using an ion exchange resin as a catalyst, but it was necessary to remove the catalyst by centrifugation or filtration. Further, in the above-mentioned conventional method, since the deactivation of the catalyst by the deactivator, the removal of the deactivator and the catalyst residue by filtration and washing with water, the removal of the catalyst by vacuum distillation, etc. are carried out in a batch system, the production amount is increased. However, there was a limit to the improvement of production efficiency, because it required additional equipment and larger size.

[0008]

The problem to be solved by the present invention is to provide a phenol and an unsaturated cyclic hydrocarbon compound having two or more carbon-carbon double bonds (hereinafter, "unsaturated cyclic hydrocarbons"). It is sometimes referred to as).) As a raw material and a method for efficiently producing a phenol resin and an epoxy resin.

[0009]

As a result of intensive studies to solve the above-mentioned problems, the present inventor has conducted a reaction between phenols and unsaturated cyclic hydrocarbons continuously, and has a specific reactor. It was found that a phenol resin and an epoxy resin can be efficiently produced by using, and the present invention has been completed.

That is, the first aspect of the present invention is a step (I) of reacting an unsaturated cyclic hydrocarbon compound having two or more carbon-carbon double bonds with a phenol as a raw material in the presence of an acid catalyst, In the method for producing a phenolic resin, which includes a step (II) of stopping the reaction and a step (III) of removing and recovering unreacted raw material from the reaction solution, the step (I) continuously connects the raw material and the acid catalyst to the reactor The present invention relates to a method for producing a phenolic resin, which is characterized in that the reaction liquid is continuously supplied and continuously extracted.

In a second aspect of the present invention, the reactor used in the step (I) in the first aspect of the present invention is a vertical type in which a rotating shaft installed vertically inside the reactor and a stirring blade attached to the rotating shaft. The present invention relates to a method for producing a phenol resin, which is a flow-through tank type reactor.

The third aspect of the present invention is the first or second aspect of the present invention.
In the step (II), the reaction liquid obtained in the step (I) is continuously passed through a deactivating tower filled with a solid deactivator to deactivate the acid catalyst. The present invention relates to a method for producing a phenol resin.

A fourth aspect of the present invention is the first or second aspect of the present invention.
In the step (II), the reaction liquid obtained in the step (I) is continuously supplied from the upper part of the catalyst separation column, heated under reduced pressure and an inert gas is introduced from the lower part of the catalyst separation column, The present invention relates to a method for producing a phenol resin, which comprises discharging an acid catalyst and an inert gas from the top of a separation tower and discharging a reaction solution in which the reaction has substantially stopped from the bottom of the catalyst separation tower.

The fifth aspect of the present invention is the third or fourth aspect of the present invention.
In the step (III), the molten resin is continuously obtained by continuously concentrating the reaction solution obtained in the step (II) to remove and recover unreacted raw materials. The present invention relates to a resin manufacturing method.

A sixth aspect of the present invention relates to the method for producing a phenol resin according to any one of the first to fifth aspects of the present invention, wherein the phenol is phenol.

A seventh aspect of the present invention is characterized in that the unsaturated cyclic hydrocarbon compound having at least two carbon-carbon double bonds in any of the first to sixth aspects of the present invention is dicyclopentadiene. A method for producing the phenolic resin according to claim 1.

An eighth aspect of the present invention relates to a method for producing a phenol resin, characterized in that the acid catalyst according to any one of the first to seventh aspects of the present invention is a boron trifluoride / phenol complex.

In a ninth aspect of the present invention, an epoxy resin is produced by the production method according to any one of the first to eighth aspects of the present invention, and then the phenol resin and epihalohydrins are reacted in the presence of a base catalyst. The present invention relates to a resin manufacturing method.

[0019]

BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The method for producing a phenol resin of the present invention comprises a step (I) of reacting an unsaturated cyclic hydrocarbon compound having two or more carbon-carbon double bonds with a phenol as a raw material in the presence of an acid catalyst, and carrying out the reaction. It includes a step (II) of stopping and a step (III) of removing and collecting unreacted raw materials from the reaction solution.

<Unsaturated Cyclic Hydrocarbons> As unsaturated cyclic hydrocarbon compounds having two or more carbon-carbon double bonds, dicyclopentadiene, 4-vinylcyclohexene, 5-vinylnorborna-2-ene, 3a, 4,7,7
Examples include a-tetrahydroindene, α-pinene, limonene and the like. These can be used alone or in combination. In particular, dicyclopentadiene is preferable because the resulting resin is excellent in heat resistance, moisture resistance and mechanical properties.

<Phenols> As phenols,
The aromatic compound having a phenolic hydroxyl group is not particularly limited as long as it is an aromatic compound, for example, phenol, o-
Cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-isopropylphenol, m-propylphenol, p-propylphenol, p-sec-butylphenol, p-tert- Butylphenol, p
-Cyclohexylphenol, p-chlorophenol,
Monohydric phenols such as o-bromophenol, m-bromophenol, p-bromophenol, α-naphthol, β-naphthol; resorcin, catechol, hydroquinone, 2,2-bis (4′-hydroxyphenyl) propane, bis Examples thereof include dihydric phenols such as (dihydroxyphenyl) methane, bis (dihydroxynaphthyl) methane, tetramethylbiphenol and biphenol; and trivalent phenols such as trishydroxyphenylmethane. Especially phenol, o-cresol, m-
Cresol, α-naphthol, β-naphthol and 2,
2-bis (4′-hydroxyphenyl) propane and the like are preferable from the viewpoints of economy and ease of production. These can be used alone or in combination. Also, for example, when the phenols are phenols, due to the difference in the phenol production method, synthetic phenol with few impurities,
Although it is roughly classified into phenol with a slightly low purity,
Either can be preferably used.

<Acid catalyst> The acid catalyst is not particularly limited, but from the viewpoint of catalytic activity, boron trifluoride and boron trifluoride-ether complex, boron trifluoride
A complex such as a phenol complex, a boron trifluoride / water complex, a boron trifluoride / alcohol complex, a boron trifluoride / amine complex, or a mixture thereof is used. Particularly preferred are boron trifluoride, boron trifluoride / phenol complex, and boron trifluoride / ether complex.

<Solvent> A solvent may be used in the reaction, but when phenols are used in excess with respect to the unsaturated cyclic hydrocarbons, the solvent may not be used.

<Reaction Step (I)> In the present invention, in the step (I), the above-mentioned raw material and acid catalyst are continuously supplied to the reactor for reaction, and the reaction liquid is continuously withdrawn. And

<Reactor> The shape and the like of the reactor are not particularly limited, but when the flow tank type reactor described below is used, a phenol resin having good physical properties can be efficiently used. It can be manufactured. As the flow tank reactor, the reactor shown in FIG. 1 can be exemplified. That is, a vertical cylindrical container 1 has a rotary shaft 2 and a stirring blade 3 extending in a direction perpendicular to the rotary shaft 2 at the center, and the rotary shaft 2 is directly or indirectly connected to a motor 4 for rotation. By rotating the shaft, the reaction liquid in the reactor can be stirred by a stirring blade. In the embodiment of FIG. 1, phenols and acid catalysts are fed from the bottom of the reaction vessel by line 12 and unsaturated cyclic hydrocarbons are fed from the side of the reaction vessel by line 13. Figure 1
Shows a mode in which the line 13 is branched and supplied to the reaction container. The reaction liquid is withdrawn through the line 14 from the top of the reaction vessel. The ratio of the inner diameter D of the cylindrical container 1 to the length L, so-called L / D, is appropriately 1 to 30, preferably 1 to 25, and more preferably 2 to 20. L
When / D exceeds 30, the reactor and the rotating shaft become long, and the operation from a long time causes a deviation from the center line of the rotating shaft, and the motor energy for stirring becomes large, which is not preferable. The shape of the stirring blade 3 is a paddle type,
Any shape represented by a turbine type and a propeller type can be used. Here, when it is assumed that the reactor is composed of a plurality of stages of blocks separated by stirring blades, the reaction liquid existing in the n-th block passes through the gap between the stirring blades and the inner surface of the reaction vessel to the next (n + 1) ) Although it is sent to the block on the downstream side to the downstream side, part of the reaction liquid that was forced to flow vertically to the inner surface of the reaction vessel by the stirring blade is reflected on the inner surface and is not sent to the next stage and goes to the upstream side. It is returned to the nth stage. In the present invention, it is preferable that a so-called back mixing occurs in which a vortex is locally wound in parallel with such a macroscopic flow direction of the reaction solution. In order to effectively generate such a stirring state, it has a disk that blocks the flow of the reaction liquid in the direction of the rotation axis near the center of the reactor, and the direction perpendicular to the direction of the rotation axis near the inner surface of the reaction vessel. It is preferable to use a turbine type blade that causes the above flow. The macro flow direction of the reaction solution is
It may be upward or downward, and a local vortex due to back mixing is pushed up or pushed down, so that the efficiently stirred reaction liquid is sent to the downstream direction.
The reaction liquid moved to the next block is similarly stirred by the next stirring blade, and is efficiently stirred by the number of stages of the attached blades. The number of stages of the stirring blades is 1 or more, preferably 2 to 15 stages. Further, the partition plate 5 may be installed between the stirring blades to improve the stirring efficiency. In that case, it is preferable that the partition plate is welded to the inner surface of the reaction container so that the reaction liquid moves through the gap between the partition plate and the rotary shaft. In addition to the flow type vertical reactor described above, as the reaction device usable in the step (I) of the present invention, any type of reactor can be used as long as it is a reactor suitable for continuous reaction. For example, a tubular reactor having a static mixer inside may be used, or a plurality of completely mixed reactors may be connected in series. The material of the reactor, the line, etc. is not particularly limited, but since an acid catalyst is used, a material having excellent corrosion resistance is preferable, and a SUS-based material is particularly preferably used. Further, the reaction temperature, that is, the temperature of the reaction liquid in the reactor can be preferably controlled by installing a jacket, a coil or the like through which steam or heat transfer oil can be circulated outside or inside the reactor.

<Feed Method> The method of feeding the raw material and the acid catalyst to the reactor is not particularly limited, but by adding unsaturated cyclic hydrocarbons to excess phenols, A phenol resin having good physical properties can be produced. For example, there is a method in which a phenol and an acid catalyst are continuously supplied from a tower bottom (or a top) of the reactor 1 through a line 12 and unsaturated cyclic hydrocarbons are continuously supplied from a side surface of the reactor through a line 13. Can be mentioned. Alternatively, phenols and unsaturated cyclic hydrocarbons may be mixed in advance, and the mixed solution may be supplied from one or a plurality of feed ports. Phenols and acid catalysts can be fed from separate feed ports,
It is also possible to previously mix the phenols and the acid catalyst in a predetermined ratio and supply the mixed solution from one feed port. Further, a plurality of each feed port may be provided.
One feed port for unsaturated cyclic hydrocarbons can be provided at any position on the side surface of the reactor, or a plurality of feed ports can be provided along the rotation axis direction as shown in FIG. The position of the feed port may be on the same plane as the rotating surface of the stirring blade, or may be in the middle between the stirring blade stages. It can also be provided in both of these positions.

<Monomer ratio> The molar ratio of unsaturated cyclic hydrocarbons to phenols supplied to the reactor is appropriately adjusted depending on the molecular weight and melt viscosity of the desired phenol resin. Usually, the range of phenols / unsaturated cyclic hydrocarbons = 1 to 20 (molar ratio) is preferable. Particularly, when the melt viscosity is lowered, the range of phenols / unsaturated cyclic hydrocarbons = 2 to 15 (molar ratio) is preferable. A phenol resin having a low melt viscosity and an epoxy resin derived from it are preferable because they can be filled with a filler at a high level when used as a semiconductor encapsulating material, have a small linear expansion coefficient, and have improved moisture resistance. When the amount of acid catalyst used is small, phenols / unsaturated cyclic hydrocarbons =
It is preferably 3 to 10 (molar ratio). By controlling in the above range, a phenol resin having good physical properties can be produced.

<Catalyst Amount> The amount of the acid catalyst supplied is preferably 0.05 to 1 mass% with respect to the total weight of the phenols, unsaturated cyclic hydrocarbons and acid catalyst supplied to the reactor. When a boron trifluoride / phenol complex is used, the boron trifluoride content is 0.05 to 1% by mass based on the total weight of unsaturated cyclic hydrocarbons, phenols and boron trifluoride / phenol complex. To do so. When the catalyst concentration is higher than 1% by mass, side reactions such as decomposition are likely to occur, which may affect the physical properties of the resin, which is not preferable. Further, if the catalyst concentration is less than 0.05% by mass, the reaction does not proceed sufficiently, and the resulting phenol resin may have low heat resistance, which is not preferable. A more preferable range of the acid catalyst concentration is 0.1 to 0.8% by mass. It is preferable that the catalyst concentration is within the above range with respect to the total weight of the phenols and the acid catalyst. That is, when the phenols and the acid catalyst are supplied from the bottom of the reactor and the unsaturated cyclic hydrocarbons are supplied from the side wall of the reactor, the catalyst concentration near the bottom of the reactor is substantially the concentration for the phenols. However, even in such a case, the catalyst concentration should be within the above range.

<Moisture / Atmosphere> In this reaction, since moisture has a great influence on the physical properties of the resin, the moisture concentration in the phenols and unsaturated cyclic hydrocarbons needs to be 200 ppm or less, preferably 100 ppm or less. Is. In particular, phenols easily contain water because they contain polar groups, and it is important to appropriately dehydrate water by a conventional method to control water. Unsaturated cyclic hydrocarbons are also preferably dehydrated before use. Also, the inside of the reaction system is usually replaced with an inert gas such as nitrogen or argon to prevent water from entering the system, and the amount of water in the reaction system is set to 200 ppm.
The following is essential.

<Reaction Control> In the phenol resin obtained by the method of the present invention, the main component is a 1: 2 adduct of unsaturated cyclic hydrocarbons and phenols, which is a compound having two phenolic hydroxyl groups. (Hereinafter, it may be referred to as a binuclear component.), But its generation mechanism is considered as follows. First, a 1: 1 adduct (having one phenolic hydroxyl group) is produced by the addition reaction of a phenol with an unsaturated cyclic hydrocarbon, and the phenol is further subjected to an addition reaction with the target dinuclear nucleus. It produces bodies or those with ether linkages. This ether bond product is an unfavorable component and is converted into the desired binuclear body by a rearrangement reaction.
It is important to control these addition reaction and rearrangement reaction. Particularly, by dividing the reactor into at least two reaction control regions on the upstream side and the downstream side and controlling the respective reaction conditions, a phenol resin having good physical properties can be efficiently produced. The first reaction control region on the upstream side is a region where the unsaturated cyclic hydrocarbons are continuously supplied to the place where the continuously supplied phenols and the acid catalyst are flowing, and are brought into contact with each other to carry out an addition reaction. And
The second reaction control region on the downstream side is a region for further advancing an addition reaction and causing a rearrangement reaction with respect to the reaction mixture obtained in the first reaction control region, thereby making the resin physical properties desired. When dividing the reaction region in this way, it is important to control the reaction temperature and the reaction time because they affect the physical properties of the resin and the production efficiency.

<Temperature of First Reaction Control Region> The reaction temperature of the first reaction control region is the melting point of phenols or 50 ° C.
Whichever is higher, up to 110 ° C. is preferred. The reaction progresses significantly slower at a temperature lower than the melting point of the phenols or 50 ° C, whichever is lower.
At a temperature higher than 0 ° C, low molecular weight impurities are generated due to decomposition of unsaturated cyclic hydrocarbons and the like, which is not preferable.

<Temperature of Second Reaction Control Region> The reaction temperature of the second reaction control region is preferably higher than that of the first reaction control region, and specifically, the range of 110 to 170 ° C. is preferable. In particular, a temperature of 140 to 150 ° C. is preferable because a resin having good resin physical properties, particularly heat resistance can be efficiently obtained. 1
When it exceeds 70 ° C, decomposition or side reaction of the catalyst occurs, and when it is less than 110 ° C, the progress of the reaction is delayed and the production efficiency is deteriorated, which is not preferable.

<Reaction time> First reaction control region and second reaction control region
The reaction time in the reaction control region is controlled by the liquid hourly space velocity LHSV (h ⁻¹ ) of the reaction liquid flowing in the reactor. In the first reaction control region, usually LHSV = 0.1-1
The range is 0, and more preferably LHSV = 0.3 to
8, more preferably LHSV = 0.5-6. By controlling in such a range, a phenol resin having good physical properties can be obtained. When the LHSV exceeds 10, the amount of unreacted substances increases, and when the LHSV is less than 0.1, the amount of heavy substances generated increases, which is not preferable because the production efficiency decreases. In the second reaction control region, the liquid space velocity of 0.
It is preferably set to 1 to 1 times, and more preferably 0.2 to 0.5 times.

<Division Method of Reaction Control Region> As a method of dividing into at least two reaction control regions as described above,
There are a method of dividing the temperature control region in one reactor and a method of using two or more reactors, but in either case, the reaction efficiency does not change and it is possible to produce a phenol resin having good physical properties. Either one can be selected according to the circumstances such as the installation space. In the case of a single reactor, the capacities of the first reaction control region and the second reaction control region are divided so that the liquid hourly space velocity has a predetermined ratio, and each reaction is controlled by a temperature control device provided in each reaction control region. The temperature can be controlled. For example, when the reaction is performed in an upflow, LHSV of the first reaction control region / LHS of the second reaction control region
When V = 3/1, the region under the reactor corresponding to 1/4 of the total volume of the reactor is the first reaction control region and the remaining 3 /
The region of the upper portion of the reactor corresponding to 4 is set as the second reaction control region, and the reaction temperature in each reaction control region is controlled. Two
When connecting two reactors in series, the volumes of the first reactor corresponding to the first reaction control region on the upstream side and the second reactor corresponding to the second reaction control region on the downstream side are set in each reaction control region. It is possible to control the entire reaction by setting the liquid hourly space velocity to a predetermined ratio and controlling the temperature in each reactor. An example of this is shown in FIG. In FIG. 2, a mixture of phenols and an acid catalyst is supplied from the line 12 to the bottom of the first reactor 1-A, and unsaturated cyclic hydrocarbons are supplied from the line 13 at a plurality of points in the first reactor 1-A side surface. Is being supplied to. The reaction liquid extracted from the top of the first reactor 1-A via the line 14 is continuously supplied to the second reactor 1-B from the bottom. In FIG. 2, the volumes of the first reactor and the second reactor are provided so that the liquid hourly space velocity has a predetermined ratio. Second reactor 1-B
The reaction liquid is withdrawn from the top of the line through line 15 and sent to the next step. When three or more reactors are used, they may all be connected in series or partly connected in parallel. The number of reactors is preferably 2 to 5 from the viewpoint of easy reaction control. Further, it is preferable to control the reaction temperature by connecting the reactors via a heat exchanger between the reactors.

<Pressure> The reaction pressure is usually 0.01 to 20M.
The pressure is in the range of Pa, preferably under a pressure of 0.1 to 1 MPa. By performing the reaction within these pressure ranges, a resin having high reaction efficiency and good physical properties can be produced.

<Phenol Resin Composition and Physical Properties> Here, the phenol resin produced by the method of the present invention will be described. Regarding the resin composition, when the phenol resin is used as a resin for encapsulating material, it exhibits excellent curability and moldability, and further exhibits excellent heat resistance and moisture resistance after curing. It is preferable to control

(Dinuclear component) The main component in the phenolic resin is a 1: 2 adduct of unsaturated cyclic hydrocarbons and phenols, which is a compound having two phenolic hydroxyl groups (hereinafter referred to as a dinuclear compound). It may be referred to as a body component), but its content has a great influence on the viscosity, fluidity, curability, etc. of the resin, so it is important to adjust it appropriately. As the content of the binuclear component in the phenol resin,
30-90 mass% is mentioned preferably, and especially 40-80.
It exhibits preferable curing characteristics in the range of mass%. When the content of the binuclear component is less than 30% by mass, the fluidity of the resin is lowered to deteriorate the moldability, and when it is more than 90% by mass, the fluidity is good but the crosslinking density after curing is high. It is not preferable because it decreases. The amount of the binuclear component can be controlled mainly by the reaction molar ratio of the phenol and the unsaturated cyclic hydrocarbon, and it is preferable to control the amount of the binuclear component by appropriately adjusting the molar ratio.

(Monofunctional component) The content of the monofunctional component in the phenol resin is preferably 2% by mass or less. The monofunctional component has only one phenolic hydroxyl group, and is a 1: 1 adduct of a phenol and an unsaturated cyclic hydrocarbon (A component), or a phenol and an unsaturated cyclic hydrocarbon. Examples thereof include 2: 1 adducts having an ether bond (component B). In particular, the content of the component A in the resin is preferably 1.5% by mass or less, the content of the component B is 0.5% by mass or less, and further, the component A is 1% by mass or less and the component B is It is preferably 0.2% by mass or less. Beyond those ranges,
It is not preferable because the heat resistance of the resin may decrease.
The amount of the monofunctional component can be controlled by the amount of catalyst in the reaction step, the reaction temperature and LHSV, and can be adjusted in the concentration step (removal / recovery of unreacted raw materials) described later. After the completion of the reaction step, if the production amounts of component A and component B are less than 2% by mass and less than 1.5% by mass of the total resin, respectively, the monofunctional component is efficiently reduced in the subsequent concentration step. You can

(Viscosity) Further, since the resin viscosity has a great influence on the flow characteristics during molding, it is necessary to adjust it appropriately. Although the viscosity is not particularly limited, for example, by the Canon-Fenske kinematic viscosity tube method,
It is effective to grasp the solution viscosity of a 50% resin solution of n-butanol.
It is preferably in the range of 250 mm ² / s, especially 7
The compounds controlled in the range of 0 to ²⁰⁰ mm ² / s exhibit favorable flow characteristics.

(Phenolic Hydroxyl Content) Further, the phenolic hydroxyl content in the resin affects the curing characteristics and the like, so it must be adjusted appropriately. Although there are no particular restrictions on the definition of the phenolic hydroxyl group content,
For example, the equivalent of hydroxyl groups in the resin measured by the alkaline back titration method of the acetylated product in a pyridine-acetic anhydride solution is 16
The range of 0 to 200 g / eq is preferable, and 165-1 is particularly preferable.
The resin adjusted to 90 g / eq not only exhibits favorable curing characteristics, but also has good balance with fluidity and very good handling during molding. According to the production method of the present invention, it is possible to produce a phenolic resin satisfying the above resin physical properties.

<Reaction Stopping Step (II)> Next, the reaction stopping step will be described. The reaction solution continuously withdrawn from the reactor contains unreacted raw materials and acid catalysts in addition to the produced phenolic resin, so the reaction must be stopped first to achieve the desired resin physical properties. It is important to let
As a method of stopping the reaction, there are a method of deactivating the acid catalyst in the reaction solution with a deactivator, and a method of removing and recovering the acid catalyst without deactivating it. As the processing method, either a batch method or a continuous method can be adopted.
They are appropriately selected in consideration of the installation location of the device and the efficiency of the entire process. In any of the methods and systems in this step, it is preferable that the residual amount of ionic impurities such as boron and fluorine in the finally obtained phenol resin is 100 ppm or less.

<Reaction Termination by Deactivator> When the acid catalyst is deactivated by the deactivator, examples of the deactivator include alkali metals, alkaline earth metals or their oxides, hydroxides, carbonates and water. Inorganic bases such as ammonium oxide and ammonia gas can be used. Especially, hydrotalcites and sodium hydroxide can be treated quickly and simply, and the residual amount of ionic impurities after treatment is small. It is preferably used. The method of contacting the reaction liquid with the quenching agent is not particularly limited, but it affects the physical properties of the resin, and therefore it is important to devise a method for making efficient contact.

<Batch type treatment> As a method of performing the deactivation treatment in a batch type, for example, a deactivation tank filled with a deactivator is separately prepared, and the reaction solution discharged from the reactor for a certain period of time is batched therein. The method of injecting is mentioned. The amount of the deactivator is preferably used in excess with respect to the amount of acid catalyst in the reaction solution to be deactivated. For example, boron trifluoride as a catalyst
When using a phenol complex and hydrotalcites as a deactivator, the deactivator amount (weight) is 1.2 to 1 of the catalyst.
The amount is preferably 0 times by mass, more preferably 1.5 to 5 times by mass. If the amount is less than 1.2 times by mass, the deactivation efficiency is poor and the undeactivated catalyst may remain in the system to cause corrosion of the apparatus or adversely affect the properties of the obtained resin, which is not preferable. . Further, if the amount used exceeds 10 times by mass, the working efficiency in the step of removing the deactivator and the catalyst residue remarkably decreases, which is not preferable.

<Continuous Treatment> As a method for carrying out the deactivation treatment in a continuous manner, for example, a vertical deactivation tower filled with a solid deactivator is used to continuously feed the reaction liquid extracted from the reactor. The method of distribution is mentioned. An example is shown in FIG. FIG. 3 shows a case where the first reactor 1-A and the second reactor 1-B are used. The reaction liquid from the second reactor 1-B is supplied from the top of the deactivation tower 6 via the line 15, the reaction liquid after deactivation is extracted from the bottom in the line 16, and then the concentrator 7 is supplied.
The unreacted raw material is fed from the line 17 and the phenol resin is fed from the line 18 at the top. The form of the deactivation column is not particularly limited, but the ratio of the inner diameter D to the length L, so-called L / D, which is a vertical cylinder, is 1 to 30, preferably 1 to 25, and more preferably 2 to. The catalyst can be deactivated efficiently by using 20. L / D
When is less than 1, a portion with a short contact time is locally generated, and efficient deactivation of the catalyst cannot be performed, and L / D is 30.
If it exceeds, there is a risk of pressure increase, which is not preferable.
The shape and the like of the solid deactivator packed in the deactivation tower are not particularly limited, but they are powdery or granular and have an average particle size of 3
It is preferably 0 to 1500 μm, an effective surface area of 50 m ² / g or more, and a bulk density of 2 cm ³ / g or more. If the average particle size is small or the effective surface area is large, there is a risk of pressure increase or clogging during the flow of the reaction solution.If the average particle size is large or the effective surface area is small, the contact efficiency with the reaction solution is low, In either case, the efficiency of the deactivation treatment is deteriorated, which is not preferable. Further, as a solid deactivator,
Those that have the ability to deactivate and adsorb the catalyst and remove impurities derived from the catalyst from the reaction solution are preferable, and for example, hydrotalcites can be preferably used. Liquid space velocity LH when flowing the reaction liquid through the deactivation tower
SV (h ⁻¹ ) is usually controlled in the range of 0.1 to 10, more preferably 0.3 to 8, and even more preferably 0.
It is 5-6. When the LHSV exceeds 10, the deactivation of the catalyst becomes insufficient and the residual amount of the catalyst residue in the resin also increases, which is not preferable. If LHSV is less than 0.1, the amount of treatment per unit time decreases, which is not preferable. The deactivation temperature is appropriately selected in the range of 30 to 150 ° C, but is preferably 50 to 100 ° C from the viewpoint of production efficiency. When the temperature is lower than 30 ° C, there is a problem that the adsorption ability is lowered and the deactivation becomes insufficient, and when the temperature is higher than 150 ° C, the deactivator may be destroyed, which may cause a line clogging or the like. Absent.

<Catalyst Removal by Decompression / Heating> As a method of substantially stopping the reaction without deactivating the acid catalyst, for example, the reaction solution is put in a catalyst recovery apparatus as shown in FIG. 4 as one embodiment. A method of continuously circulating and continuously removing and recovering the catalyst can be mentioned. Hereinafter, FIG. 4 will be described.

(Catalyst Separation Tower) FIG. 4 shows an embodiment comprising a catalyst separation tower 8, a catalyst recovery tank 9, a purification line 10 and a condenser 11 as a catalyst recovery device. The form of the catalyst separation column 8 is not particularly limited, but the number of effective theoretical plates is 3 to 50.
Stages are preferred, and more preferably in the range of 5 to 20 stages. In order to improve the separation efficiency, a filler is filled inside the catalyst separation column as needed. The filler is not particularly limited, but from the viewpoint of corrosion resistance to acid catalysts and the like, mercarbo type packing, meladur type packing, etc. are preferably used. The system temperature is 100 to 200 ° C., preferably 1
Controlled in the range of 30 to 160 ° C., the system pressure is 1 to 10
0, preferably 13 kPa (100 torr) to 66.
Control is performed within a range of 5 kPa (500 torr). The reaction liquid obtained in the reaction step is fed from the upper part of the catalyst separation tower to the line 19
(This is connected to the line 14 of FIG. 1 or the line 15 of FIG. 2), and an inert gas is fed from a lower part of the catalyst separation column through a line 20. The inert gas is not particularly limited, but usually nitrogen or argon is preferably used. The reaction liquid moves to the lower side of the catalyst separation column, and the inert gas moves to the upper side in the opposite direction to the flow of the reaction liquid. There, the reaction solution and the inert gas come into contact with each other, and the acid catalyst is efficiently separated from the reaction solution. The separated acid catalyst is discharged together with the inert gas from the top of the catalyst separation column through a line 21. At that time, a part of the unreacted raw material is also discharged at the same time. When the inert gas is not flowed, the acid catalyst once separated stays inside the catalyst separation column and is contacted with the continuously flowing reaction solution to be redissolved and absorbed again to efficiently separate the catalyst components. It is not preferable because it will not be possible. The separation efficiency of the acid catalyst can be controlled by adjusting the feed amount of the inert gas. The residual amount of boron or fluorine in the catalyst-removed reaction liquid obtained through the line 22 from the bottom of the catalyst separation column is preferably 500 ppm or less. 500ppm
Even if the temperature exceeds the limit, the next step is to remove unreacted raw materials.
Although it can be used in the recovery step, it is not preferable because the impurity concentration in the final product becomes high.

(Catalyst Recovery Tank) The acid catalyst and the inert gas discharged from the top of the catalyst separation tower and a part of the unreacted raw materials are recovered, reused or discarded as necessary. When recovering the acid catalyst, the mixed gas discharged from the top of the catalyst separation tower 8 through the line 21 is introduced into the catalyst recovery tank 9 filled with phenols to allow the phenols to absorb the acid catalyst. It is preferable to carry out. The catalyst recovery tank is a cylindrical container having a rotating shaft in the center and a plurality of stirring blades extending in a direction perpendicular to the rotating shaft. The rotating shaft is directly or indirectly connected to the motor. It is preferable to use the one equipped with a stirring blade having a function of rotating and stirring the contents. The ratio L / D of the inner diameter D and the length L of the catalyst recovery tank is 3 to 30, and preferably 5 to 5.
Twenty. If L / D is less than 3, the distance from the introduction part of the mixed gas to the upper surface of the liquid becomes short, and the catalyst gas may jump out to the space before the absorption is completed.
When it is 0 or more, the reaction tank and the rotating shaft become long, and the operation may be deviated from the center line of the rotating shaft due to long-term operation.
Further, the motor energy for stirring becomes large, which is not preferable. In addition, in order to maximize the stirring efficiency by maximizing the contact time between the phenols filled in the catalyst recovery tank and the mixed gas and maximizing the stirring efficiency, install a mixed gas inlet between the bottom of the catalyst recovery tank and the stirring blade. Is preferred.
The temperature of the catalyst recovery tank is preferably in the range of 50 to 120 ° C. More preferably, it is performed at 70 to 100 ° C. If the temperature is lower than 50 ° C, the viscosity becomes high and the stirring efficiency becomes poor, and if the temperature exceeds 120 ° C, the acid catalyst tends to volatilize and the efficient dissolution in the phenols is hindered, which is not preferable. The acid catalyst absorbed by the phenols and recovered can be reused in the reaction step. Therefore, it is necessary to efficiently absorb the entire amount in the absorption step without deactivating the acid catalyst. In particular, it is preferable to carry out the following procedure. That is, the amount of phenols filled in the catalyst recovery tank is preferably such that the acid catalyst content calculated by the following formula is 30% by mass or less. Acid catalyst content (mass%) = (acid catalyst amount k used in reaction k
g / (phenol loading amount + catalyst kg)) × 100 When the acid catalyst content exceeds 30 mass%, the absorption efficiency becomes low due to the solubility of the acid catalyst in the phenols, and the recovery of the acid catalyst becomes difficult. Is not preferable. Phenols that have dissolved and absorbed acid catalysts in the catalyst recovery tank are transferred to the reactor or raw material storage tank and reused in the reaction process, but the phenols and acid catalysts supplied to the reactor are in specified amounts. Thus, it is preferable to appropriately adjust the concentration based on the above-mentioned acid catalyst content.

(Catalyst Disposal Treatment) On the other hand, when it is necessary to discard the catalyst discharged from the catalyst separation column due to a long-term operation stop, etc., a deactivator may be appropriately used for treatment. As the deactivator, for example, when boron trifluoride is used as a catalyst, an aqueous solution of silver chloride, an aqueous solution of sodium hydroxide or the like can be used.

(Purification Treatment) Since the reaction liquid discharged from the bottom of the catalyst separation tower 8 usually contains almost no catalyst component, it can be used as it is in the next step of removing and recovering unreacted raw materials. The purification treatment may be appropriately performed in consideration of the possibility that a slight amount of catalyst component remains. The purification treatment is not particularly limited, but it is preferable to use a means such that the residual amount of ionic impurities such as boron and fluorine in the finally obtained phenol resin is 100 ppm or less. For example, a purification tower filled with a solid deactivator or
The purification line 10 shown in can be used. The deactivator is not particularly limited as long as it deactivates and adsorbs the acid catalyst, but alkali metals, hydrotalcites and the like are preferable. Since the reaction solution transferred from the catalyst separation tower contains almost no acid catalyst, the purification line 10
It does not particularly hinder the distribution in the case of processing through such as.

<Step of Removing Deactivator> (Filtration) When the reaction stopping operation is carried out in a batch method using the deactivator,
A step of removing the quenching agent and the like is required. The means for separating / removing the quenching agent from the reaction solution is not particularly limited, but filtration is preferable from the viewpoint of work efficiency and versatility of the apparatus. The filtering means is not particularly limited, but as the filtering device, a spakler type, a funder back type, or a Rosenmund type with a scraping device for discharging the cake after filtration is preferably used. The filtration conditions are not particularly limited, but from the viewpoint of work efficiency of filtration, it is preferable to carry out filtration at 30 to 150 ° C, and more preferably 50 to 120 ° C. Further, although the filtration can be carried out under normal pressure,
The filtration rate may be appropriately adjusted by pressurizing or depressurizing.
Incidentally, when the reaction stop operation is carried out by circulating a deactivation tower filled with a solid deactivator, or when the reaction stop operation is carried out by heating under reduced pressure to remove the acid catalyst, the above operation such as filtration is not necessarily required. Is not necessary, but may be appropriately implemented.

<Unreacted raw material removal / collection process (III)>
(Concentration step) The reaction liquid that has undergone the reaction stopping step and the step of removing the deactivator and the like is then provided to a step for removing and recovering unreacted raw materials (hereinafter, sometimes referred to as concentration). It FIG. 4 shows an embodiment using the concentrator 11 as an example. In FIG. 4, the reaction liquid is supplied to the top of the concentrator 11 from the purification line 10 through the line 23, and the line 24 is supplied from the upper portion.
Thus, the unreacted raw material is obtained, and the phenol resin is obtained through the line 25 from the bottom. Concentration conditions are not fixed under the conditions of temperature and pressure in the concentration system and vapor pressure, but efficient concentration can be achieved under the following conditions. That is, the temperature in the system is not particularly limited as long as it does not cause the decomposition of the resin, but is preferably 250 ° C. or lower, more preferably 18 ° C. or lower.
It is in the range of 0 to 220 ° C. The pressure in the system may be any of normal pressure, reduced pressure, and increased pressure, but it is preferable to reduce the pressure in the system in order to carry out the concentration smoothly and quickly in the above temperature range. Specifically, 66.5 kP
The range of a (500 torr) or less is preferable, and particularly 40
It is preferably kPa (300 torr) or less.
Furthermore, in order to efficiently remove unreacted phenols and monofunctional components, it is preferable to blow nitrogen or high-pressure steam into the system under reduced pressure conditions. The pressure of the steam introduced into the system is not particularly limited, but specifically, the range of 0.3 to 2 MPa is preferable, and the blowing operation is more preferably performed in the range of 0.5 to 1.5 MPa. In this case, the impurities can be removed efficiently. The concentration method is not particularly limited, but the following example can be given as a method of performing concentration in a batch system. The reaction liquid that has undergone the reaction stopping step and the step of removing the deactivator, etc. is transferred to a kettle for concentration, and heating is started, and at the same time, the pressure in the system is continuously reduced. When the temperature in the system reached 200 ° C, the system was fully depressurized to 13 kPa (100 torr).
Below. After concentrating for an arbitrary time in this state, it is preferable to further inject nitrogen or high-pressure steam into the system under reduced pressure. Further, a method of continuously concentrating can also be adopted as an efficient concentration method. For example, a thin film distiller is used, and although not particularly limited, it is possible to raise the temperature in the system to at least 200 ° C. and the pressure in the system to 13 kPa (100 tons).
Those that can be set to rr) or less are preferable. In the present invention, each of the above-mentioned concentration methods may be carried out independently, but a batch type concentrator or a plurality of continuous type concentrators may be connected, or preconcentration by a batch type concentrator to main concentration by a continuous type concentrator. It is possible to further improve the concentration efficiency by a combined method such as The end point of concentration is GP
Determined by confirming the amount of unreacted phenols and monofunctional components in the resulting phenolic resin by C analysis. The content of unreacted phenols is not particularly limited, but from the viewpoint of the environment when using the resin, the residual amount in the resin is preferably 500 ppm or less, more preferably 200 ppm or less. , And more preferably 100 ppm or less. Further, as described above, it is preferable to control the content of the monofunctional component.

<Uses of Phenolic Resin> The phenol resin obtained as described above is used as a raw material for epoxy resin because of its excellent heat resistance, and also as an electrical insulating material.
In particular, it is useful as a curing agent for epoxy resin for semiconductor encapsulating materials or laminated plates, but its use is not particularly limited.

<Epoxidation> Next, a method for producing an epoxy resin will be described. (Glycidylation reaction) The epoxy resin can be obtained by reacting the above-mentioned phenol resin with epihalohydrins in the presence of a base catalyst to glycidylate.
The glycidylation reaction can be carried out by a conventional method.
Specifically, for example, in the presence of a base such as sodium hydroxide or potassium hydroxide, a phenol resin is usually added to glycidyl such as epichlorohydrin or epibromhydrin at a temperature of 10 to 150 ° C, preferably 30 to 80 ° C. It can be obtained by reacting with an agent and then washing with water and drying. The amount of the glycidylating agent used is preferably 2 to 20 times the molar equivalent of the phenol resin, and particularly preferably 3
~ 7 times molar equivalents. Further, during the reaction, the water can be distilled off by azeotropic distillation with a glycidylating agent under reduced pressure, so that the reaction can proceed faster. (Washing) When the epoxy resin is used in the electronic field, salts such as sodium chloride produced as a by-product must be completely removed in the water washing step. At this time, the unreacted glycidylating agent may be recovered by distillation to concentrate the reaction solution, and then the concentrate may be dissolved in a solvent and washed with water. Preferred solvents include methyl isobutyl ketone, cyclohexanone, benzene, butyl cellosolve and the like. The concentrate washed with water is concentrated by heating.

<Physical properties of epoxy resin> Physical properties of epoxy resin
As for, epoxy resin was used as the resin for the sealing material
In some cases, it shows excellent curability, moldability, etc., and is excellent after curing
In order to impart heat resistance, moisture resistance, etc.,
It is important to control the physical properties of oil. Two core components are green
Compound with two sidyl groups added (hereinafter referred to as binuclear epoxy
(Sometimes expressed as a chemical component) in the epoxy resin
The amount has a great influence on the viscosity, fluidity and curability of the resin.
Therefore, it is important to make appropriate adjustments. Epoxy resin
The content of the binuclear epoxidation component in the composition is 30 to 9
0 mass% is preferable, and the range of 40 to 80 mass% is particularly preferable.
Good When it is less than 30% by mass, the fluidity is lowered and the composition is cured.
It greatly affects the moldability of the product, and is more than 90% by mass.
Good flowability, but low crosslink density
It is not preferable because it deteriorates the curing property. Resin viscosity
Moderately affects the flow characteristics during molding, so it should be adjusted appropriately.
Need to save. There is no particular limitation on this viscosity regulation.
Although it is not done, for example Canon-Fenske movement
50% resin dissolution of 1,4-dioxane by viscous tube method
It is effective to grasp the solution viscosity of the liquid, and
100 mm in solution viscosity ^Two/ S or less range is preferred
Especially 70mm^Two/ S controlled compound within the range
The article exhibits favorable flow characteristics. E in epoxy resin
The content of poxy groups is usually 200 to 500 g / gram equivalent.
Amount, preferably 250-450 g / gram equivalent
Is desirable. Epoxy group content is 500 g / gram equivalent
In the above cases, the crosslinking density becomes too low, which is preferable.
No According to the production method of the present invention, the above physical properties are
A satisfactory epoxy resin can be produced.

<Use of Epoxy Resin> The epoxy resin thus obtained is superior in heat resistance to the epoxy resin having a similar structure obtained by the conventional method, and particularly excellent in solder crack resistance. The semiconductor encapsulation material application is extremely useful because of its advantages. Further, it is also useful as a raw material for an epoxy resin composition for a laminated board, and can be used as a varnish or the like for an electric laminated board due to its excellent solubility of the epoxy resin in a solvent.

[0056]

EXAMPLES The present invention will be described in detail below with reference to Examples and Comparative Examples. The characteristics of the phenolic resin in the following examples and comparative examples were measured by the following methods. 1) amount of dinuclear component, amount of dinuclear epoxidized component, and amount of monofunctional component 1% by mass THF solution of phenol resin,
It was detected by a differential refraction detector "WATERS 410" manufactured by RS Co., Ltd. and measured using a high performance liquid chromatography manager "Millennium" manufactured by the same company. 2) Solution viscosity Siz in a constant temperature bath controlled at 25 ° C. according to the Canon-Fenske kinematic viscosity tube method described in ASTM D446.
e No. It was measured using a 300 viscosity tube. In addition,
For measurement of phenolic resin, n-butanol 50%
The resin solution and the epoxy resin were measured using a 1,4-dioxane 50% resin solution. 3) The phenol resin obtained by OH equivalent production was heated to reflux in a pyridine-acetic anhydride mixed solution, and the solution after the reaction was determined by back titration with potassium hydroxide. 4) Softening point The softening point was measured according to the ring and ball softening point measuring method described in JIS K2207. 5) Boron content Using a sequential type high frequency plasma emission spectrometer ICPS-1000II type manufactured by Shimadzu Corporation
It was measured by comparing a 5% n-butyl cellosolve solution with a standard solution. 6) Fluorine content Using a wick bolt type combustor manufactured by Heraeus (Germany), after burning a 20% acetone solution of the resin, increase and decrease in pH due to the fluorine content absorbed in the sodium carbonate solution was changed to HORIBA, Ltd. It was measured by examining with an ion meter N-8M manufactured by Seisakusho.

Example 1 (Production of Phenolic Resin (I)) As shown in FIG. 2, an apparatus in which a first reactor 1-A and a second reactor 1-B were connected in series was used. The reactor was a tank reactor with L / D = 5/1 equipped with four stirring blades and a partition plate between them, and the internal volume was 1 liter for the first reactor and 3 liters for the second reactor. used. Phenol and dicyclopentadiene were used as raw materials, and it was previously confirmed that the water content was 100 ppm or less. Also, the water content in the reaction system is 100 p
It was confirmed that it was pm or less. As the acid catalyst, a boron trifluoride phenol complex was used and was dissolved in the starting phenol at a concentration of 0.3 mass% in advance. Phenol in which the acid catalyst was dissolved was continuously supplied at 1880 g (20 mol) / h from the bottom of the first reactor 1-A through the line 12, and the inside of the first reactor was controlled at 70 ° C. Dicyclopentadiene was continuously added via line 13 from four points on the side surface of the first reactor 1-A at a total of 264 g (2 mol) / h. Line 14 from the top of the first reactor 1-A
The reaction liquid discharged by means of the above was continuously circulated as an upflow from the bottom of the second reactor 1-B controlled at 140 ° C. As a result of analyzing the reaction liquid extracted through the line 15 from the top 1-B of the second reactor, the monofunctional component was 2.2% by mass (1.2% by mass of the component A and B).
Was 1.0 mass%). The reaction liquid discharged from the top of the second reactor 1-B was continuously charged in a 20 liter separable flask filled with 100 g of hydrotalcites (trade name KW-1000) while maintaining 80 ° C. It was injected for 6 hours and stirred at the same temperature for 2 hours to deactivate the catalyst. The reaction liquid from which the deactivator and the catalyst residue were removed by filtration was heated at 190 ° C. under a reduced pressure of 13 kPa (100 torr).
Unreacted phenol was removed by distillation and concentration for 7 hours to obtain 3490 g of phenol resin (I). A production time of 18 hours was required from the start of the addition of dicyclopentadiene, and the production amount per unit time was about 194 g / h. The obtained phenol resin has a softening point of 92.5 ° C., a phenolic hydroxyl group equivalent of 169 g / eq, and a solution viscosity of 89 mm ^2.
Was / s. Further, the content of the binuclear component was 67% by mass, and the content rate of the monofunctional component was 1.4% by mass (component A was 1.1% by mass, component B was 0.3% by mass). Further, boron was 50 ppm and fluorine was 18 ppm. As described above, the resin having the desired physical properties could be efficiently obtained without any particular problem.

Example 2 (Production of Epoxy Resin (I)) Example 1 was placed in a 3-liter four-necked flask equipped with a stirrer, a reflux condenser and a thermometer.
After charging 169 g of the phenol resin (I) produced in 1 above and 400 g of epichlorohydrin, the mixture was stirred and dissolved. The pressure in the reaction system was adjusted to 20 kPa (150 torr) and the temperature was raised to 68 ° C. 100 g of sodium hydroxide aqueous solution having a concentration of 48% by mass was continuously added thereto and reacted for 3.5 hours. The water generated by the reaction and the water of the sodium hydroxide aqueous solution were decomposed by refluxing the water-epichlorohydrin azeotrope, and continuously removed outside the reaction system. After the reaction is completed, the reaction system is returned to normal pressure, 110 ° C
The temperature was raised to and the water in the reaction system was completely removed. Excess epichlorohydrin was distilled off under normal pressure, and further 2 kPa
Distillation was performed at 140 ° C. under a reduced pressure of (15 torr).
300 g of methyl isobutyl ketone and 36 g of a 10 mass% sodium hydroxide aqueous solution were added to the resulting mixture of the resin and sodium chloride, and the mixture was reacted at 85 ° C. for 1.5 hours. After completion of the reaction, methyl isobutyl ketone 750
g and 300 g of water were added, and the lower layer sodium chloride aqueous solution was separated and removed. Next, 150 g of water was added to the methyl isobutyl ketone liquid layer to wash it, and the solution was neutralized with phosphoric acid to separate the aqueous layer, and then washed with 800 g of water to separate the aqueous layer. The oil layer and the water layer have good separability, and after quantitatively recovering the inorganic salt, the methyl isobutyl ketone liquid layer is distilled under normal pressure, followed by vacuum distillation at 140 ° C. at 0.67 kPa (5 torr) to give 216 g. The epoxy resin (I) of was obtained. The obtained epoxy resin has an epoxy equivalent of 263 g.
/ Eq, the solution viscosity was 25 mm ² / s, the content of the binuclear epoxidized component was 53% by mass, and a resin having desired physical properties was obtained without any particular problem.

Example 3 (Production of Phenol Resin (II)) As shown in FIG. 3, thin film distillation was performed as the first reactor 1-A, the second reactor 1-B, the deactivation tower 6 and the condenser 7. A device in which the vessels were connected in series was used. The same reactor as in Example 1 was used. The deactivation tower is a cylindrical container having an internal volume of 2 liters, L / D = 10/1, and inside has hydrotalcites having an average particle diameter of 50 μm and a bulk specific gravity of 2.2 cc / g (trade name: KW-1000). Was used. Further, a jacket capable of circulating hot water or heat transfer oil was attached around the reactor and the deactivation tower for temperature control. The reaction was started in the same manner as in Example 1. The reaction liquid discharged from the top of the first reactor was then continuously circulated with an upflow from the bottom of the second reactor whose temperature was controlled at 140 ° C. As a result of analyzing the reaction liquid extracted from the top of the second reactor, the monofunctional component was 2.2% by mass (1.3% by mass of component A and 0.9% by mass of component B) with respect to the resin. ) Was included. The reaction liquid discharged from the top of the second reactor was allowed to flow downflow from the top of the deactivation tower controlled at 90 ° C. The reaction liquid discharged from the bottom of the deactivation tower was 13 kPa in the thin film distiller.
(100 torr), 210 ° C., 1 liter /
The molten resin from which unreacted phenol had been removed by concentrating with h was continuously recovered from the bottom of the thin film distiller. 4 hours after the start of the addition of dicyclopentadiene, the molten resin started to flow out from the bottom of the thin film distillation apparatus, and after 3 hours, 3450 g.
Of phenol resin (II) was recovered. The production amount per unit time was 345 g / h. The obtained phenol resin has a softening point of 92 ° C. and a phenolic hydroxyl group equivalent of 17
The solution viscosity was 0 g / eq and the solution viscosity was 90 mm ² / s. Further, the content of the binuclear component is 66% by mass, the content rate of the monofunctional component is 1.5% by mass (component A is 1.1% by mass, component B is
Was 0.4% by mass). Also, boron is 60 pp
m and fluorine were 20 ppm. As described above, the resin having the desired physical properties could be efficiently obtained without any particular problem.

<Example 4> (Production of epoxy resin (II)) The same operation as in Example 2 was carried out except that 170 g of the phenol resin (II) synthesized in Example 3 was used, and 215 g of the epoxy resin (II) ) Got. The obtained epoxy resin has an epoxy equivalent of 264 g.
/ Eq, the solution viscosity was 25 mm ² / s, the content of the binuclear epoxidized component was 54% by mass, and a resin having desired physical properties was obtained without any particular problem.

Example 5 (Production of Phenol Resin (III)) As shown in FIG.
A reactor 1-A, a second reactor 1-B, a catalyst separation tower 8, a catalyst recovery tank 9, a purification line 10 and a condenser 11 were used, and a thin film distillation apparatus was connected in series. The reactor is Example 1
Used the same. The catalyst separation column used had a capacity of 1 liter, L / D = 10/1, and was filled with a filler inside, and a nitrogen feed line was connected to the bottom of the catalyst separation column. Further, an absorption tank for recovering the acid catalyst contained in the gas discharged from the top of the catalyst separation tower was provided. The catalyst recovery tank has a capacity of 5 liters and is equipped with a stirrer and a jacket and a coil through which heat oil can be circulated. The catalyst recovery tank is filled with 3 liters of phenol to dissolve the acid catalyst. did. The reaction was started in the same manner as in Example 1. The reaction liquid discharged from the top of the second reactor was allowed to flow downflow from the upper part of the catalyst separation column controlled at 150 ° C. 2m from the bottom of the catalyst separation tower
Nitrogen gas was fed at ³ / h to cross-flow the reaction liquid and nitrogen gas. The gas containing the acid catalyst discharged from the top of the catalyst separation column was introduced into a catalyst recovery tank whose liquid temperature was maintained at 120 ° C., and the acid catalyst was continuously dissolved and recovered while stirring. The reaction liquid discharged from the bottom of the catalyst separation column was passed through a purification line for the purpose of surely removing the catalyst component, and then, in a thin film distiller, at 13 kPa (100 torr),
The molten resin from which unreacted phenol had been removed by concentrating treatment at 1 liter / h under conditions of 10 ° C. was continuously recovered from the bottom of the thin film distiller. Four hours after the start of the addition of dicyclopentadiene, the molten resin began to flow out from the bottom of the thin-film distiller, and after 10 hours, 3470 g of phenol resin (II
I) was recovered. The production amount per unit time is 347 g /
It was h. The obtained phenolic resin has a softening point of 95.
C., the phenolic hydroxyl group equivalent was 170 g / eq, and the solution viscosity was 90 mm ² / s. Further, the content of the binuclear component is 65% by mass, and the content of the monofunctional component is 1.5% by mass.
(Component A is 1.1 mass%, Component B is 0.4 mass%). Also, boron is 52 ppm and fluorine is 16 ppm.
Met. When the concentration of the acid catalyst in the phenol charged in the catalyst recovery tank was measured, it was 10.4% by mass, and most of the catalyst used was recovered. As described above, the resin having the desired physical properties could be efficiently obtained without any particular problem.

<Example 6> (Production of epoxy resin (III)) Example 2 except that 170 g of the phenol resin (III) synthesized in Example 5 was used.
182 g of epoxy resin (III)
Got The obtained epoxy resin has an epoxy equivalent of 25.
4 g / eq, the solution viscosity was 17 mm ² / s, the content of the binuclear epoxidized component was 66% by mass, and a resin having desired physical properties was obtained without any particular problem.

Example 7 (Production of Phenol Resin (IV)) Phenol in which the acid catalyst was dissolved was used in the catalyst recovery tank of Example 5, and phenol and boron trifluoride / phenol complex were newly added. Then, the production was performed in the same manner as in Example 5 except that a phenol solution of 0.3 mass% of boron trifluoride / phenol complex catalyst was prepared and used. After starting the addition of dicyclopentadiene, the operation was carried out for 10 hours to obtain 3390 g of phenol resin (IV). The production amount per unit time is 339g
Was / h. The obtained phenolic resin has a softening point of 9
1.5 ° C., phenolic hydroxyl group equivalent 170 g / eq,
The solution viscosity was 89 mm ² / s. Further, the content of the binuclear component is 65% by mass, and the content of the monofunctional component is 1.6.
It was mass% (1.2 mass% of component A, 0.4 mass% of component B). As described above, a resin having desired physical properties could be efficiently obtained without any particular problem.

Comparative Example 1 (Production of Phenol Resin (V)) 5640 g (60 mol) of phenol was charged into a glass separable flask having a capacity of 10 liter equipped with a stirrer and a cooling coil, and trifluoride was added. After 16 g of the boron-phenol complex was added and homogenized, 792 g (6 mol) of dicyclopentadiene was gradually dropped from the dropping funnel while maintaining the liquid temperature at 80 ° C. to carry out the reaction in the first stage. Since the amount of the reaction solution was large and it took time to remove the heat, it took 7 hours to drop all the dicyclopentadiene. After the dropping is completed,
The temperature was raised to 140 ° C. over 2 hours, and the mixture was stirred at 140 ° C. for 4 hours to carry out the second stage reaction. In addition, it was confirmed that the water content of the phenol was dehydrated to 100 ppm or less before the reaction, and that the water content of dicyclopentadiene and the reaction system was 100 ppm or less before the reaction. Also,
The reaction was performed under a nitrogen atmosphere. At the end of the reaction step of the second stage, the content of the monofunctional component in the reaction solution is 2.0% by mass (1.2% by mass of the component A, B is the component B).
Is 0.8% by mass), and then the reaction solution is
Cooled to 0 ° C. Subsequently, 15 g of magnesium hydroxide / aluminum hydroxide / hydrotalcite (Kyoward 1000) was added to the reaction solution as a deactivator and stirred for 2 hours to deactivate the catalyst. The reaction liquid from which the deactivator and the catalyst residue were removed by filtration was concentrated by distillation at 190 ° C. for 5 hours under reduced pressure of 13 kPa (100 torr) to remove unreacted phenol, and 1750 g of a phenol resin was obtained. The obtained phenol resin has a softening point of 95 ° C., a phenolic hydroxyl group equivalent of 170 g / eq, and a solution viscosity of 90 mm ² /
It was s. Further, the content of the binuclear component is 65% by mass,
The content of the monofunctional component is 1.5% by mass (component A is 1.1
Mass% and component B was 0.4 mass%). Then, the above process was repeated again to obtain 1740 g of resin. The obtained phenol resin has a softening point of 94 ° C., a phenolic hydroxyl group equivalent of 168 g / eq, and a solution viscosity of 89 mm ^2.
Was / s. The content of the binuclear component was 67% by mass, and the content of the monofunctional component was 1.5% by mass (component A was 1.0% by mass and component B was 0.4% by mass). Although the same formulation was used for production, the physical properties of the resin obtained in the first and second times were slightly different. In addition, 3490 g of resin was obtained in total from the two productions, which required a total production time of 48 hours, and the production amount per unit time was about 73 g.
/ H, and the production efficiency was low.

[0065]

EFFECTS OF THE INVENTION According to the present invention, since phenols and unsaturated cyclic hydrocarbons are continuously reacted using a flow reactor, the reaction control is easier than in a batch type reaction, It is possible to reduce the installation space of the device. Further, it is possible to efficiently and inexpensively produce a phenol resin having good physical properties and little variation. further,
By adopting a series of continuous processes in which the reaction solution is continuously subjected to the reaction stopping step and the unreacted raw material collecting step, it is possible to more efficiently and inexpensively produce the phenol resin. Thereby, the epoxy resin can also be provided at a low cost.

[Brief description of drawings]

FIG. 1 is an explanatory view schematically showing an embodiment of a reactor used in step (I) of the present invention.

FIG. 2 is an explanatory view schematically showing an embodiment in which two reactors are connected in series to control the division of the reaction in step (I) of the present invention.

FIG. 3 shows a reactor and a process (I) used in the process (I) of the present invention.
It is explanatory drawing which shows typically the embodiment which connected the deactivation tower and concentrator used in I).

FIG. 4 is an explanatory view schematically showing an embodiment in which a catalyst separation column and a catalyst recovery tank are used in step (II) of the present invention, and a purification line and a concentrator are used in step (III).

FIG. 5 is a schematic explanatory view showing one embodiment of the whole phenol resin production process by the method of the present invention.

[Explanation of symbols]

1 Reactor (1-A 1st reactor, 1-B 2nd reactor) 2 Rotating shaft 3 Stirring blade 4 Motor 5 Partition plate 6 Deactivation tower 7 Concentrator 8 Catalyst separation tower 9 Catalyst recovery tank 10 Purification line 11 Concentrator 12 Phenol and acid catalyst supply line 13 Unsaturated cyclic hydrocarbons supply lines 14, 15 Reaction liquid line 16 Reaction liquid line after deactivation 17 Unreacted phenols extraction line 18 Phenol resin extraction line 19 Reaction liquid supply line 20 inert gas supply line 21 catalyst and inert gas extraction line 22 reaction liquid line after catalyst removal 23 reaction liquid line after purification 24 unreacted phenols extraction line 25 phenol resin extraction line

Claims (9)

[Claims] 1. A step (I) of reacting an unsaturated cyclic hydrocarbon compound having two or more carbon-carbon double bonds with a phenol as a raw material in the presence of an acid catalyst, and a step (II) of stopping the reaction. ), In the method for producing a phenolic resin including the step (III) of removing and recovering unreacted raw material from the reaction solution, the step (I) continuously supplies the raw material and the acid catalyst to the reactor, A method for producing a phenol resin, which comprises continuously extracting the phenol resin. 2. The reactor used in the step (I) is a vertical flow type tank reactor equipped with a rotating shaft vertically installed inside the reactor and a stirring blade on the rotating shaft. The method for producing a phenolic resin according to claim 1, wherein 3. The step (II) deactivates the acid catalyst by continuously circulating the reaction liquid obtained in the step (I) into a deactivation tower filled with a solid deactivator. The method for producing a phenolic resin according to claim 1 or 2, characterized in that. 4. In the step (II), the reaction liquid obtained in the step (I) is continuously supplied from the upper part of the catalyst separation column, heated under reduced pressure, and an inert gas is supplied from the lower part of the catalyst separation column. 3. The acid catalyst and the inert gas that are introduced and discharged from the top of the catalyst separation column, and the reaction liquid in which the reaction has substantially stopped is discharged from the bottom of the catalyst separation column.
The method for producing a phenolic resin according to 1. 5. The step (III) comprises continuously obtaining a molten resin by continuously concentrating the reaction solution obtained in the step (II) to remove and recover unreacted raw materials. The method for producing a phenol resin according to claim 3 or 4, which is characterized in that. 6. The method for producing a phenol resin according to claim 1, wherein the phenol is phenol. 7. The method for producing a phenol resin according to claim 1, wherein the unsaturated cyclic hydrocarbon compound having two or more carbon-carbon double bonds is dicyclopentadiene. 8. The method for producing a phenol resin according to claim 1, wherein the acid catalyst is a boron trifluoride / phenol complex. 9. A method for producing an epoxy resin, which comprises producing a phenol resin by the method according to claim 1 and then reacting the phenol resin with epihalohydrins in the presence of a base catalyst.