TW201542614A - Phenol novolac resin with narrow dispersity and manufacturing method thereof - Google Patents

Abstract

This invention provides a narrowly dispersed phenol novolac resin with a narrow molecular weight distribution that can be made using phenol and aldehyde as raw materials at high yield, and a manufacturing method thereof. The processes comprise: (a) a preparation process for adding phenol and formaldehyde to bisphenol F with 85 or higher area% of dicaryon content as measured by gel permeation chromatography to induce reaction in the presence of acid catalyst; removing acid catalyst, water and unreacted phenol from the reaction product obtained so as to obtain a crude phenol novolac resin; and (b) a distillation process using distillation operation to remove evaporated components mainly comprising dicaryon ingredient from the crude phenol novolac resin so as to obtain the narrowly dispersed phenol novolac resin having a content of dicaryon content below 20 area% and a content of polymers of six or more nuclides below 12 area% as measured by gel permeation chromatography.

Description

Narrowly dispersed phenol novolak resin and preparation method thereof

The present invention relates to a method for producing a narrowly dispersed phenol novolak resin, and a narrowly dispersed phenol novolak resin obtained by the production method.

The phenol novolak resin is excellent in properties as an organic or inorganic substrate bonding material, and is used as a curing agent for an epoxy resin composition for sealing a semiconductor device such as an IC device such as an IC or an LSI, or heat resistance and electricity. A resin for a molding material having excellent insulation properties. With regard to the market trend of electronic equipment in recent years, miniaturization, light weight, and high performance are being carried out. In order to cope with this market trend, high-level integration of semiconductor components is carried out every year. In addition, the semiconductor device is increased in size, and the semiconductor device is mounted in a TSOP (Thin Small Outline Package) or TQFP (Thin type). In the form of a quad flat pack, a Thin Quad Flat Package, or a BGA (Ball Grid Array), it becomes a surface mount type semiconductor device. Therefore, regarding the required performance of the phenol novolak resin as a curing agent, it is also required to develop a higher level of performance such as higher fluidity, higher heat resistance, higher strength, and lower moisture absorption. In order to improve these properties, it is considered to be effective to use a phenol novolac resin obtained by narrow molecular weight distribution with a narrow molecular weight distribution. In addition, it is considered that by using a phenol novolac type epoxy resin obtained by narrowing the molecular weight distribution and having a narrow molecular weight, it is possible to improve heat resistance, high strength, low moisture absorption, etc. in sealing applications and injection molding applications. The effect is that, even in the use of the raw material, a phenol novolak resin obtained by narrow molecular weight distribution having a narrow molecular weight distribution is advantageous.

Typically, phenol novolac resins are made by reacting phenol and formaldehyde in the presence of an acidic catalyst. It is obtained by carrying out a reaction, and the general phenol novolak resin is obtained by the range of the initial feeding molar ratio = 1 to 2 (the ratio of phenol (P) to formaldehyde (F), hereinafter abbreviated as molar ratio, P/F). Manufactured by reacting phenol with formaldehyde, the average number of nuclei obtained by gel permeation chromatography (GPC) is 4 to 5, and the content of 2 nucleus is 10 to 30 area%. It is also known that the nucleus distribution of the phenol novolak resin is determined by the molar ratio (P/F), and the 2-nuclear content is also determined to some extent by the molar ratio (P/F), no matter how the reaction is carried out. It will not be reduced to a certain extent below. For example, when the reaction is carried out at a molar ratio (P/F) of 2, a 2-nuclear body content of about 25 area%, a trinuclear body content of about 20 area%, and a tetranuclear body content of about 15 area% are obtained. A phenol novolak resin having a composition of a core component or more of about 40% by area or more. When the molar ratio (P/F) is increased, the polymer region is reduced, the softening point is lowered, and the fluidity of the compound is improved. However, the amount of the two nucleus is large, and for example, the heat resistance of the molded article is lowered. And so on. On the other hand, when the molar ratio (P/F) is lowered, the amount of the two nucleus is decreased, but on the contrary, there is a disadvantage that the polymer region is increased, the softening point is increased, and the fluidity of the mixture is deteriorated.

Use of phenol novolak resin as raw material or curing agent for epoxy resin When the content of the dinuclear body in the phenol novolak resin is increased, there is a problem that the molded article is burred, and the strength of the crosslinked density is lowered to cause a decrease in strength. Therefore, it has been desired to develop a phenol phenolic aldehyde having a small amount of a dinuclear body. Varnish resin. Further, when used as a curing agent for an epoxy resin or a matrix resin of an epoxy resin, in order to increase the strength of the cured product, it is also required to reduce the content of the unreacted raw material and the component below the two-nuclear body which do not contribute to the crosslinking reaction. On the other hand, as one of the properties required for phenolic resins, there is a low viscosity. If the properties of the heat resistance and strength of the phenolic resin can be maintained and the viscosity is lowered, then Workability, reactivity, fluidity, and impregnation are improved. Further, there is an advantage that a filler such as an inorganic filler can be added depending on the use. In the case of use as a binder for the production of a mold, in addition to a low viscosity, in order to reduce the generated soot, it is also required to reduce a component below the dinuclear body in the resin, that is, a dinuclear body and an unreacted raw material. In addition, in the phenol-based curing agent for epoxy resin for electrical/electronic use, which has been required in recent years, low viscosity and low nucleus content are also required.

In general, when manufacturing a low-viscosity resin, the ratio of the molar ratio (P/F) = 2 to 3 is used. The reaction is carried out to produce a low molecular weight resin. However, when a low molecular weight resin is used as a curing agent, since there are many components below the two-core body which do not contribute to the crosslinking reaction, there is a disadvantage that the strength of the cured product is insufficient. For example, in order to reduce the viscosity and react at a molar ratio (P/F) = 5/2, a low molecular weight resin is obtained as a reaction product, and has a low melt viscosity. However, since it contains many unreacted raw materials and a 2 nucleus which do not contribute to a crosslinking reaction, the problem of insufficient intensity|strength arises in a hardening reaction. Therefore, if the two-core body is further removed, a resin having a composition having a 3-nuclear body content of about 35 area% and a tetranuclear body content of about 23 area% in the portion where the two-core body is removed can be obtained, and a cured product can be obtained. A resin that is also strong in strength. However, due to the removal of the 2 nucleus, a sufficiently low viscosity cannot be achieved. Therefore, in the case where the content of the dinuclear body in the resin is reduced, for example, when the reaction is carried out at a molar ratio (P/F) = 5/4, it is possible to obtain a 2-nuclear body content of about 9 area%, 3 A phenol novolak resin having a composition having a core content of about 8 area% and a tetranuclear body content of about 6 area%. In this case, the content of the dinuclear body of the resin is small, but a large amount of a high molecular weight reaction product is formed, so that the viscosity is increased, and problems such as workability, reactivity, fluidity, and impregnation property are caused. Thus, in order to reduce the content of the dinuclear body in the phenol novolak resin, it is necessary to reduce the molar ratio (P/F) in the conventional method, and as a result, the softening point of the obtained phenol novolak resin is changed. The viscosity is high and the fluidity at the time of molding is deteriorated.

Therefore, as a method for producing a narrowly dispersed phenol novolak resin having a small amount of a dinuclear body, It has been proposed that, after the reaction, a method of extracting a 2-nuclear body using hot water (Japanese Patent Publication No. 4-71947), a slightly soluble solvent is added to the water, and then a water-soluble alcohol and water are added to remove the low-nucleus. The method of the body (Japanese Patent No. 2536600) or the like, but these methods do not show the effective use of the removed 2 nucleus, and as a result, the 2 nucleus of about 20% by mass relative to the phenol novolak resin is discarded. ingredient. Further, a method is disclosed in which a phenol resin and an aldehyde are first subjected to a resolization reaction using a basic catalyst, followed by addition of a phenol and an acid catalyst to carry out novolak-forming to synthesize a phenol novolak resin. However, the process is complicated, and the reduction of the two-core body is also insufficient (Japanese Patent Publication No. 7-119268). Further, a method in which a phenolic novolak resin is synthesized by a condensation reaction of a phenol with an aldehyde by using a hydroxycarboxylic acid having a carboxyl group and an alcoholic hydroxyl group in one molecule as a catalyst to synthesize a nucleus is also disclosed. It is insufficient and causes a problem of residual catalyst (JP-A-8-3257). Further, a production method in which a monomer and a catalyst are added to a phenol novolak resin, and a high molecular weight body of a phenol novolak resin is decomposed by heat treatment to cause low molecular weight and narrow dispersion, thereby obtaining narrow dispersion The phenol novolak resin has a poor yield of about 10% and has no practicality (JP-A-2008-81707). Further, a production method in which a step of obtaining high-purity bisphenol F by distillation of bisphenol F is used, and a distillation residue is directly formed into a phenol novolak resin, or further polymerized to produce a polymer phenol novolac A varnish resin, or a method for producing a general bisphenol F by mixing the crude bisphenol F before the recovery with the high-purity bisphenol F, but the process is increased and the productivity is greatly deteriorated, even in terms of quality, in comparison with the respective separate processes. The general bisphenol F also contains a large amount of high molecular weight bodies and has a bad influence on physical properties, or a phenol novolac having a molecular weight distribution equivalent to that of a general phenol novolak resin. In addition, the production of a phenol novolak resin having a small amount of two nucleuses is determined by the production of high-purity bisphenol F, and there are many problems in actual production (JP-A-6-128183).

The present invention has been made in view of the above circumstances, and an object thereof is to provide a method for producing a narrow-dispersed phenol novolak resin which can obtain a narrow molecular weight distribution using a phenol and an aldehyde as a raw material in a high yield.

The present inventors have found that the dinuclear component is forcibly removed from the crude phenol novolak resin, and the narrowly dispersed phenol novolak resin is obtained in a high yield, and the removed 2 nucleus can be used in the production of the crude phenol novolak resin. The present invention has been accomplished in view of the fact that a narrowly dispersed phenol novolac resin having a small environmental burden and a cost reduction is also found in general.

That is, the present invention is a method for producing a narrowly dispersed phenol novolak resin, which comprises the steps of: (a) adding phenol and formaldehyde to bisphenol F having a 2 nucleus content of 85 area% or more by GPC measurement. Reacting in the presence of an acid catalyst, removing an acid catalyst, water, and unreacted phenol from the obtained reaction product, thereby obtaining a crude phenol novolak resin preparation process; (b) using a distillation operation from a crude phenol novolac In the resin, an evaporation component containing a dinuclear body as a main component is removed, and a narrow-dispersed phenol novolak resin having a content of a high-molecular weight of 20 or less or more and a content of a high-molecular weight of 6 or more or more is obtained by GPC. Distillation process.

In the present specification, the area % associated with the content of each nucleus in the phenol novolak resin and the distillation component is GPC (column: Tosoh Corporation: trade name: G4000 _HXL + G2500 _HXL + G2000) The area % obtained by measuring _HXL × 2, eluent: tetrahydrofuran).

Further, it is preferable that the bisphenol F is a 2-nuclear body mainly obtained by the above (b) distillation step. The evaporation component of the ingredients.

In addition, the above crude phenol novolac resin is determined to have a 2 nucleus content of 30 to 70 based on GPC. The area %, the content of the high molecular weight body of 6 or more core bodies is preferably 20% by area or less, the weight average molecular weight is preferably 250 to 800, and the degree of dispersion [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1.01. 1.4.

Further, in the above (a) preparation step, it is preferred that the mass of the evaporation component is 100 The phenol is added in a range of 100 to 3000 parts by mass, and the molar ratio of phenol to formaldehyde (P/F) is 3.0 to 6.0 to react with formaldehyde.

Further, in the above (b) distillation step, it is preferable that the evaporator has a holding pressure of 1 to 10 mmHg and a heat medium temperature of 250 to 320 ° C, and the supply amount is 30 to 200 kg/h with respect to the heat transfer area of the evaporator of 1 m ² . In the manner, the crude phenol novolac resin is continuously supplied, and the evaporated component and the bottom product are continuously taken out from the evaporator.

Further, the content of the dinuclear body obtained by the GPC measurement of the above-mentioned evaporation component is preferably 85 faces. More than % of the product.

In addition, the above evaporator is preferably a vertical rotary thin film evaporation having an external condenser. Device.

Further, the present invention is a narrowly dispersed phenol novolac obtained by the above production method. Resin.

The manufacturing method of the present invention is a method for producing a narrowly dispersed phenol novolak resin. It obtains a narrowly dispersed phenol novolak resin in a high yield, and is also advantageous in terms of environmental burden and reduction in cost.

Peak a‧‧‧2 nuclear composition

Peak b‧‧3 core composition

Peak c‧‧4 nuclear composition

Peak d‧‧5 nuclear composition

Peak e‧‧6 core composition or above

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a GPC chart of a narrowly dispersed phenol novolak resin of Example 1 of the present invention.

Fig. 2 is a GPC chart of the phenol novolak resin of Comparative Example 1 of the present invention.

Embodiments of the present invention will be described in detail below.

The narrow-dispersed phenol novolak resin obtained by the present invention has a molecular weight distribution in which the content of the two-core body is 20% by area or less and the content of the high-molecular weight body having a size of 6 or more or more is 12% by area or less based on GPC. The content of the 2 core body is more preferably 12 area% or less, further preferably 10 area% or less, and most preferably 5 area% or less. Further, the content of the high molecular weight body having a hexa-nuclear body or more is preferably 10% by area or less, and more preferably a high-molecular weight body containing no more than 7 nucleus or more. The content of the nucleus is preferably from 30 to 60% by area, the content of the 4-nuclear body is preferably from 20 to 35 area%, and the content of the 5-nuclear body is preferably from 10 to 20% by area. Further, Mw is preferably from 300 to 550, more preferably from 350 to 500, still more preferably from 400 to 450, and the degree of dispersion (Mw/Mn) is preferably from 1.05 to 1.3, more preferably from 1.08 to 1.2, still more preferably from 1.10 to 1.15. When the amount of unreacted phenol and the dinuclear body is large, when it is used as a curing agent, it does not contribute to the crosslinking reaction, and thus heat resistance may be lowered. Further, in the case of using as a raw material of an epoxy resin, burrs may be generated on the obtained molded article, or the strength of the molded article may be lowered. In addition, if the sum of the contents of the 3-nuclear body and the 4-nuclear body is 55 to 80 area%, Then, a phenol novolak resin having a low melt viscosity can be realized, and thus it is preferably more preferably 60 to 76 area%. When the sum of the contents of the 3 nucleus and the 4 nucleus is large, the average number of nuclei may be lowered, and the heat resistance of the cured product may be lowered, which is not preferable. Further, when the content of the 5-nuclear body is 10 to 20% by area, it is preferable since it has a low melt viscosity and a phenol novolak resin having heat resistance. Further, when the content of the 6-nuclear body is small or completely absent, the decrease in heat resistance is remarkable, which is not preferable.

In addition, the narrowly dispersed phenol novolac resin is removed from the crude phenol novolac by distillation. In the lacquer resin, a distillation component containing a dinuclear body as a main component is removed, and the distilled component removed by distillation is not discarded, and a crude phenol novolak resin can be produced together with phenol and fumarin to form a narrowly dispersed phenol novolak resin. Distillation used.

Excellent crude phenol novolac resin for obtaining narrowly dispersed phenol novolac resin Since the high molecular weight body of 6 or more nucleus is not excessively included, the 2 nucleus is necessary to some extent, and therefore the content of the 2 nucleus obtained by GPC measurement is preferably 30 to 70 area%, more preferably 35 to 65. The area % is more preferably 45 to 60 area%, and most preferably 50 to 57 area%. Therefore, Mw is from 250 to 800, preferably from 280 to 600, more preferably from 310 to 450, and the degree of dispersion (Mw/Mn) is from 1.01 to 1.4, preferably from 1.05 to 1.3, more preferably from 1.1 to 1.2.

The above crude phenol novolak resin can also be passed through a conventional production method, that is, Phenol, formaldehyde, and an acid catalyst are introduced into a reactor equipped with a stirrer, a temperature adjusting device, a reflux condenser, a condenser, a pressure reducing device, and the like, and reacted at a predetermined temperature for a predetermined hour while stirring, and then reacted from the reaction. The acid catalyst, the produced water, and the unreacted phenol are removed from the product to obtain a crude phenol novolak resin; and as in the preparation step (a) of the present invention, a mixer, a temperature adjusting device, a reflux condenser, and a full condenser may be provided. In a reactor such as a pressure reducing device, 100 parts by mass of the distillation component removed by the (b) distillation step, and 100 to 4000 parts by mass of phenol, formaldehyde and an acid catalyst are charged, and under stirring, The reaction was carried out at a predetermined temperature for a predetermined period of time, and then the acid catalyst, the produced water, and the unreacted phenol were removed from the reaction product to obtain a crude phenol novolak resin.

In the (a) preparation step, the distillation component 100 removed by the (b) distillation step is used. In parts by mass, if the phenol is 100 to 3000 parts by mass, a crude phenol novolak resin having a target molecular weight distribution can be obtained. The phenol is preferably 200 to 2500 parts by mass, more preferably 300 to 2000 parts by mass, even more preferably 500 to 1000 parts by mass, per 100 parts by mass of the distillation component. In the case of the distillation component removed by the (b) distillation step, when the amount of phenol is small, the components of the even number of nucleus such as the two-nuclear body, the tetranuclear body, and the six-nuclear body may be increased, and the molecular weight distribution may be different. Crude phenol novolac resin.

In the present invention, the distillation component obtained by the (b) distillation step is used, in (a) A crude phenol novolak resin is produced in the preparation process, and this process is repeated continuously to obtain a large effect. In particular, the distillation component obtained by the (b) distillation step is not taken out of the process system, and is directly used in the next step, so that the adverse effect due to oxidation can be greatly reduced, which is preferable.

In addition to phenol, for example, cresol, ethyl phenol, butyl phenol, octyl can also be used. An alkylphenol such as phenol, nonylphenol or dodecylphenol or a (o-, m-, p-) positional substituent or a (n-, sec-, tert-, etc.) substituent structural isomer. Among them, phenol is preferred in view of reactivity with formalin and ease of distillation recovery. Phenol may be used singly or in combination of two or more.

As formaldehyde, for example, formalin, paraformaldehyde, hexamethylenetetramine, trioxane Alkane and cyclic formal, and the like. Among them, fumarin is preferred, and up to 42% by mass of a formalin aqueous solution can be used, and more preferably 37 to 42% by mass of a formalin aqueous solution. Formaldehyde may be used singly or in combination of two or more.

Further, the molar ratio (P/F) is preferably 3.0 to 6.0, more preferably 3.5 to 5.5, further preferably It is 4.0 to 5.0, and most preferably 4.3 to 4.7. When the molar ratio (P/F) is large, the content of the 2 nucleus increases and thus the dispersion is narrow. The amount of phenol novolac resin obtained may be reduced, and productivity may be lowered. Further, when the molar ratio (P/F) is small, the polymer component of the 6-nuclear or higher body is increased, and thus the molecular weight distribution may be broadened, and a narrowly dispersed phenol novolak resin may not be obtained. If the molar ratio (P/F) is in this range, it is not necessary to particularly consider the dinuclear content and the amount of the distillation component, and a crude phenol novolak resin having a desired molecular weight distribution can be obtained.

Further, the acid catalyst used in the (a) preparation step may be a cation exchange resin. The fixed bed of the solid acid catalyst may also be an organic acid such as hydrochloric acid, sulfuric acid, salicylic acid, p-toluenesulfonic acid or oxalic acid, or an inorganic acid. The reaction temperature and the reaction time vary depending on the type and amount of the catalyst to be used, or the molar ratio (P/F), but are usually 0.5 to 10 hours at 50 to 110 °C. When a fixed bed catalyst such as a cation exchange resin is used, after the reaction, the removal of the catalyst can be omitted, and unreacted formaldehyde, produced water, and the like can be removed by a method such as vacuum distillation. When a mineral acid such as hydrochloric acid or oxalic acid is used, after the reaction, the acid catalyst is simultaneously removed by a method such as vacuum distillation, together with unreacted formaldehyde, water, and water.

Next, unreacted phenol is removed by distillation under reduced pressure or the like. Their separation and removal Alternatively, the phenol may be subjected to partial condensing by providing a fractionator, and water or the like may be further condensed by a full condenser. Of course, the recovered phenol can be reused as a raw material. The content of the dinuclear body in the crude phenol novolak resin obtained by the above operation is, for example, 40% by mass using oxalic acid as a catalyst and having a molar ratio (P/F) of 3 In the case where the molar ratio (P/F) is 4.5, it is about 54% by mass, and when it is carried out with a molar ratio (P/F) = 6, it is about 63% by mass.

Further, in the distillation step of (b), the two-core body is mainly formed by vacuum distillation. The distillation component of the fraction is removed. Regarding the content of the 2-nuclear body based on the GPC measurement in the distillation component, the steaming according to (b) The distillation conditions in the distillation step vary, but are preferably 85% by area or more, more preferably 90% by area or more, and still more preferably 95% by area or more. When the content of the dinuclear body in the distillation component is small, the content of the dinuclear body in the target narrow-dispersed phenol novolak resin may increase. Therefore, in the distillation step, although the content of the dinuclear body in the crude phenol novolak resin is also involved, 30 to 60% by mass of the supplied crude phenol novolak resin is removed as a distillation component.

(b) The evaporator used in the distillation step is preferably an evaporator having a fractionator, the fraction The distilling device can return the condensate obtained by coagulating a part of the evaporation component derived from the evaporator to the evaporator, and the evaporator is preferably an evaporator such as a falling film type or a centrifugal film type. Further, when a plurality of evaporators are used, each of the evaporators may be an evaporator having a fractionator or an evaporator not having a fractionator, but it is preferable that the evaporator used at least in the final stage is provided with fractionation. The evaporator of the device. In this case, the form of the evaporator preferably used is also the same as described above.

In the distillation step, the evaporator is continuously supplied to the evaporator having a holding pressure of 1 to 10 mmHg and a film surface heat medium temperature of 250 to 320 ° C in a manner that the supply amount is 30 to 200 kg/h with respect to the heat transfer area of the evaporator of 1 m ² . The crude phenol novolak resin can obtain a narrowly dispersed phenol novolak resin while continuously taking out the evaporated component and the bottom product from the evaporator. When the temperature of the heat medium is high, decomposition or coloring of the phenol novolak resin may occur, and when the temperature is low, a high vacuum, for example, a pressure of less than 1 mmHg is required, which is uneconomical. Further, when the amount of supply is large, the removal of the two-core body may be insufficient.

In the distillation process, as a preferred full-coagator, a multi-tube cylindrical change is exemplified. Heaters, coil heat exchangers, etc. As the fractionator to be preferably used, a multitubular cylindrical heat exchanger, a coil heat exchanger, or the like is exemplified. Further, it may be a type of heat exchanger that externally cools the evaporation line from the evaporator to the full condenser.

In addition, a narrowly dispersed phenol novolac obtained by using a bottom product as a distillation step When the dinuclear content of the lacquer resin is less than 3% by mass, the distillation temperature becomes high, which may cause decomposition and coloration of the bottom product. The molecular weight distribution of the narrowly dispersed phenol novolak resin obtained as the bottom product can be controlled by appropriately selecting the pressure conditions and temperature conditions in the above range.

By withdrawing the bottom product of the distillation process, letting it cool in the atmosphere, or forcibly cooling Alternatively, it is cooled to about 40 ° C or lower, preferably pulverized to prepare a narrowly dispersed phenol novolak resin. The method of pulverization is not particularly limited, and a pulverizer such as a ball mill or a jet mill is preferably used. In addition, in the case of being a raw material of an epoxy resin, it may be sent to the epoxidation step in a liquid state by heat preservation, or may be sent to a separately granulated step and granulated to obtain a granulated form. Products.

Example

Hereinafter, the present invention will be more specifically described based on examples and comparative examples, but the present invention is not This limit. In the examples, the parts represent "parts by mass" and % means "% by mass" unless otherwise specified. Incidentally, the evaluation or measurement of various characteristic values in the examples and the comparative examples was carried out by the following methods (1) to (6).

(1) a narrow phenol novolak resin, a crude phenol novolak resin, and a distillation component Determination of the content of each nucleus, molecular weight (Mw), and degree of dispersion (Mw/Mn): The content of each nucleus is the area % obtained by GPC measurement. The molecular weight (Mw) and the degree of dispersion (Mw/Mn) were calculated by calculating the molecular weight corresponding to the number of phenol nuclei in accordance with the respective peaks measured in the same manner, that is, calculating the molecular weight of the two-nuclear body to be 200, and calculating 3 The molecular weight of the core was 306, the molecular weight of the tetranuclear body was calculated to be 412, the molecular weight of the 5-nuclear body was calculated to be 518, the molecular weight of the 6-nuclear body was calculated to be 624, and the molecular weight of the 7-nuclear body was calculated to be 730, and the fraction of the 8-nuclear body was calculated. The sub-quantity was 836, and the molecular weight of the 9-nuclear body was calculated to be 942, and the molecular weight of the 10-nuclear body was calculated to be 1048. The measurement conditions of GPC are as follows.

Column: G4000 _HXL + G2500 _HXL + G2000 _HXL × 2 (Tosoh Corporation)

Column temperature: 40 ° C

Eluent: tetrahydrofuran

Flow rate: 1mL/min

Sample concentration: 0.1g/10mL tetrahydrofuran

Detector: RI detection

(2) Melt viscosity: It was measured at 120 ° C using an ICI cone-and-plate type viscometer (manufactured by Research Equipment Co., Ltd.).

(3) Gel time: The epoxy resin composition was poured into the concave portion of a gelation tester (manufactured by Nisshin Scientific Co., Ltd.) which was previously heated to 175 ° C, and the rod made of a fluororesin was rotated twice in one second. The stirring speed was investigated, and the gelation time required for the epoxy resin composition to be cured was examined.

(4) Spiral flow: The mold for spiral flow measurement according to EMMI-1-66 was measured under the conditions of a mold temperature of 175 ° C, an injection pressure of 6.9 MPa, and a curing time of 120 seconds.

(5) Glass transition temperature (Tg): It was measured by a TMA (thermomechanical measurement) method at a temperature elevation rate of 10 ° C /min.

(6) Flexural strength and flexural modulus: Measured in accordance with JIS K-6911.

Example 1

(Preparation process)

To a stirred tank type reactor equipped with a stirrer, a temperature adjusting device, a reflux condenser, a full condenser, a pressure reducing device, etc., 100 parts of bisphenol F having a nucleus amount of 90% by area as bisphenol F and 100 parts by area were added. 600 parts of phenol was heated to 80 ° C, then 1.55 parts of oxalic acid dihydrate was added, stirred for 10 minutes, and then 115 parts of 37.5% fumarin was added dropwise over 30 minutes. Thereafter, the reaction temperature was maintained at 92 ° C and the reaction was continued for 3 hours. After the reaction was terminated, the temperature was raised to 110 ° C, and dehydration was carried out, and then the residual phenol was recovered under a recovery condition of 150 ° C and 60 mmHg for about 90%, and then recovered under a recovery condition of 160 ° C and 5 mmHg, and then further at 160. Under a condition of ° C and 80 mmHg, 10 parts of water was added dropwise for 90 minutes to remove residual phenol, thereby obtaining a crude phenol novolak resin. Regarding the composition of the obtained crude phenol novolak resin, the amount of the two nucleus was 55.1 area%, the amount of the three nucleus was 24.9 area%, the amount of the 4 nucleus was 11.1 area%, and the amount of the 5 nucleus was 5.0 area%, 6 nucleus. The content above the body was 3.9 area%, Mw was 339, and the degree of dispersion (Mw/Mn) was 1.190.

(distillation process)

The obtained crude phenol novolak resin was continuously supplied at 21 kg/h for 1 hour in a centrifugal thin film evaporator operated under the conditions of a rotor rotation speed of 250 rpm and a vacuum degree of 3 to 5 mmHg, and the evaporation component and the phenol novolac resin were continuously supplied. Take out. The centrifugal thin film evaporator was jacketed with a heating conduction surface of 0.21 m ² and a 260 ° C heat medium was passed through the jacket. Further, the centrifugal thin film evaporator had an external condenser, a cooling conductive surface of 1.3 m ² and flowing warm water of 120 ° C, and the total amount of the evaporated components was coagulated and extracted.

Regarding the composition of the obtained phenol novolak resin, the amount of the 2-nuclear body was 9.1 area%, 3 The amount of core is 48.9 area%, the amount of 4 nucleus is 22.9 area%, the amount of 5 nucleus is 10.4 area%, the content of 6 nucleus or more is 8.7 area%, Mw is 423, and the degree of dispersion (Mw/Mn) is 1.122. . The amount of the two nucleus of the evaporated component was 97.9 area%, the amount of the three nucleus was 2.1 area%, the Mw was 203, and the degree of dispersion (Mw/Mn) was 1.006. No coloration was observed in the obtained phenol novolak resin.

Example 2

(Preparation process)

210 parts of the evaporated component obtained in Example 1 was used as bisphenol F, and phenol was changed to 680. A crude phenol novolak resin was obtained in the same manner as in Example 1 except that the oxalic acid dihydrate was changed to 1.78 parts and the 37.5% fumarine was changed to 115 parts. Regarding the composition of the obtained crude phenol novolak resin, the amount of the two nucleus is 52.8 area%, the amount of the three nucleus is 25.0 area%, the amount of the 4 nucleus is 12.7 area%, and the amount of the 5 nucleus is 5.2 area%, 6 nucleus. The content above the body was 4.3 area%, Mw was 347, and the degree of dispersion (Mw/Mn) was 1.192.

(distillation process)

To the centrifugal thin film evaporator used in Example 1, continuous supply at 10 kg/h was obtained. The crude phenol novolak resin was continuously extracted from the evaporated component and the phenol novolak resin for 1 hour. Regarding the operating conditions, the rotor speed was 250 rpm, the degree of vacuum was 6 to 8 mmHg, and the temperature of the heat medium was 290 °C.

Regarding the composition of the obtained phenol novolak resin, the amount of the 2-nuclear body was 6.3 area%, 3 The amount of core is 49.6 area%, the amount of 4 nucleus is 25.2 area%, the amount of 5 nucleus is 10.2 area%, the content of 6 nucleus or more is 8.7 area%, Mw is 425, and the degree of dispersion (Mw/Mn) is 1.113. . The amount of the two nucleus of the evaporated component was 98.2 area%, the amount of the three nucleus was 1.8 area%, the Mw was 203, and the degree of dispersion (Mw/Mn) was 1.005. No coloration was observed in the obtained phenol novolak resin.

Example 3

(Preparation process)

25 parts of the evaporation component obtained in Example 2 was used as bisphenol F, phenol was changed to 600 parts, oxalic acid dihydrate was changed to 1.25 parts, and 37.5% fumarin was changed to 170 parts, and real The same operation as in Example 1 was carried out, thereby obtaining a crude phenol novolak resin. Regarding the composition of the obtained crude phenol novolak resin, the amount of the two nucleus was 38.0 area%, the amount of the three nucleus was 24.5 area%, the amount of the 4 nucleus was 20.4 area%, and the amount of the 5 nucleus was 9.3 area%, 6 nucleus. The content above the body was 7.8 area%, Mw was 403, and the degree of dispersion (Mw/Mn) was 1.195.

(distillation process)

To the centrifugal thin film evaporator used in Example 1, continuous supply at 31 kg/h was obtained. The crude phenol novolac resin continuously extracts the evaporated component and the phenol novolak resin. Regarding the operating conditions, the rotor speed was 250 rpm, the degree of vacuum was 4 to 5 mmHg, and the temperature of the heat medium was 270 °C.

Regarding the composition of the obtained phenol novolak resin, the amount of the 2-nuclear body was 10.1 area%, 3 The amount of core is 35.6 area%, the volume of 4 nucleus is 29.6 area%, the amount of 5 nucleus is 13.4 area%, the content of 6 nucleus or more is 11.3 area%, Mw is 448, and the degree of dispersion (Mw/Mn) is 1.124. . The amount of the two nucleus of the evaporated component was 97.9 area%, the amount of the three nucleus was 2.1 area%, the Mw was 203, and the degree of dispersion (Mw/Mn) was 1.006. No coloration was observed in the obtained phenol novolak resin.

Example 4

(Preparation process)

120 parts of the evaporated component obtained in Example 3 was used as bisphenol F, and phenol was changed to 550. A crude phenol novolak resin was obtained in the same manner as in Example 1 except that the oxalic acid dihydrate was changed to 1.52 parts and the 37.5% fumarline was changed to 86 parts. Regarding the composition of the obtained crude phenol novolak resin, the amount of the two nucleus was 61.0 area%, the amount of the three nucleus was 24.0 area%, the amount of the 4 nucleus was 13.0 area%, and the amount of the 5 nucleus was 1.1 area%, 6 nucleus. The content of the above body was 0.9 area%, Mw was 293, and the degree of dispersion (Mw/Mn) was 1.121.

(distillation process)

To the centrifugal thin film evaporator used in Example 1, continuous supply at 21 kg/h was obtained. The crude phenol novolak resin was continuously extracted from the evaporated component and the phenol novolak resin for 1 hour. Regarding the operating conditions, the rotor rotation speed was 200 rpm, the degree of vacuum was 5 to 6 mmHg, and the heat medium temperature was 280 °C.

Regarding the composition of the obtained phenol novolak resin, the amount of the 2-nuclear body was 11.5 area%, 3 The amount of core is 54.4 area%, the volume of 4 nucleus is 29.6 area%, the amount of 5 nucleus is 2.5 area%, the content of 6 nucleus or more is 2.0 area%, Mw is 361, and the degree of dispersion (Mw/Mn) is 1.069. . The amount of the two nucleus of the evaporated component was 98.9 area%, the amount of the three nucleus was 1.1 area%, the Mw was 202, and the degree of dispersion (Mw/Mn) was 1.003. No coloration was observed in the obtained phenol novolak resin.

Example 5

(Preparation process)

350 parts of the evaporated component obtained in Example 4 was used as bisphenol F, and phenol was changed to 365. A crude phenol novolak resin was obtained in the same manner as in Example 1 except that the oxalic acid dihydrate was changed to 1.50 parts and the 37.5% fumarline was changed to 65 parts. Regarding the composition of the obtained crude phenol novolak resin, the amount of the two nucleus was 51.4 area%, the amount of the three nucleus was 26.7 area%, the amount of the 4 nucleus was 13.1 area%, and the amount of the 5 nucleus was 4.8 area%, 6 nucleus. The content above the body was 4.0 area%, Mw was 345, and the degree of dispersion (Mw/Mn) was 1.184.

(distillation process)

To the centrifugal thin film evaporator used in Example 1, continuous supply at 21 kg/h was obtained. The crude phenol novolak resin was continuously extracted from the evaporated component and the phenol novolak resin for 1 hour. Regarding the operating conditions, the rotor speed was 300 rpm, the degree of vacuum was 5 to 6 mmHg, and the temperature of the heat medium was 280 °C.

Regarding the composition of the obtained phenol novolak resin, the amount of the 2-nuclear body was 11.8 area%, 3 The amount of core is 46.4 area%, the amount of 4 nucleus is 22.8 area%, the amount of 5 nucleus is 10.3 area%, the content of 6 nucleus or more is 8.7 area%, Mw is 421, and the degree of dispersion (Mw/Mn) is 1.129. . The amount of the two nucleus of the evaporated component was 95.6 area%, the amount of the three nucleus was 4.4 area%, the Mw was 207, and the degree of dispersion (Mw/Mn) was 1.011. No coloration was observed in the obtained phenol novolak resin.

Example 6

(Preparation process)

60 parts of the evaporation component obtained in Example 5 was used as bisphenol F, phenol was changed to 600 parts, oxalic acid dihydrate was changed to 1.65 parts, and 37.5% of fumarin was changed to 115 parts, and The same operation was carried out in Example 1, whereby a crude phenol novolac resin was obtained. Regarding the composition of the obtained crude phenol novolak resin, the amount of the two nucleus was 51.4 area%, the amount of the 3 nucleus was 24.7 area%, the amount of the 4 nucleus was 13.1 area%, and the amount of the 5 nucleus was 5.8 area%, 6 nucleus. The content above the body is 5.0 area%, Mw is 359, and the degree of dispersion (Mw/Mn) is 1.207.

(distillation process)

The centrifugal thin film evaporators used in the two Examples 1 were connected in series, and the bottom product of the first evaporator was used as the second evaporator to supply the crude phenol novolak resin, and the continuous operation was carried out. At this time, the evaporation components obtained by the first and second evaporators were mixed to obtain an evaporation component. In addition, the first and second evaporators were operated under the same operating conditions. That is, the obtained crude phenol novolak resin was continuously supplied at 21 kg/h for 1 hour, and the evaporation component and the phenol novolak resin were continuously extracted. Regarding the operating conditions, the rotor rotation speed was 200 rpm, the degree of vacuum was 5 to 6 mmHg, and the heat medium temperature was 280 °C.

Regarding the composition of the obtained phenol novolak resin, the amount of the 2-nuclear body was 4.3 area%, 3 The amount of core is 48.7 area%, the volume of 4 nucleus is 25.9 area%, the amount of 5 nucleus is 11.5 area%, the content of 6 nucleus or more is 9.6 area%, Mw is 437, and the degree of dispersion (Mw/Mn) is 1.115. . The amount of the two nucleus of the evaporated component was 96.9 area%, the amount of the three nucleus was 3.1 area%, the Mw was 205, and the degree of dispersion (Mw/Mn) was 1.008. No coloration was observed in the obtained phenol novolak resin.

Comparative example 1

(Preparation process)

Without using bisphenol F, the phenol was changed to 772 parts, and the oxalic acid dihydrate was changed to 2.20 parts. A crude phenol novolak resin was obtained in the same manner as in Example 1 except that 37.5% of fumarline was changed to 246 parts. Regarding the composition of the obtained crude phenol novolak resin, the amount of the two nucleus was 36.4 area%, the amount of the three nucleus was 22.7 area%, the amount of the 4 nucleus was 14.9 area%, and the amount of the 5 nucleus was 11.4 area%, 6 nucleus. The content above the body was 14.6 area%, Mw was 461, and the degree of dispersion (Mw/Mn) was 1.254.

(distillation process)

To the centrifugal thin film evaporator used in Example 1, continuous supply at 21 kg/h was obtained. The crude phenol novolak resin was continuously extracted from the evaporated component and the phenol novolak resin for 1 hour. Regarding the operating conditions, the rotor speed was 250 rpm, the degree of vacuum was 3 to 5 mmHg, and the temperature of the heat medium was 260 °C.

Regarding the composition of the obtained phenol novolak resin, the amount of the 2-nuclear body was 10.6 area%, 3 The amount of core is 33.3 area%, the amount of 4 nucleus is 20.8 area%, the amount of 5 nucleus is 13.8 area%, the amount above 6 nucleus is 21.5 area%, Mw is 515, and the degree of dispersion (Mw/Mn) is 1.179. . The amount of the two nucleus of the evaporated component was 97.4 area%, the amount of the three nucleus was 2.6 area%, the Mw was 204, and the degree of dispersion (Mw/Mn) was 1.007. No coloration was observed in the obtained phenol novolak resin.

Comparative example 2

(Preparation process)

Without using bisphenol F, the phenol was changed to 1150 parts, and the oxalic acid dihydrate was changed to 3.50 parts. A crude phenol novolak resin was obtained in the same manner as in Example 1 except that 37.5% of fumarline was changed to 122 parts. Regarding the composition of the obtained crude phenol novolak resin, the amount of the two nucleus was 71.3 area%, the amount of the 3 nucleus was 20.5 area%, the amount of the 4 nucleus was 6.4 area%, and the amount of the 5 nucleus was 1.0 area%, 6 nucleus. The content of the above body was 0.8 area%, Mw was 269, and the degree of dispersion (Mw/Mn) was 1.108.

(distillation process)

To the centrifugal thin film evaporator used in Example 1, continuous supply at 21 kg/h was obtained. The crude phenol novolak resin was continuously extracted from the evaporated component and the phenol novolak resin for 1 hour. Regarding the operating conditions, the rotor speed was 250 rpm, the degree of vacuum was 3 to 5 mmHg, and the temperature of the heat medium was 260 °C.

Regarding the composition of the obtained phenol novolak resin, the amount of the 2-nuclear body was 14.2 area%, 3 The amount of core is 42.1 area%, the volume of 4 nucleus is 26.3 area%, the amount of 5 nucleus is 9.5 area%, the content of 6 nucleus or more is 7.9 area%, Mw is 415, and the degree of dispersion (Mw/Mn) is 1.124. . The amount of the two nucleus of the evaporated component was 97.9 area%, the amount of the three nucleus was 2.1 area%, the Mw was 203, and the degree of dispersion (Mw/Mn) was 1.006. No coloration was observed in the obtained phenol novolak resin.

Comparative example 3

The rotor speed is 250 rpm, the vacuum is 8-10 mmHg, and the heat medium temperature is 300. In the centrifugal thin film evaporator used in Example 1 which was stably operated under the operating conditions of ° C, the crude phenol novolak resin obtained in Comparative Example 2 was continuously supplied at 10 kg/h, but benzene was formed by decomposition of the supplied resin. Phenol cannot maintain the pressure in the evaporator and cannot operate stably. Thereafter, the supply was interrupted, and the operating conditions were again set to a rotor rotation speed of 250 rpm, a vacuum degree of 8 to 10 mmHg, a heat medium temperature of 300 ° C, and stable operation, and then continuously supplied at 21 kg/h, but the resin was also supplied in the centrifugal thin film evaporator. Decomposition occurs to form phenol, so that the pressure in the evaporator cannot be maintained and the operation cannot be performed stably. In addition, the bottom product was found to have a yellow coloration.

Each nucleus of the phenol novolak resin obtained in Examples 1 to 6 and Comparative Examples 1 and 2 The amount, molecular weight (Mw), degree of dispersion (Mw/Mn), and melt viscosity are shown in Table 1.

Unlike the embodiment in which the evaporated component is reused, in the comparative example, it is evaporated into Further processing is added to the reuse of the points. For example, in the case of distillation of bisphenol F, general steaming The amount of the dinuclear body of the bisphenol F is 99% by area or more, and the amount of the dinuclear body of the evaporated component of the comparative example is 97.4% by area, which is less than 97.9 area%, and thus cannot be used as the distilled bisphenol F as it is. Therefore, it is necessary to re-distill the evaporated component, the environmental burden is large, and it becomes disadvantageous in terms of cost. In addition, when the distillation component is directly discarded, the yield of the phenol novolak resin is deteriorated, and the environmental burden is further increased, which is disadvantageous in terms of cost. In contrast, in the examples, since the evaporation component is reused, the yield as a phenol novolak resin is high, and the environmental burden such as disposal is small.

O-cresol novolac type epoxy resin (Nippon Steel & Sumitomo Chemical Co., Ltd.) was used. Epotohto YDCN-700-7, epoxy equivalent 202 g/eq, softening point 72 ° C) As the epoxy resin component, the narrowly dispersed phenol novolak resin synthesized in Examples 1 to 6 was used, and Comparative Example 1 was used. ~2 Synthesized phenol novolak resin As a curing agent, triphenylphosphine was used as a curing accelerator. Further, spheroidal vermiculite (average particle diameter: 18 μm) was used as a filler, carbon black was used as a coloring agent, and carnauba wax was used as a releasing agent. With respect to 100 parts of the epoxy resin component, 52 parts of a curing agent, 1.2 parts of a curing accelerator, 808 parts of a filler, 5.1 parts of a coloring agent, and 3 parts of a releasing agent were kneaded to obtain an epoxy resin composition. The gel time and spiral flow of the obtained epoxy resin composition were measured. Further, the obtained epoxy resin composition was compression-molded at 175 ° C, and then post-cured at 175 ° C for 12 hours to obtain a cured product test piece. The obtained cured product test piece was used to measure various physical properties. These results are shown in Table 2.

Peak a‧‧‧2 nuclear composition

Peak b‧‧3 core composition

Peak c‧‧4 nuclear composition

Peak d‧‧5 nuclear composition

Peak e‧‧6 core composition or above

Claims (8)

A method for producing a narrowly dispersed phenol novolak resin, comprising the steps of: (a) adding phenol and formaldehyde to bisphenol F having a binuclear content of 85 area% or more by gel permeation chromatography; Reacting in the presence of an acid catalyst, removing an acid catalyst, water, and unreacted phenol from the obtained reaction product, thereby obtaining a preparation process of a crude phenol novolak resin; (b) using a distillation operation from a crude phenol novolak resin The evaporating component containing the dinuclear body as a main component is removed, and a narrowly dispersed phenol novolac having a content of a high-molecular weight body having a dinuclear body content of 20% by area or less and a content of 6 or more cores of 12 or less or less is obtained by gel permeation chromatography. Distillation process of varnish resin. The method for producing a narrow-dispersed phenol novolak resin according to claim 1, wherein the bisphenol F is an evaporation component obtained by a distillation step. The method for producing a narrow-dispersed phenol novolak resin according to claim 1 or 2, wherein the crude phenol novolak resin has a 2-nuclear content of 30 to 70% by area, 6 cores, determined by gel permeation chromatography. The content of the high molecular weight body or more is 20% by area or less, the weight average molecular weight is 250 to 800, and the degree of dispersion (weight average molecular weight / number average molecular weight) is 1.01 to 1.4. The method for producing a narrowly dispersed phenol novolak resin according to claim 1, wherein In the preparation step, phenol is added in an amount of 100 to 3000 parts by mass based on 100 parts by mass of the evaporation component, and formaldehyde is reacted in a molar ratio (P/F) of phenol to formaldehyde of 3.0 to 6.0. The method for producing a narrow-dispersed phenol novolak resin according to claim 1, wherein in the distillation step, the evaporator is maintained at a pressure of 1 to 10 mmHg and a heat medium temperature of 250 to 320 °C. The crude phenol novolak resin was continuously supplied to the evaporator at a heat transfer area of 1 m ² of 30 to 200 kg/h, and a narrow dispersion of the phenol novolak resin was obtained while continuously taking out the evaporated component and the bottom product from the evaporator. The method for producing a narrow-dispersed phenol novolak resin according to claim 1, wherein the content of the dinuclear body measured by the gel permeation chromatography is 85 area% or more. The method for producing a narrowly dispersed phenol novolac resin according to claim 1, wherein the evaporator is a vertical rotary thin film evaporator having an external condenser. A narrowly-dispersed phenol novolac resin obtained by the production method according to any one of claims 1 to 7.