KR20200002668A - Method for producing polyhydric hydroxy resin - Google Patents

Abstract

Provided by the present invention are: epoxy resin which has high heat resistance and provides an epoxy resin cured product with excellent reliability and molding workability; and a polyvalent hydroxy resin producing method which is a useful raw material to obtain the epoxy resin efficiently. The present invention is the method for producing polyvalent hydroxy resin represented by chemical formula 1 by making 4,4′-dihydroxybiphenyl react with bischloromethylbiphenyl. When producing the polyvalent hydroxy resin, components of n=0 are 30% or less and 15% or more with an area% measured by a gel permeation chromatography (GPC area%), a high molecular weight component of n=6 or more is 30% or less, and the total amount of chlorine is 1,000 wtppm or less. The method for producing polyvalent hydroxy resin performs the reaction under the presence of a non-catalyst or an acid catalyst in a solvent and causes a reaction by recovering a part of a solvent under a reduced pressure in a rear end reaction and adjusting the amount of a solvent. According to chemical formula 1, n represents a number of 0 to 20.

Description

Production method of polyhydric hydroxy resin {METHOD FOR PRODUCING POLYHYDRIC HYDROXY RESIN}

TECHNICAL FIELD This invention relates to the manufacturing method of polyhydric hydroxy resin, and relates to the manufacturing method of polyhydric hydroxy resin obtained by making biphenyl and a chlorine containing aromatic condensation agent react as a raw material.

Epoxy resins have been used industrially for a wide range of applications, but their required performance has been further advanced in recent years. In the meantime, in the power device which is being developed recently, the improvement of the power density of a device is calculated | required, As a result, since the temperature of the chip surface at the time of operation becomes 200 degreeC or more, it can endure the temperature. The development of the sealing material which is present is desired.

Among these, Patent Document 1 discloses an epoxy resin having an biphenol biphenyl aralkyl structure, an epoxy resin composition, and a cured product, and shows that it is excellent in heat resistance, moisture resistance, and thermal conductivity. Patent documents 2 and 3 similarly disclose the epoxy resin composition which has a biphenol biphenyl aralkyl structure, the manufacturing method of an epoxy resin hardened | cured material, and a semiconductor device, and shows that the hardened | cured material excellent in heat resistance and thermal decomposition stability is obtained. However, Patent Literatures 1 to 3 disclose polyhydric hydroxy resins and epoxy resins obtained by using a compound containing chlorine in a raw material, but the amount of chlorine is not mentioned, and in practice, polyhydric hydroxy resins are used. Since the amount of chlorine remaining is high, the amount of chlorine also increases in the epoxy resin obtained by subsequent epoxidation, and there exists a problem that the reliability of hardened | cured material deteriorates.

Patent Literature 4 discloses a method of making the total amount of chlorine of the polyhydric hydroxy resin 1000 wtppm or less by using an alkali metal hydroxide, but it does not describe the improvement in yield and reaction time during epoxidation. Although patent document 5 describes the improvement of the yield at the time of epoxidation by reducing the polymer component of polyhydric hydroxy resin, it does not describe the improvement of reaction time. In the conventional manufacturing method, the solid content concentration at the time of manufacture of a polyhydric hydroxy resin is constant, and in order to make reduction of a polymer component and reduction of the total chlorine quantity compatible, reaction time was 20 hours or more and it was industrially disadvantageous. In order to promote the reaction time, it was difficult to increase the solid content concentration and react at a high concentration in view of the solvent solubility of the raw materials.

WO2011 / 074517 WO2014 / 065152 WO2015 / 146606 Japanese Unexamined Patent Publication No. 2017-119768 WO2017 / 170703

SUMMARY OF THE INVENTION An object of the present invention is to provide an epoxy resin having a high heat resistance, providing an epoxy resin cured product having excellent reliability and molding workability, and a method for producing a useful polyhydric hydroxy resin which is a raw material for efficiently obtaining the epoxy resin. In particular, the present invention provides a method for producing a polyhydric hydroxy resin effective for low chlorination and shortening of production time.

The present invention is a method for producing a polyhydric hydroxy resin represented by the general formula (1) by reacting 4,4'-dihydroxybiphenyl and bischloromethylbiphenyl, the area% measured by gel permeation chromatography. In the preparation of a polyhydric hydroxy resin having a high molecular weight component of 30% or less, 15% or more, n = 6 or more, and a total chlorine content of 1000 wtppm or less in terms of (GPC area%), the reaction is carried out. It is a manufacturing method of the polyhydric hydroxy resin characterized by carrying out in presence of a catalyst or an acid catalyst in a solvent, and recovering a part of solvent under reduced pressure in a post stage reaction, and adjusting the amount of a solvent and making it react.

[Formula 1]

(Where n represents a number from 0 to 20).

The manufacturing method of this invention uses 0.3-0.6 mol of bischloromethyl biphenyls with respect to 1 mol of 4,4'- dihydroxyphenyls, and uses a solvent so that solid content concentration at the time of injection may be 30-65 wt%. It is preferable to make it react.

Moreover, after content of bischloromethyl biphenyl at the time of reaction becomes 0.3% or less in GPC area%, it is preferable to carry out a reduced pressure solvent and to adjust and react a solvent amount so that solid content concentration may be 55-75 wt%. And after the said reaction, you may add an alkali metal hydroxide and make it neutralize.

According to the present invention, even though bischloromethylbiphenyl is used as the aromatic condensing agent, a polyhydric hydroxy resin having a reduced total chlorine amount can be produced, and an increase in the polymer component can be suppressed to significantly shorten the reaction time. Industrially advantageous manufacturing is attained in that point. Moreover, the epoxidation reaction using this polyhydric hydroxy resin can be manufactured efficiently from the point which has few polymer components, and an effect can be anticipated to reduce cost. When the epoxy resin composition blended with the epoxy resin is cured by heating, the cured product is excellent in terms of high Tg property and thermal decomposition stability, and also provides an excellent effect of reducing the extraction water chlorine ions. It can be used suitably for uses, such as sealing material, a high heat radiation sheet, and a circuit board material, such as a high heat radiation board | substrate.

1 is a GPC chart after the main reaction in Example 1
2 is a GPC chart after the aging reaction in Example 1

EMBODIMENT OF THE INVENTION Hereinafter, this invention is demonstrated in detail.

The manufacturing method of this invention is a method of making polyhydric hydroxy resin represented by Formula (1) by making 4,4'- dihydroxy biphenyl react with bischloromethyl biphenyl as an aromatic condensing agent.

This reaction is carried out in the presence of a non-catalyst or an acid catalyst in a solvent, reacts at least one functional group of a bifunctional aromatic condensing agent (hereinafter also referred to as a main reaction or a shearing reaction), and then the remaining single-terminal functional group. Is reacted while concentrating under reduced pressure (hereinafter also referred to as a aging reaction or a post stage reaction). The polyhydric hydroxy resin thus obtained has a total chlorine content of 4000 wtppm or less, preferably 2000 wtppm or less, and more preferably 1000 wtppm or less. Even when the total amount of chlorine exceeds 1000 wtppm after the aging reaction, the total amount of chlorine of the polyhydric hydroxy resin can be controlled to 1000 wtppm or less by the subsequent neutralization reaction. When the total amount of chlorine is higher than this, in the cured product cured using an epoxy resin obtained by epoxidizing the present polyvalent hydroxy resin, a decrease in the glass transition point (Tg) and a decrease in thermal decomposition stability are caused.

The polyhydric hydroxy resin obtained by the manufacturing method of this invention is represented by General formula (1), and is a mixture of the component from which the value of repeating unit n differs, and n = 0 component is 30% or less 15% or more, Preferably it is 30% or less 20% or more and n = 6 or more of components are 30% or less, Preferably they are 20% or less. When n = 0 component is larger than 30%, the hardened | cured material hardened | cured using the epoxy resin obtained by epoxidizing this polyhydric hydroxy resin WHEREIN: The fall of glass transition point (Tg) and the fall of thermal decomposition stability are caused, and it is 15% When smaller, the epoxy resin melt viscosity obtained by epoxidizing this polyhydric hydroxy resin becomes high. On the other hand, when a component of n = 6 or more is larger than 30%, since the gelation is produced abundantly in the manufacturing process of the epoxy resin obtained by epoxidizing this polyhydric hydroxy resin, there exists a tendency for the yield of resin to fall, and also Since the high molecular weight component of the epoxy resin obtained increases, the melt viscosity of an epoxy resin will become high. Although n is a number of 0-20, Preferably it is 1.0-5.0 as an average value (number average). In addition, although the polyhydric hydroxy resin of this invention is resin which the main component is represented by General formula (1), it is a minor component which is inevitably produced | generated in reaction, and there exists a trace amount which has chlorine and a hydroxyl group in a polybranched polyhydric hydroxy resin and the terminal of a multi-branch. You may also

4,4'-dihydroxybiphenyl used as a raw material is another divalent hydroxybiphenyl compound, for example, 2,2'- dihydroxybiphenyl, etc., unless the effect of this invention is impaired. You may use together the dihydroxy biphenyls. These bivalent hydroxybiphenyl compounds may be substituted by the C1-C6 hydrocarbon group.

As an aromatic condensing agent, 4,4'-bischloromethyl biphenyl is preferable from a reactive viewpoint with 4,4'- dihydroxy biphenyl. However, as another aromatic condensing agent, 4,4'-bishydroxymethyl biphenyl, 4,4'-bisbromomethyl biphenyl, 4,4'-bismethoxymethyl biphenyl, 4,4'- Although biphenyl aralkyl compounds, such as bisethoxy methyl biphenyl, may be used together, the compounding quantity in the whole condensing agent is 50 weight% or less, Preferably it is 30 weight% or less. When aromatic condensing agents other than 4,4'-bischloromethyl biphenyl are more than 50 wt%, since reaction time decreases and reaction product becomes long and a by-product easily arises, hardened | cured material, such as Tg and heat stability, There is a possibility that the physical properties are lowered.

In reaction of 4,4'- dihydroxy biphenyl and bischloromethyl biphenyl as an aromatic condensing agent, 4,4'- dihydroxy biphenyl which is an excess of bifunctional phenolic compound with respect to an aromatic condensing agent is used. do. That is, the usage-amount of an aromatic condensing agent is 0.3-0.6 mol with respect to 1 mol of 4,4'- dihydroxy biphenyl, Preferably it is 0.4-0.5 mol. When the amount of the aromatic condensing agent is less than 0.3 mol, since the n = 0 component increases, the crystallinity is strong, solubility in epichlorohydrin when synthesizing the epoxy resin decreases, and the melting point of the obtained epoxy resin It becomes high, handleability falls, and the hardened | cured material cannot express sufficient high Tg property. On the other hand, when more than 0.6 mol, the production | generation of n = 0 components becomes small, but molecular weight itself becomes high, since the softening point and melt viscosity of resin become high, it causes an impairment in molding workability. Moreover, it becomes difficult for the sock end of bischloromethyl biphenyl which is an aromatic condensation agent to react together, it remains with the component which has a chloromethyl group at one end, and it becomes difficult to reduce all chlorine.

This reaction is first carried out in the presence of a catalyst-free or acid catalyst such as an inorganic acid or an organic acid. Side reactions such as chloromethyl group and OH group react with ether bonds may occur, but they are carried out under acidic conditions to suppress this. Even if the catalyst is non-catalyst, the hydrogen chloride is produced by the substitution reaction to the aromatic ring of the chloromethyl group and becomes an acidic condition. Therefore, the acid catalyst is not essential, but rather an impurity may contaminate the reaction product. Can cause a reaction. Such acid catalysts include, for example, mineral acids such as hydrochloric acid, sulfuric acid and phosphoric acid, organic acids such as formic acid, oxalic acid, trifluoroacetic acid and p-toluenesulfonic acid, zinc chloride, aluminum chloride, iron chloride and boron trifluoride. Lewis acids, solid acids, such as activated clay, silica-alumina, and zeolite, etc. are mentioned.

This reaction may be performed at a temperature of 100 to 250 ° C, preferably at 100 to 180 ° C, and more preferably at 140 to 180 ° C. When the reaction temperature is low, the reactivity between bischloromethylbiphenyl and 4,4'-dihydroxybiphenyl is insufficient, and the reaction takes time, and 4,4'-dihydroxybiphenyl is precipitated to form bischloro. The molar ratio of methylbiphenyl and 4,4'-dihydroxybiphenyl is shifted, and many high molecular weights are produced. On the other hand, when reaction temperature is too high, there exists a possibility of resin decomposition.

In the production method of the present invention, a aging reaction in which at least one functional group in bischloromethylbiphenyl which is a bifunctional aromatic condensing agent reacts with 4,4'-dihydroxybiphenyl, and a remaining terminal functional group react with each other. It is divided into two steps, and the end point of a main reaction may be based on the area bischloromethyl biphenyl which is 3% or less, Preferably it is 1% or less by area% measured, for example by gel permeation chromatography. The main reaction is 1 to 5 hours, preferably 3 to 5 hours at a temperature of 100 ° C or higher, preferably 160 ° C or higher. When the main reaction does not proceed sufficiently, if the solid content concentration is increased and concentrated under reduced pressure, high molecular weight progresses and it becomes difficult to obtain the target polyhydric hydroxy resin. In order to obtain the target polyhydric hydroxy resin, 0.3-0.6 mol of 4,4'-bischloromethyl biphenyl is used with respect to 1 mol of 4,4'- dihydroxyphenyls, and solid content concentration at the time of main reaction is It is good to set it as 30-55 wt%. If the solid content is lower than 30 wt%, the reaction of 4,4'-bischloromethylbiphenyl and 4,4'-dihydroxybiphenyl is insufficient, and the reaction takes time, and the unreacted 4,4 ' Since bischloromethylbiphenyl tends to remain, there exists a tendency for the total amount of chlorine of the polyhydric hydroxy resin obtained to become easy to become high. On the other hand, when it is thicker than 55 wt%, 4,4'-dihydroxybiphenyl tends to precipitate, and the molar ratio of 4,4'-bischloromethylbiphenyl and 4,4'-dihydroxybiphenyl is shifted. The ratio of the high molecular weight body increases. Here, solid content concentration is the density | concentration of solid content except a solvent and a catalyst among all the raw materials used for manufacturing polyhydric hydroxy resin.

Next, a aging reaction in which a polyhydric hydroxy resin having a single-terminal functional group represented by formula (2) reacts with 4,4'-dihydroxybiphenyl or a polyhydric hydroxy resin of formulas (1) and (2) ( Post-stage reaction). Since the single-terminal functional group-containing polyhydric hydroxy resin of the formula (2) reacts with a compound having a phenol ring, not only 4,4'-dihydroxybiphenyl but also the polyhydric hydroxy resin of the other formula (2) Although it may react with the polyhydric hydroxy resin of Formula (1) which is a reaction product, it is mainly reaction with 4,4'- dihydroxy biphenyl.

In the aging reaction, the reactivity is significantly lower than that of the main reaction, and the reaction time requires 20 hours or more in the range of the solid content concentration in the range of 30 to 55 wt% similarly to the main reaction. However, the production method of the present invention can significantly shorten the reaction time by recovering a part of the solvent under reduced pressure in the aging reaction to reduce the amount of the solvent. That is, compared with the case where the solid content concentration of main reaction and aging reaction are made to react uniformly, the aging reaction can be accelerated | stimulated significantly by making solid content concentration of aging reaction higher than the concentration in main reaction.

The end point of the aging reaction may be based on, for example, the total chlorine of 4000 wtppm or less, preferably 2000 wtppm or less, and more preferably 1000 wtppm or less.

The mechanism which can shorten reaction time by adjusting the amount of a solvent in a aging reaction (post-stage reaction) is demonstrated, considering typical reaction example at the time of manufacture of polyhydric hydroxy resin by the following formula.

The reaction by which the polyhydric hydroxy resin which has the chloromethyl terminal represented by Formula (2) on one side is obtained as a main reaction, and the chloromethyl terminal of Formula (2) further has unreacted 4,4'- dihydroxybiphenyl Or the process of reacting with the polyhydric hydroxy resin of another Formula (2) or Formula (1) is made into aging reaction. 4,4'-bischloromethylbiphenyl is preferably 0.5 mol or less with respect to 1 mol of 4,4'- dihydroxyphenyl at the time of injection, and has a chloromethyl terminal of Formula (2) after a main reaction. The structure becomes difficult to occur. Moreover, in the state where 4,4'-bischloromethyl biphenyl which is a crosslinking condensing agent is 1% or less in GPC area%, the fluctuation | variation of the molecular weight distribution at the time of a aging reaction is very small unless local thermal history generate | occur | produces. Lose. In addition, since the content rate of 4,4'- dihydroxy biphenyl of the raw material which is lacking in solvent solubility falls as reaction progresses, the solubility at the start of a aging reaction is improved significantly compared with the start of a main reaction, and a aging reaction is carried out. Concentration in becomes possible. Precipitation was confirmed at 55 wt% of the solid content concentration in the main reaction, whereas precipitation was remarkable at about 70 wt% in the aging reaction. As mentioned above, industrial production can be performed efficiently by optimizing the main reaction conditions for obtaining the target molecular weight distribution, and the manufacturing conditions of the aging reaction which makes the terminal of the chloromethyl group which remain | survives slightly remain.

[Formula 2]

(Wherein m and n each independently represent a number from 0 to 20).

The solid content concentration at the time of aging reaction is preferably 55 to 75 wt%, more preferably 60 to 70 wt%. When the solid content concentration is 60 wt% or less, the promotion of the reaction is insufficient, and no effect can be expected to shorten the reaction time. Moreover, when it is 70 wt% or more, a aging reaction advances but it becomes easy to be nonuniform in the precipitation of a crystal component becoming remarkable, and there exists a manufacturing concern. In the case of non-uniformity, there is a tendency for a local polymerization reaction to occur to increase the high molecular weight component.

In order to raise solid content concentration to the said predetermined | prescribed range, it is necessary to remove a part of solvent, Although there exist means, such as pressure reduction and heating, distillation removal by reduced pressure is preferable. Moreover, what is necessary is just to set the pressure reduction conditions in a aging reaction in the range required in order to control solid content concentration stably. As pressure reduction conditions, 200-700 mmHg is preferable, More preferably, it is 300-500 mmHg. The aging reaction is 1 to 8 hours, preferably 3 to 8 hours at a temperature of 100 ° C or higher, preferably 160 ° C or higher. If the aging reaction temperature is 1 hour or less, the effect of reducing the total chlorine due to reaction promotion is low, and if the aging reaction time is 8 hours or more, the effect of reducing the load on production by shortening the process time is low.

After the aging reaction, a slightly remaining unreacted chloromethyl terminal may be neutralized with alkali metal hydroxides such as sodium hydroxide and potassium hydroxide in order to reduce total chlorine. If the total chlorine is 1000 wtppm or less in the aging reaction, this neutralization reaction is not necessary.

When the neutralization reaction is carried out after the main reaction and the aging reaction of the present invention, the neutralization reaction is carried out at a temperature of 10 to 200 ° C, preferably at 80 to 150 ° C for 1 to 10 hours, preferably 1 to 5 hours. do. In this case, an alkali metal hydroxide is made to exist in excess, and it can react, and the excess part can be used for the alkali metal hydroxide of epoxidation as it is.

As a solvent at the time of reaction, For example, alcohol, such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, ethyl cellosolve, diethylene glycol dimethyl ether, and triglyme, benzene, toluene, chloro It is preferable to use aromatic compounds such as benzene and dichlorobenzene, and of these, ethyl cellosolve, diethylene glycol dimethyl ether, triglyme and the like are particularly preferable. After completion | finish of reaction, although the obtained polyhydric hydroxy resin may remove a solvent by methods, such as distillation under reduced pressure, water washing, or reprecipitation in a poor solvent, you may use as a raw material of an epoxidation reaction leaving a solvent.

Although the polyhydric hydroxy resin represented by General formula (1) obtained by the manufacturing method of this invention can be used, for example in the hardening | curing agent of an epoxy resin, etc., by further reacting with epichlorohydrin, it is represented by following General formula (3) The epoxy resin shown can be obtained. This reaction can be performed similarly to a normal epoxidation reaction. For example, after dissolving a polyhydric hydroxy resin in excess epichlorohydrin, it reacts at 50-150 degreeC, Preferably it is 60-120 degreeC in presence of alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, for 1 to 10 hours. The method of making it come can be mentioned. At this time, the usage-amount of alkali metal hydroxide is 0.8-1.2 mol with respect to 1 mol of hydroxyl groups in a polyhydric hydroxy compound, Preferably it is 0.9-1.1 mol. Moreover, although epichlorohydrin is used excessively with respect to the hydroxyl group in a polyhydric hydroxy resin, it is 1.5-15 mol with respect to 1 mol of hydroxyl groups in a polyhydric hydroxy compound, Preferably it is 2-8 mol. After completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene, methyl isobutyl ketone, filtered, washed with water to remove the inorganic salt, and then the solvent is distilled off. A small amount of epoxy resins represented by the following general formula (3) can be obtained. In the reaction of epoxidation, this epoxy resin tends to increase a little high molecular weight because the epoxy groups in the resin may bond with each other, but almost reflects the molecular weight distribution of the polyhydric hydroxy resin as a raw material, where n = 0 component is 35% or less and n = 6 or more components are 30% or less. However, when there are too many high molecular weight polymers of polyhydric hydroxy resin as a raw material, since the high molecular weight resin becomes gelatinized and removes out of the system by the above-mentioned reaction, the peak ratio of a high molecular weight body reduces and n = 0 component It tends to increase. Moreover, also in epoxy resin, repeating unit n is the number of 0-20, and is about 1.0-5.0 as average value (number average).

[Formula 3]

(Wherein n represents a number from 0 to 20, and G represents a glycidyl group.)

In addition, when epoxidation, although the epoxy group of the produced epoxy compound ring-opens and condensates, the oligomerized oligomer may produce a small amount of byproducts, but such an epoxy compound may exist.

The purity of the epoxy resin, particularly the total amount of chlorine, is preferably less from the viewpoint of improving the performance of the electronic component to be applied. Especially in this invention, in the hardened | cured material obtained using the epoxy resin derived from polyhydric hydroxy resin which reduced the total chlorine amount, high Tg property, thermal decomposition stability, and thermal conductivity improve. The range of the total amount of chlorine of this epoxy resin becomes like this. Preferably it is 2000 ppm or less, More preferably, it is 1500 ppm or less.

In addition, although the softening point or melting point of this epoxy resin can be easily adjusted by changing the molar ratio of the biphenols and aromatic condensing agent at the time of synthesize | combining the polyhydric hydroxy resin which is an epoxy resin raw material, when mixing-processing as an epoxy resin composition From a viewpoint of suppressing the physical property fall by the dissolution residue of a high melting point component, the softening point or melting | fusing point is 140 degrees C or less, More preferably, it is 130 degrees C or less. When the softening point or melting point is higher than this, there exists a tendency which causes physical property fall, such as hardenability and heat resistance.

The said epoxy resin becomes an epoxy resin composition by mix | blending with a hardening | curing agent. Moreover, you may mix | blend a hardening accelerator, an inorganic filler, and an additive.

In the epoxy resin composition, as an additive for improving physical properties, a crosslinked elastomer, a thermoplastic resin, a pigment, a flame retardant, a thixotropic imparting agent, a coupling agent, a fluidity improving agent, a mold releasing agent, a lubricant and the like can be blended.

The said epoxy resin composition can be advantageously used as a varnish state (called varnish) which melt | dissolved one part or all in the organic solvent. When it contains a solvent insoluble content, such as an inorganic filler, it is not necessary to melt | dissolve it, but it is preferable to set it as suspension state and to make it as uniform solution as possible.

The epoxy resin composition used as a varnish can be made into the prepreg which combined the epoxy resin composition and the fibrous base material by performing solvent removal after impregnating into fibrous base materials, such as a glass cross and an aramid nonwoven fabric. Moreover, it can be set as a laminated body by apply | coating the said varnish on sheet-like objects, such as copper foil, stainless steel foil, and a polyimide film, as the case may be. Moreover, it is also possible to form a laminate by laminating a plurality of the prepregs or laminating the prepreg and the sheet-like article.

When an epoxy resin composition is heat-hardened, it can be set as an epoxy resin hardened | cured material, and this hardened | cured material becomes an excellent thing from the point of low hygroscopicity, high heat resistance, adhesiveness, and flame retardance. This cured product can be obtained by molding the epoxy resin composition by a method such as casting, compression molding or transfer molding.

Example

A synthesis example, an Example, and a comparative example are given and this invention is concretely demonstrated to it. However, this invention is not limited to these. "Part" represents a weight part, and "%" represents weight% unless there is particular notice. In addition, the measuring method measured by the following method, respectively.

1) Measurement of hydroxyl equivalent

Using a potentiometric titration apparatus, 1,4-dioxane was used in the solvent to acetylate with 1.5 mol / L acetyl chloride, excess acetyl chloride was decomposed into water and 0.5 mol / L potassium hydroxide was used. Titration.

2) Determination of epoxy equivalent

The potentiometric titration apparatus was used, the tetraethylammonium bromide solution was added using chloroform as a solvent, and it measured using the 0.1 mol / L perchloric acid-acetic acid solution with the potentiometric titration apparatus.

3) Softening point

It measured by the round ball method according to JIS-K-2207 using the automatic softening point apparatus (ASP | M4SP by Meiho Co., Ltd.).

4) melt viscosity

It measured at 150 degreeC using the Brookfield-made CAP2000H type rotational viscometer.

5) whole chlorine

After 1.0 g of the sample was dissolved in 25 ml of butylcarbitol, 25 ml of 1N-KOH propylene glycol solution was added and heated to reflux for 10 minutes, then cooled to room temperature, and 100 ml of 80% acetone water was further added, followed by 0.002N a -AgNO ₃ aqueous solution was measured by carrying out potentiometric titration.

6) Molecular Weight Distribution of Resin

Using a GPC measuring device (manufactured by Tosoh, HLC-8220GPC), 1 TSK Guardclumn (manufactured by Tosoh), 1 TSKgel 2000H XL (manufactured by Tosoh), 1 TSKgel 3000H XL (manufactured by Tosoh), TSKgel 4000H XL ( Tosoh was used), the detector was set as RI, and it measured by making tetrahydrofuran, 1.0 mL / min of a flow volume, and column temperature 40 degreeC in a solvent.

Example 1

Into a 1000 mL four-necked flask, 77.5 g of 4,4'-dihydroxybiphenyl, 119.3 g of diethylene glycol dimethyl ether and 41.8 g of 4,4'-bischloromethylbiphenyl were charged and stirred under a nitrogen stream. It heated up to 160 degreeC, and made it react for 5 hours. In this reaction, the reaction molar ratio is 0.40 and the solid content concentration at the time of injection is 50 wt%. Then, it confirmed that content after main reaction of 4,4'-bischloromethyl biphenyl was 1% or less in GPC area%. Subsequently, the solvent was gradually distilled off under reduced pressure at 160 ° C and 300 mmHg, and concentrated over 8 hours until the solid content concentration was 65 wt%. After the reaction, the mixture was dropped into a large amount of pure water and collected by reprecipitation to give 104 g of a pale yellow resin. The n = 0 component in General formula (1) calculated | required by GPC measurement was 29.1%, and the component of n = 6 or more was 13.7%. Mw / Mn = 2.58 and Mw = 1810 after the main reaction, and Mw / Mn = 2.57 and Mw = 1800 after the aging reaction. The total chlorine was 940 wtppm.

Example 2

Into a 1000 mL four-necked flask, 77.5 g of 4,4'-dihydroxybiphenyl, 119.3 g of diethylene glycol dimethyl ether and 41.8 g of 4,4'-bischloromethylbiphenyl were injected and stirred under a nitrogen stream. It heated up to 160 degreeC, and made it react for 5 hours. In this reaction, the reaction molar ratio is 0.40 and the solid content concentration at the time of injection is 50 wt%. Then, it confirmed that content after main reaction of 4,4'-bischloromethyl biphenyl was 1% or less in GPC area%. Subsequently, the solvent was gradually distilled off under reduced pressure at 160 ° C and 300 mmHg, and concentrated over 5 hours until the solid content concentration was 64 wt%. Then, 2.8g of 48% potassium hydroxide solution was added at 130 degreeC, and it was made to react for 3 hours. After the reaction, the mixture was dropped into a large amount of pure water and collected by reprecipitation to give 103 g of a pale yellow resin. The n = 0 component in General formula (1) calculated | required by GPC measurement was 29.1%, and the component of n = 6 or more was 13.8%. The total chlorine was 1430 wtppm before the neutralization and 230 wtppm after the neutralization.

Comparative Example 1

Into a 1000 mL four-necked flask, 77.5 g of 4,4'-dihydroxybiphenyl, 119.3 g of diethylene glycol dimethyl ether and 41.8 g of 4,4'-bischloromethylbiphenyl were charged and stirred under a nitrogen stream. It heated up to 160 degreeC, and made it react for 20 hours. In this reaction, the reaction molar ratio was 0.40 and the solid content concentration was 50 wt%, and the solvent amount was not adjusted by solvent distillation. After the reaction, the mixture was dropped into a large amount of pure water and collected by reprecipitation to give 104 g of a pale yellow resin. OH equivalent of obtained resin was 129 g / eq. The component of n = 0 in General Formula (1) determined by GPC measurement was 28.9%, and the component of n = 6 or more was 14.1%. The total chlorine was 2300 wtppm.

Comparative Example 2

Into a 1000 mL four-necked flask, 77.5 g of 4,4'-dihydroxybiphenyl, 90.0 g of diethylene glycol dimethyl ether and 41.8 g of 4,4'-bischloromethylbiphenyl were injected and stirred under a nitrogen stream. It heated up to 160 degreeC. It reacted at 160 degreeC for 20 hours. In this reaction, the reaction molar ratio was 0.40 and the solid content concentration was 57 wt%, and the solvent amount was not adjusted by solvent distillation. After the reaction, the mixture was dropped into a large amount of pure water and collected by reprecipitation to give 104 g of a pale yellow resin. The hydroxyl equivalent of the obtained resin is 129 g / eq. The component of n = 0 in General Formula (1) determined by GPC measurement was 29.9%, and the component of n = 6 or more was 22.2%. The total chlorine was 1900 wtppm.

Comparative Example 3

Into a 1000 mL four-necked flask, 77.5 g of 4,4'-dihydroxybiphenyl, 97.9 g of diethylene glycol dimethyl ether, and 52.3 g of 4,4'-bischloromethylbiphenyl were charged and stirred under a nitrogen stream. It heated up to 160 degreeC, and made it react for 10 hours. In this reaction, the reaction molar ratio was 0.50 and the solid content concentration was 57 wt%, and the solvent amount was not adjusted by solvent distillation. After the reaction, the mixture was dropped into a large amount of pure water and collected by reprecipitation to give 112 g of a pale yellow resin. The hydroxyl equivalent of the obtained resin is 138 g / eq. The n = 0 component in General formula (1) calculated | required by GPC measurement was 21.7%, and the component of n = 6 or more was 35.0%. The total chlorine was 3000 wtppm.

Comparative Example 4

Into a 1000 mL four-necked flask, 77.5 g of 4,4'-dihydroxybiphenyl, 119.3 g of diethylene glycol dimethyl ether and 41.8 g of 4,4'-bischloromethylbiphenyl were charged and stirred under a nitrogen stream. It heated up to 160 degreeC, and made it react for 5 hours. In this reaction, the reaction molar ratio is 0.40 and the solid content concentration at the time of injection is 50 wt%. Then, it confirmed that content after main reaction of 4,4'-bischloromethyl biphenyl was 1% or less in GPC area%. Subsequently, the solvent was gradually distilled off at atmospheric pressure at 170 ° C., and then concentrated over 20 hours until the solid content concentration became 57 wt%. After the reaction, the mixture was dropped into a large amount of pure water and recovered by reprecipitation to give 105 g of a pale yellow resin. The n = 0 component in General formula (1) calculated | required by GPC measurement was 29.1%, and the component of n = 6 or more was 13.4%. The total chlorine was 1700 wtppm.

Example 3

449 g of epichlorohydrin was added to 104 g of the resin obtained in Example 1 to dissolve it. Subsequently, 65.8 g of an aqueous 49% sodium hydroxide solution was added dropwise at 65 ° C. under reduced pressure over 3 hours, and water and epichlorohydrin, which had been refluxed and distilled off during this dropping, were separated in a separation tank, and epichlorohydrin was returned to the reaction vessel. , Water was removed out of the system and reacted. After the reaction was completed, epichlorohydrin was distilled off and dissolved in toluene. Thereafter, the salt was removed by washing with water, and toluene was distilled off to obtain 145 g of an epoxy resin. As for the epoxy equivalent of obtained resin, melt viscosity in 126 degreeC and 150 degreeC was 197 g / eq., The softening point was 0.25 Pa.s, and all the chlorine was 1020 wtppm. The n = 0 component in General formula (3) was 27.6%, and the n = 6 or more component was 23.4%.

Claims (4)

A method for producing a polyhydric hydroxy resin represented by the general formula (1) by reacting 4,4'-dihydroxybiphenyl and bischloromethylbiphenyl, the area% measured by gel permeation chromatography (GPC area% In the preparation of a polyvalent hydroxy resin having a high molecular weight component of 30% or less, 15% or more, n = 6 or more, and a total chlorine content of 1000 wtppm or less in the n = 0 component, the reaction is free from solvents. A method for producing a polyhydric hydroxy resin, which is carried out in the presence of a catalyst or an acid catalyst, and recovers a part of the solvent under reduced pressure in the subsequent reaction to adjust the amount of the solvent.

(Where n represents a number from 0 to 20). The method of claim 1,
It is characterized by using 0.3-0.6 mol of bischloromethyl biphenyls with respect to 1 mol of 4,4'- dihydroxyphenyls, and using a solvent so that solid content concentration at the time of injection may be 30-55 wt%, It characterized by the above-mentioned. And manufacturing method of polyhydric hydroxy resin. The method according to claim 1 or 2,
After content of bischloromethyl biphenyl at the time of reaction becomes 0.3% or less in GPC area%, pressure reduction desolvent is performed and it reacts by adjusting a solvent amount so that solid content concentration may be 55-75 wt%, It characterized by the above-mentioned. And manufacturing method of polyhydric hydroxy resin. The method according to any one of claims 1 to 3,
The manufacturing method of polyhydric hydroxy resin which adds alkali metal hydroxide and neutralizes after the said reaction.

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