JP3398181B2 - Method for producing polyphenols and method for producing condensate of polyphenols - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to heat resistance, moisture resistance, toughness,
Excellent preparation of polyphenols such as electric characteristics, relates to the preparation of condensates of polyphenols.

[0002]

2. Description of the Related Art Recently, science and technology have been making rapid progress mainly in the electronics industry, but in particular, semiconductor-related technologies and laminated plates have progressed remarkably.

With the increase in the degree of integration of memory in semiconductors,
Although wiring is becoming finer and chips are becoming thinner, the mounting method is also shifting from through-hole mounting to surface mounting as the degree of integration is improved.

In an automated surface mounting line, the semiconductor package undergoes a rapid temperature change during soldering of the lead wire, cracks occur in the resin molding portion, and the interface between the lead wire and the resin deteriorates. There is a problem that the moisture resistance decreases.

In order to solve the above-mentioned problems, methods such as addition of a silicone compound, addition of a thermoplastic oligomer, or silicone modification have been proposed for the purpose of mitigating thermal shock when the semiconductor package is immersed in a solder bath. However, in any of the methods, a crack is generated in the molded product after dipping the solder, and a reliable resin composition for semiconductor encapsulation cannot be obtained.

Phenolic resins are often used in combination with epoxy resins in semiconductor resin compositions,
As the phenol resin, novolac phenol resin or novolac cresol resin is generally used. However, when the above-mentioned phenol resin is used, the hygroscopicity of the semiconductor package is strong, and as a result, there is a problem that cracks cannot be avoided when the solder bath is immersed. Therefore, recently, in order to improve the heat resistance of the resin for semiconductor encapsulation, for example, a dicyclopentadiene-modified phenol resin has been proposed as a phenol resin having excellent moisture resistance (Japanese Patent Laid-Open No. 62-201922). . However, although the above-mentioned dicyclopentadiene-modified product has excellent moisture resistance, there is a problem that satisfactory heat resistance cannot be obtained because of its low crosslink density.

In the field of high-speed electronic equipment, signal delay and heat generation of the device have become a problem in recent years as the density of electronic elements increases, the speed of signals increases, and the frequency increases. Since the signal delay time increases in proportion to the square root of the relative dielectric constant, a printed wiring board for high-speed electronic equipment having a low dielectric constant is required. Laminates having a glass cloth as a base material, which are widely used in general, have a considerably large dielectric constant of 4.5 to 5.0 and are insufficient for high-speed electronic devices and high-frequency devices. Therefore, in order to lower the dielectric constant, a laminated plate using polyethylene, polytetrafluoroethylene, polyphenylene oxide, polysulfone, or the like has been developed. However, since these are thermoplastic resins, there is a problem that strength, solder heat resistance, etc. are not sufficient.

Epoxy resin laminates are generally manufactured by incorporating a novolac epoxy resin as a main component and a brominated epoxy resin for the purpose of flame retardancy. Although the dielectric constant is generally due to the structure of the epoxy resin used, it also varies greatly depending on the curing agent combined.

Dicyandiamide is usually used as a curing agent for epoxy resin laminates. However, when this curing agent is used, not only the dielectric constant of the obtained substrate deteriorates but also the moisture resistance remarkably deteriorates. Therefore, in recent years, studies have been conducted to replace them with phenolic resins to improve their properties.However, ordinary phenolic resins such as novolac phenolic resins and novolac cresol resins have moisture resistance, dielectric properties and heat resistance. At present, there is no laminated plate satisfying all the characteristics of the property. At this time, generally, as a method for increasing the crosslink density of the novolac phenol resin and improving the heat resistance, a method of increasing the number of nuclei is adopted, but the hygroscopicity is increased, the moisture resistance is reduced, and the brittleness is remarkable. However, there is a drawback that the toughness is deteriorated.

Therefore, in order to manufacture a printed circuit board suitable for high-speed electronic equipment and high-frequency equipment, it is necessary to develop a new phenol resin and combine it with an epoxy resin to satisfy the above-mentioned respective characteristics. It has been demanded.

Further, in the case of electrical insulating materials, fiber reinforced composite materials, coating materials, molding materials, adhesive materials, etc., the epoxy resin composition which has the disadvantages of the conventional products improved in order to similarly improve the moisture resistance, adhesiveness, heat resistance and the like. Development of things is desired.

[0012]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for producing a polyphenol or a condensate thereof having a low hygroscopicity, a small steric hindrance and a high crosslinking rate.

[0013]

[0014]

[0015]

According to the invention, butadiene, isoprene, piperylene or mixtures thereof,
Production of polyphenols characterized by reacting a dimer monophenoxy compound obtained by reacting with a C6-12 phenol with a C6-12 phenol in the presence of an acid catalyst. Law is provided.

The present invention also provides a method for producing polyphenols, which comprises reacting octatriene and / or dimethyloctatriene with phenols having 6 to 12 carbon atoms in the presence of an acid catalyst. It

Further, according to the present invention, the polyphenol obtained by each of the above-mentioned production methods and a ketone or an aldehyde having 1 to 12 carbon atoms are subjected to a condensation reaction in the presence of an acid catalyst. Methods of making condensates of the class are provided.

Furthermore, according to the present invention, a mixture of 5 to 95% by weight of polyphenols and 95 to 5% by weight of phenols having 6 to 12 carbon atoms obtained by each of the above production methods,
Provided is a method for producing a polyphenol condensate, which comprises subjecting a ketone or an aldehyde having 1 to 12 carbon atoms to a condensation reaction in the presence of an acid catalyst.

[0019]

[0020]

[0021]

The present invention will be described in more detail below.

The method for producing polyphenols of the present invention is a method for producing a specific monophenoxy compound in the presence of an acid catalyst having 6 to 6 carbon atoms.
12 phenols (hereinafter referred to as the first production method) or octatriene and / or dimethyloctatriene are reacted with C 6-12 phenols in the presence of an acid catalyst (hereinafter referred to as 2)
Is the way.

The specific monophenoxy compound in the first production method is obtained by reacting butadiene, isoprene, piperylene or a mixture thereof (hereinafter appropriately referred to as a dimer component) with a phenol having 6 to 12 carbon atoms. Can be obtained. The reaction is, for example, a known telomerization reaction described in Kodansha, edited by Shin Okawara, 1976, "Oligomer", page 58, and R, BaKer, Chemical Review, 73 (5), 487 (1973). Can be done by.
Specifically, nickel, palladium, platinum, cobalt,
In the presence of a metal catalyst such as rhodium, iridium, iron, titanium or hafnium, butadiene, isoprene or piperylene and phenol, o-cresol, m-cresol, p-cresol, diethylphenol, hydroquinone, catechol, resorcin, pyrogallol, α , Β
-Phenols having 6 to 12 carbon atoms such as naphthol, bisphenol A and dihydroxybiphenyl can be produced by telomerization reaction at preferably 30 to 150 ° C for 0.5 to 5 hours. At this time, the amount of the butadiene, isoprene or piperylene and the phenol having 6 to 12 carbon atoms to be charged is preferably 1: 1 to 1:10 in weight ratio. Further, in order to selectively carry out the dimerization of butadiene, isoprene or piperylene, it is preferable to use a phosphine such as triphenylphosphine as a ligand, an amine, and a solvent that does not affect the reaction in the reaction, Specifically, benzene, toluene,
Xylene or the like can also be used.

Examples of the dimeric monophenoxy compound obtained by the above reaction include 1-phenoxy-2,7-
Octadiene, 3-phenoxy-1,7-octadiene, 3-phenoxydimethyloctadiene, phenoxymethyloctadiene and the like can be mentioned, but for use in the next reaction, a cyclic one may be included, It is preferable to use a chain monophenoxy compound in order to improve the curability of the obtained polyphenols. In addition, in the above reaction, a small amount of 1,3,7-octatriene, dimethyloctatriene and the like are produced in addition to the monophenoxy compound, which can be separated by a known purification method.

On the other hand, in order to prepare octatriene and dimethyloctatriene used in the second production method, the presence of a metal catalyst similar to that in the telomerization reaction is used in a system in which an active hydrogen solvent such as alcohol or phenol is not present. It can be obtained by, for example, a method of dimerizing butadiene, isoprene or piperylene (hereinafter referred to as "oligomerization reaction") and the like, and specifically can be produced by the method described in the above-mentioned document. Further, as a method other than the oligomerization reaction, butadiene, isoprene or piperylene,
It can also be obtained by chain-like dimerization by a known reaction such as thermal reaction, radical reaction or cationic polymerization.
The octatriene and dimethyloctatriene used in the next reaction may include cyclic ones, but it is preferable to use chain ones in order to improve the curability of the obtained polyphenols.

Next, in the first method, the monophenoxy compound is used, and in the second production method, the octatriene and / or dimethyloctatriene is used in the presence of an acid catalyst to obtain phenols having 6 to 12 carbon atoms. The reaction (hereinafter referred to as “alkylation reaction”) can produce the target polyphenols.

As the acid catalyst used in the first and second methods, inorganic acids such as sulfuric acid; alkanesulfonic acids having 1 to 10 carbon atoms such as p-toluenesulfonic acid and methanesulfonic acid; trifluoromethanesulfonic acid, Examples thereof include trifluoroacetic acid, anion exchange resin, AlCl ₃ , and boron trifluoride. Particularly, the boron trifluoride-based catalyst, specifically, boron trifluoride phenol complex is used because of its activity and ease of post-treatment. , Boron trifluoride ether complex, boron trifluoride amine complex and the like are preferable. The amount of the acid catalyst used varies depending on the type of the catalyst and the purpose. For example, in the case of a boron trifluoride phenol complex, the dimer component 10 of the raw material is used.
It is usually 0.1 to 15 parts by weight, preferably 1 to 8 parts by weight, relative to 0 parts by weight.

Examples of the phenols having 6 to 12 carbon atoms include the same compounds as those listed in the telomerization reaction.

The molar ratio of the monophenoxy compound or octatriene and / or dimethyloctatriene to the phenols having 6 to 12 carbon atoms is 1: 2.
The ratio is preferably from about 1:20, and is appropriately selected depending on the purpose.

Although the reaction conditions of the alkylation reaction differ depending on the type of catalyst, the reaction temperature is usually 10 to 170 ° C.,
It is desirable to carry out the reaction at 50 to 150 ° C. for 1 to 5 hours. Further, in the reaction, a solvent such as benzene, toluene, xylene, chlorobenzene or the like can be used as long as it does not affect the reaction.

The removal of the acid catalyst in the alkylation reaction can be carried out by a known and conventional method. Specifically, the catalyst can be removed by deactivating with an aqueous solution of sodium hydroxide or potassium hydroxide and washing with water. A method of deactivating with calcium hydroxide or magnesium oxide and then filtering is also preferable.

The polyphenol obtained by the method for producing polyphenols of the present invention has a number average molecular weight of 296 to 150.
0, the softening point is 70 to 120 ° C., the hydroxyl equivalent is 130 to 1
It is preferably 85 g / eq.

The method for producing a condensate of polyphenols of the present invention is a method in which the polyphenols obtained by the first production method or the second production method and aldehydes or ketones having 1 to 12 carbon atoms are treated with an acid. Polyphenols 5 to 95 obtained by a condensation reaction (hereinafter referred to as a third production method) in the presence of a catalyst or obtained by the first production method or the second production method.
And a mixture of 95% to 5% by weight of phenols having 6 to 12 carbon atoms and an aldehyde or ketone having 1 to 12 carbon atoms are subjected to a condensation reaction in the presence of an acid catalyst (hereinafter referred to as the fourth production method). Method).

Examples of the aldehydes having 1 to 12 carbon atoms used in the third and fourth production methods include formaldehyde, acetaldehyde, propylaldehyde,
Butyraldehyde, benzaldehyde, hydroxybenzaldehyde and the like can be mentioned, and the carbon number is 1 to 1.
Examples of the ketones of 2 include acetone, 2-butanone, cyclohexanone, and acetophenone.

In the third production method, the charging equivalent ratio of the polyphenols and the aldehydes or ketones having 1 to 12 carbon atoms is different depending on the purpose, but is usually 1: 1 to 20: 1. It is desirable to have.

The carbon number of 6 to 6 in the fourth manufacturing method is also used.
Preferable examples of 12-phenols include the same compounds as listed in the first and second production methods. At this time, the charging equivalent ratio of the mixture of polyphenols and phenols having 6 to 12 carbon atoms and the aldehydes or ketones having 1 to 12 carbon atoms varies depending on the purpose, but is usually 1: 1 to 20: A value of 1 is desirable. In the condensation reaction in the fourth production method, the polyphenols and the phenols having 6 to 12 carbon atoms react with the ketones or the aldehydes, so that the content of the phenolic hydroxyl group greatly changes. Therefore,
It is preferable to carry out the production in consideration of the content of the phenolic hydroxyl group depending on the purpose. Further, in the fourth production method, after the polyphenols are produced by the first and second production methods, an acid catalyst and an unreacted carbon number of 6 to 1 are used.
It is also possible to add the aldehydes or ketones having 1 to 12 carbon atoms and carry out the condensation reaction without removing the phenols of 2, the solvent and the like.

As the acid catalyst in the third and fourth production methods, the same compounds as those listed in the first and second production methods, organic acids such as oxalic acid, inorganic acids such as hydrochloric acid and the like can be used. Can be used. The amount of acid catalyst used is
0.1 to 15 per 100 parts by weight of polyphenols
It is preferably about 1 to 8 parts by weight, especially 1 to 8 parts by weight.

The reaction conditions in the third and fourth production methods differ depending on the kind of the catalyst, but the reaction temperature is preferably 40 to 170 ° C., particularly preferably 50 to 150 ° C.
It is desirable to react for ~ 5 hours. Further, in the reaction, a solvent may be used if necessary, and as the solvent, aromatic hydrocarbons such as benzene and toluene, ketones such as methyl ethyl ketone and methyl isobutyl ketone,
Examples thereof include ethers such as diethyl ether and diethylene glycol dimethyl ether, and esters such as ethyl acetate cellosolve. Further, in order to carry out the reaction smoothly, it is preferable to remove water produced during the reaction.

The removal of the acid catalyst in the condensation reaction can be carried out in the same manner as the removal of the acid catalyst in the alkylation reaction.

The number average molecular weight of the condensate obtained by the third and fourth production methods is 402 to 2500, and the softening point is 78 to
It is preferably 150 ° C. and the hydroxyl equivalent is 124 to 250 g / eq.

The polyphenols and the condensates of polyphenols of the present invention can be used as a main resin for laminates, encapsulants, etc., as an epoxy resin epoxidized with epichlorohydrin, etc., and also with naphthoquinone diazide sulfonyl chloride, etc. It can be modified and used as a positive resist.

Polyphenols and / or polyphenol condensates and epoxies obtained by the above-mentioned first to fourth production methods
To obtain an epoxy resin composition using a resin as an essential component
You can

[0044] As the epoxy resin used in the e epoxy resin composition, for example bisphenol A diglycidyl ether type epoxy resin, phenol novolak type epoxy resin, ortho-cresol novolak type epoxy resin, bisphenol A novolac type epoxy resin, bisphenol F novolac Examples thereof include epoxy resin, brominated phenol novolac type epoxy resin, brominated bisphenol A diglycidyl ether, naphthol novolac type epoxy resin, trifunctional epoxy resin, tetrafunctional epoxy resin and biphenyl type epoxy resin. The molecular weight, epoxy equivalent and the like of these can be appropriately selected according to the application.

[0045] In the epoxy resin composition, said epoxy resin containing as essential components, the mixing ratio of the condensate of polyphenols and / or polyphenols, be variously selected depending on the components to the application and uses However, it is most preferable that the number of epoxy groups contained in one molecule of the epoxy resin and the number of phenolic hydroxyl groups in the polyphenols and / or the condensate of the polyphenols are in the vicinity of an equivalent amount, and the epoxy resins 30 to 70 It is desirable that the amount of the polyphenols and / or the polyphenol condensate is 70 to 30% by weight.

[0046] The epoxy resin composition, in addition to the essential ingredients, further known phenolic resin, a curing accelerator,
Various fillers, additives and the like can be used together depending on the application.

Examples of the phenol resin include bisphenol A, brominated bisphenol A, novolac phenol resin, novolac orthocresol resin, bisphenol A novolac type phenol resin, bisphenol F novolac type phenol resin, brominated novolac phenol resin, naphthol novolac type resin. Examples thereof include phenolic resins and mixtures thereof. The compounding ratio of the phenol resin is 1 with respect to 100 parts by weight of polyphenols and / or polyphenol condensates.
It is preferably not more than 00 parts by weight.

Any known curing accelerator may be used. Examples thereof include tertiary amines, imidazoles, organic acid metal salts, Lewis acids, amine complex salts, phosphorus compounds, and mixtures thereof. be able to. The mixing ratio of the curing accelerator is preferably 8 parts by weight or less with respect to 100 parts by weight of the essential components.

Further, as the above-mentioned fillers and additives, colorants, flame retardants, release agents, coupling agents, crystalline silica powder, fused silica powder, alumina powder, talc, quartz glass powder, calcium carbonate powder, glass. Fiber, pitch, amino resin, alkyd resin and the like can be mentioned, and the mixing ratio thereof can be appropriately selected according to the application.

[0050] The epoxy resin composition for electronic material described below, laminates, in addition to a sealing material, can also be used in applications such as an insulating powder coating composition.

[0051] and condensate of the polyphenols obtained in the first to fourth manufacturing methods and / or polyphenols, Epo
Electronic material using xy resin and curing accelerator as essential components
Epoxy Resin Composition for Materials and Epoxy Resin Composition for Laminated Board
You can get things.

As the above-mentioned essential components, those specifically listed in the above-mentioned epoxy resin composition can be preferably mentioned, but in the case of using for electronic materials, as the polyphenols and / or polyphenols condensates. In the production of polyphenols, a monophenoxy compound, or octatriene and / or dimethyloctatriene, and a phenol having 6 to 12 carbon atoms were charged at a molar ratio of 1: 5 to 1:20 to produce a softening point. When producing low-curing polyphenols and polyphenols condensates, polyphenols, or a mixture of polyphenols and phenols having 6 to 12 carbons, and aldehydes or ketones having 1 to 12 carbons It has a low softening point and is excellent in curability. Preferably used condensates of polyphenols was. On the other hand, when it is used for a laminated plate, as a polyphenols and / or a condensate of polyphenols, a monophenoxy compound, or octatriene and / or dimethyloctatriene, and a carbon number of 6 to 12 are used in the production of polyphenols. In the production of a relatively high molecular weight polyphenols produced by adjusting the molar ratio of the phenols to phenols to be 1: 3 to 1: 5, or a polyphenol condensate, polyphenols, or polyphenols and 6 to 12 carbon atoms are produced. It is preferable to use a condensate of high molecular weight polyphenols produced by adjusting the charged molar ratio of the mixture of the phenols of 1 to the aldehydes or ketones having 1 to 12 carbon atoms to 1: 1 to 6: 1. Further, in the epoxy resin composition for electronic materials, formalin, hexamethylenetetramine, melamine, methylated melamine usually used as a curing agent for phenolic resins,
A curing agent such as butylated melamine can also be included. The amount of these curing agents used is not particularly limited as long as it is an amount that cures the composition. Further, in the epoxy resin composition for laminated board, a halogenated phenolic resin or the like is further added to the above polyphenols or condensate, or a modified phenolic resin or an epoxy resin is prepared by addition reaction of a halogenated polyvalent epoxy compound or the like. It is also possible to mix the resin component and the like.

In the epoxy resin composition for electronic materials or laminates, the mixing ratio of the essential components is the epoxy resin and the polyphenols and / or polyphenol condensates obtained by the first to fourth production methods. The mixing ratio of the curing accelerator is the same as that of the epoxy resin composition, and the mixing ratio of the curing accelerator is 100 parts by weight of the epoxy resin and the polyphenols and / or polyphenol condensates obtained by the first to fourth production methods. On the other hand, it is preferably 0.1 to 8 parts by weight.

To use the above-mentioned epoxy resin composition for electronic materials, for example, after mixing the above-mentioned components, it is used as a casting material, or an inorganic powder is added to form an insulating powder coating. On the other hand, in order to use the epoxy resin composition for laminated boards, a method of impregnating a glass cloth or the like with a solution of the composition and laminating and molding a dried prepreg can be used.

[0055] and condensate of the polyphenols obtained in the first to fourth manufacturing methods and / or polyphenols, Epo
An epoxy resin composition for encapsulant can be obtained by using a xy resin, a curing accelerator, and an inorganic filler as essential components.
Wear.

As the above-mentioned essential components, those specifically listed in the above-mentioned epoxy resin composition can be preferably cited. Particularly, as the inorganic filler, crystalline silica powder, alumina powder, talc, quartz glass powder, calcium carbonate are preferred. Powder, glass fiber, etc. can be mentioned. Further, as the polyphenols and / or polyphenols condensates, in the production of polyphenols, a monophenoxy compound, or octatriene and / or dimethyloctatriene, and a charging molar ratio of phenols having 6 to 12 carbon atoms, When producing low molecular weight polyphenols produced as 1: 7 to 1:20, or a condensate of polyphenols, polyphenols, or a mixture of polyphenols and phenols having 6 to 12 carbon atoms, and 1 to 1 carbon atoms are produced.
Charge molar ratio of 12 with aldehydes or ketones to 1
It is preferable to use a condensate of low molecular weight polyphenols produced as 0: 1 to 20: 1.

In the epoxy resin composition for the encapsulant, the blending ratio of the essential components is 4 to 30% by weight of the epoxy resin, and the polyphenols and / or polyphenol condensates obtained by the first to fourth production methods are used. 4-30% by weight,
The inorganic filler is preferably 50 to 90% by weight, and the mixing ratio of the curing accelerator is 100 parts by weight of the epoxy resin and the polyphenols and / or polyphenols condensates obtained by the first to fourth production methods. On the other hand, it is preferably 0.1 to 5 parts by weight. At this time, if the compounding ratio of the inorganic filler is less than 50% by weight, the volume change due to the heat change is large and cracks are likely to occur, and if it exceeds 90% by weight, the impact resistance is deteriorated, which is not preferable.

[0058] To use the encapsulant epoxy resin composition, for example fillers to be added depending on the each essential components and necessary additives, were mixed well uniformly by a mixer or the like, further hot roll Alternatively, melt kneading with a kneader or the like,
It can be used by a method such as crushing after cooling.
At this time, it is usually 120 to 220 with a transfer molding machine or the like.
℃, preferably 150 ~ 200 ℃, usually 10 ~ 300
Second molding, usually 160-220 ℃, preferably 17
It is desirable to cure at 0 to 200 ° C. for usually 0.5 to 5 hours.

[0059]

According to the production method of the present invention, it is possible to obtain polyphenols and their condensates having a high crosslinking rate, a low hygroscopicity, a high heat resistance and a high toughness.

[0060]

[0061]

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples.

[0062]

Example 1 5.0 g of palladium (II) acetylacetonate and 15.5 g of triphenylphosphine were placed in an autoclave having a capacity of 10 liters, which was replaced with nitrogen and equipped with a stirrer.
After charging 3500 g of phenol and raising the temperature to 90 ° C., 1000 g of isoprene was sequentially added over 3 hours. Although heat was generated with the addition of isoprene, the reaction temperature was maintained at 90 ° C. by removing heat, and after the addition, stirring was continued for 3 hours to carry out the telomerization reaction. After completion of the reaction, 2000 g of 2% dilute hydrochloric acid water was added to the reaction solution to deactivate the catalyst, and then 3000 g of toluene was added. Then, separate the toluene layer,
After washing with water and distillation under reduced pressure, a dimer component of isoprene consisting of 985 g of 1-phenoxydimethyloctadiene, 112 g of 3-phenoxydimethyloctadiene and 100 g of dimethyloctatriene was obtained. Of this dimer component, 1-phenoxydimethyloctadiene and 3-
The following alkylation reaction was carried out using phenoxydimethyloctadiene.

Phenol 1 dehydrated to a water content of 60 ppm in a 5-liter four-necked flask equipped with a stirrer and a thermometer
After 880 g and 36 g of boron trifluoride / phenol complex were added and thoroughly mixed, 400 g of the dimer component was added over 1 hour while maintaining the system temperature at 90 to 100 ° C. Then, the temperature in the system was raised to 130 ° C., and the mixture was heated and stirred for 3 hours. After the reaction, 700 g of a 3 wt% sodium hydroxide aqueous solution was added to the reaction solution, the mixture was stirred for 2 hours to deactivate the catalyst, and 1500 g of toluene was added, and the washing operation with water was repeated 3 times to recover a toluene layer. Next, the toluene layer is concentrated by distillation to give a softening point of 85 ° C. and an OH equivalent of 175 g.
/ Eq, polyphenols with a number average molecular weight of 450 (1)
650 g were obtained.

[0064]

Example 2 5.0 g of palladium (II) acetylacetonate, 15.5 g of triphenylphosphine, and 3000 g of benzene were charged into a 10-liter autoclave equipped with a stirrer that had been replaced with nitrogen, and after heating to 90 ° C., 1000 g of isoprene was added. Sequentially added over 3 hours. Heat was generated with the addition of isoprene, but the reaction temperature was 90 ° C due to heat removal.
After the addition, the mixture was further stirred for 3 hours to carry out an oligomerization reaction. After completion of the reaction, 2000 g of 2% dilute hydrochloric acid water was added to the reaction solution to deactivate the catalyst, and then 3000 g of benzene was added. Then, the benzene layer was separated, washed with water, and distilled under reduced pressure to obtain dimethyl octatriene 7
A fraction consisting of 20 g and 50 g of cyclic isoprene dimer was obtained. The following reaction was performed using this dimer component.

Phenol 30 dehydrated to a water content of 60 ppm in a 5-liter four-necked flask equipped with a stirrer and a thermometer
00g and 36g of boron trifluoride / diethyl ether complex
Was added and mixed well. While maintaining the system temperature at 90 to 100 ° C, 400 g of the dimer component was added over 1 hour. Then, the temperature in the system was kept at 100 ° C., the mixture was heated and stirred for 3 hours, and 700 g of a 3 wt% sodium hydroxide aqueous solution and 1500 g of toluene were added to the obtained reaction product solution,
The catalyst was deactivated by stirring for a period of time. Then, after standing for 2 hours, the washing operation with water was repeated 3 times to collect the organic layer. Then, unreacted phenol and toluene were removed by distillation to obtain 550 g of polyphenol (2) having a softening point of 82 ° C., an OH equivalent of 165 g / eq and a number average molecular weight of 400.

[0066]

Example 3 A telomerization reaction was carried out under the same conditions as in Example 1 except that butadiene was used instead of isoprene, followed by deactivation, extraction and distillation under reduced pressure to obtain 950 g of 1-phenoxyoctadiene and 3-phenoxydimethyl. A butadiene dimer component consisting of 90 g of octadiene and 110 g of octatriene was obtained. When an alkylation reaction was carried out in the same manner as in Example 1 using the dimer components except octatriene, 480 g of polyphenols (3) having a softening point of 77 ° C., an OH equivalent of 168 g / eq and a number average molecular weight of 430 were obtained. Was given.

[0067]

[Example 4] Octatriene 900 was prepared by conducting an oligomerization reaction under the same conditions as in Example 2 except that butadiene was used instead of isoprene, followed by deactivation, extraction and distillation under reduced pressure.
g was obtained. When an alkylation reaction was carried out in the same manner as in Example 1 using this octatriene, the softening point was 75 ° C. and OH
490 g of polyphenols (4) having an equivalent weight of 160 g / eq and a number average molecular weight of 395 were obtained.

[0068]

Example 5 Dimethyloctatriene 800 was prepared by performing the oligomerization reaction under the same conditions as in Example 2 except that isoprene was replaced with piperylene, followed by deactivation, extraction and distillation.
g was obtained. When an alkylation reaction was carried out in the same manner as in Example 1 using this dimethyl octatriene, a softening point of 82
As a result, 505 g of a polyphenol (5) having an OH equivalent of 166 g / eq and a number average molecular weight of 420 was obtained.

[0069]

Example 6 Alkylation was carried out in the same manner as in Example 1 using 180 g of 1-phenoxydimethyloctadiene obtained in Example 1, 20 g of 3-phenoxydimethyloctadiene, 1200 g of α-naphthol and 1200 g of chlorobenzene. After the reaction, the softening point is 105 ° C and the OH equivalent is 220.
450 g of polyphenols (6) having g / eq and a number average molecular weight of 520 were obtained.

[0070]

Example 7 A 5 liter reactor equipped with a reflux condenser and a Liebig condenser was charged with 1600 g of phenol and 300 g of toluene and heated to 170 ° C. to distill 250 g of toluene, and the water content in the system becomes 60 ppm. Dehydrated until. Then, the system was cooled to 70 ° C., 16 g of boron trifluoride / phenol complex was added and uniformly mixed, and then the polyphenols (1) synthesized in Example 1 (360 g) was reacted for 1.0 hour at a reaction temperature of 70 ° C. It dripped gradually over it. After the dropping was completed, the reaction was continued at 70 ° C for 30 minutes and then 140
The temperature was raised to 0 ° C., and the mixture was further heated and stirred for 2.5 hours. After the temperature inside the system was lowered to 70 ° C., 30 g of paraformaldehyde was added, and the reaction was continued at 70 ° C. for another hour. After completion of the reaction, 40 g of magnesium compound "KW-1000" (trade name; manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes to deactivate the catalyst, and then the reaction solution was filtered. The obtained transparent reaction liquid was distilled under reduced pressure at 200 ° C. to obtain 400 g of a condensate (1) having a softening point of 93 ° C., an OH equivalent of 156 and an average molecular weight of 640.

[0071]

Example 8 A 5 liter reactor equipped with a reflux condenser and a Liebig condenser was charged with 20 parts of methyl isobutyl ketone.
After adding 00 liters, 10 g of p-toluenesulfonic acid, and 400 g of the polyphenols (1) synthesized in Example 1, 40 g of 40% formalin aqueous solution was added at 70 ° C., and the reaction was continued at 70 ° C. for another hour. . After completion of the reaction, magnesium compound "KW-1000" (trade name;
40 g of Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes to deactivate the catalyst, and then the reaction solution was filtered. The obtained transparent reaction solution was distilled under reduced pressure at 200 ° C to give a softening point of 110 ° C,
Condensate (2) 39 with OH equivalent 178 and average molecular weight 720
0 g was obtained.

[0072]

[Reference Examples 1 to 8] In order to prepare a test piece of a cured product of a resin alone, polyphenol resins (1) to (6) or condensates (1) and (2) synthesized in Examples 1 to 8 were used as a curing agent. )
In addition, cresol novolac type epoxy resin (trade name "Epochlon N-660", Dainippon Ink and Chemicals, Inc., epoxy equivalent 214 g / eq) was used as the main agent, and benzyldimethylamine was used as the curing accelerator. Each epoxy resin composition was obtained by blending with the composition shown in.

These epoxy resin compositions were treated at 100 ° C. for 2 hours, then at 160 ° C. for 2 hours, then at 180 ° C. for 2 hours.
A test piece was obtained by curing under the conditions of time, JIS K-6
According to 911, bending strength at room temperature, tensile strength, tensile elongation, and water absorption under conditions of 85 ° C. and 85% RH were measured. In addition, DMA (Dynamic Mechanical Analysi
s, dynamic viscoelasticity test) to measure the glass transition temperature and the dynamic viscoelasticity. The results are shown in Table 1.

[0074]

[Reference Comparative Examples 1 to 3] Novolac phenol resin (trade name "Tamanol 758", manufactured by Arakawa Chemical Industry Co., Ltd., OH equivalent 104 g / eq), dicyclopentadiene-modified phenol resin (OH equivalent 173 g / e) as a curing agent.
q), limonene modified phenolic resin (OH equivalent 172 g
/ Eq) was used, and the same procedure as in Reference Examples 1 to 8 was performed. Table 1 shows each measurement result.

[0075]

[Table 1]

[0076]

[Reference Examples 9 to 16] Polyphenols (1) to (6) or condensates (1) and (2) synthesized in Examples 1 to 8 were used as a curing agent, and a cresol novolac type epoxy resin (trade name) was used as a main component. "Epochron N-660",
Dainippon Ink and Chemicals, Inc., epoxy equivalent 214g
/ Eq) with other additives shown in Table 2 in Table 2
After blending with the above blending, kneading temperature is 7 using a heating roll.
Kneading was performed at 0 to 120 ° C. for about 8 minutes. afterwards,
The epoxy resin composition for semiconductor encapsulation was produced by pulverizing to about 5 mmφ. Then, each of the obtained compositions was subjected to measurements of copper foil adhesive strength, solder crack resistance test, and solder moisture resistance test by the following methods. The results are shown in Table 2.

(1) Copper foil adhesive strength The epoxy resin composition for semiconductor encapsulating material is heated and mixed, and 35
A sample was prepared by pouring it into a mold lined with a μm electrolytic copper foil and curing it at 175 ° C. for 6 hours. The obtained sample is J
The copper foil adhesive strength was determined according to IS C6481.

(2) Solder cracking property test The epoxy resin composition for semiconductor encapsulant was molded using a transfer molding machine (molding conditions; mold temperature 175 ° C., curing time 2 minutes), and 175 ° C. for 8 hours. Post-cured. After curing, 16 test elements (chip size 36 mm x 36 mm, package pressure 2.0 mm) obtained were treated under steam at 85 ° C and 85% RH for 48 hours and 72 hours, and then solder bath at 250 ° C. It was dipped in the glass for 10 seconds and the generation of external cracks was observed with a microscope.

(3) Solder moisture resistance test The test element sealed in (2) was absorbed at 85 ° C. and 85% RH for 72 hours, immersed in a solder bath at 250 ° C. for 10 seconds, and then subjected to a pressure cooker test (125). ℃, 100% R
H) was performed to measure the oven failure of the circuit.

[0080]

[Reference Comparative Examples 4 to 6] Novolak phenol resin (trade name "Tamanol 758", manufactured by Arakawa Chemical Industry Co., Ltd., OH equivalent 104 g / eq), dicyclopentadiene-modified phenol resin (OH equivalent 173 g / e) as a curing agent.
q), limonene modified phenolic resin (OH equivalent 172 g
/ Eq) was used, and an epoxy resin composition for semiconductor encapsulating material was prepared in the same manner as in Reference Examples 9 to 16, and each measurement was performed. The results are shown in Table 2.

[0081]

[Table 2]

Front page continued (72) Inventor Yu Otsuki 8 Chidori-cho, Naka-ku, Yokohama-shi, Kanagawa Japan Petroleum Co., Ltd. Central Research Laboratory (56) Reference JP-A-55-45761 (JP, A) JP-A-6 −40982 (JP, A) (58) Fields investigated (Int.Cl. ⁷ , DB name) C07C 37/14 C07C 39/15 C07C 39/21 C07C 41/06 C07C 43/23

Claims (4)

(57) [Claims] 1. A dimeric monophenoxy compound obtained by reacting butadiene, isoprene, piperylene or a mixture thereof with a phenol having 6 to 12 carbon atoms is used in the presence of an acid catalyst to have 6 to 6 carbon atoms. A method for producing polyphenols, which comprises reacting with 12 phenols. 2. A method for producing polyphenols, which comprises reacting octatriene and / or dimethyloctatriene with phenols having 6 to 12 carbon atoms in the presence of an acid catalyst. 3. A polyphenol, characterized in that a polyphenol obtained by the production method according to claim 1 or 2 and a ketone or aldehyde having 1 to 12 carbon atoms are subjected to a condensation reaction in the presence of an acid catalyst. For the production of condensates of the same class. 4. The polyphenols obtained by the production method according to claim 1 or 2, 5 to 95% by weight, and 6 to 1 carbon atoms.
A mixture of 2 to 95% by weight of phenols and 1 carbon atom
A method for producing a condensate of polyphenols, which comprises subjecting the ketones or aldehydes of to 12 to a condensation reaction in the presence of an acid catalyst.