JPH0912674A - Epoxy resin and manufacturing method thereof - Google Patents

Abstract

(57) Abstract: A stilbene-based epoxy resin having a low melting point and good solubility in a solvent, and a method for producing the same. SOLUTION: General formula (1) (Here, R _{1 to} R ₈ each independently represent a chain or cyclic alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom. Two aryl groups bonded to a carbon-carbon double bond are Are not the same as each other) and have a melting point of 15
A stilbene-based epoxy resin having a temperature of 0 ° C. or lower, or one or two or more thereof, and a compound represented by the general formula (2): (Wherein R _{9 to} R ₁₂ each independently represents a chain or cyclic alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom), and is bonded to a carbon-carbon double bond. An epoxy resin mixture having a melting point of 150 ° C. or lower, which comprises one or more stilbene-based epoxy resins having the same two aryl groups as each other as essential components, and a method for producing the same.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electric / electronic material such as an adhesive, a paint, an insulating material and a laminated board, and more particularly to an epoxy resin useful for sealing electronic parts or a mixture thereof, and a method for producing the same.

[0002]

2. Description of the Related Art There are many studies on epoxy resins having a stilbene skeleton. For example, glycidyl ethers of bisphenol compounds having a stilbene skeleton, which is unsubstituted or substituted with an alkyl group, preferably a methyl group is symmetrically substituted, are disclosed (US Pat. No. 4,762,901). German Patent No. 362
2613, JP-A-63-23931). There are also reported examples of stilbene-type bisphenol compounds in which the same aryl group is substituted on the carbon-carbon double bond, which is the raw material of the epoxy resin, 4,4'-dihydroxystilbene, 4,4'-dihydroxy.
-3,3'-dimethylstilbene, 4,4'-dihydroxy-3,3 ',
Manufacturing methods and physical properties of compounds such as 5,5'-tetramethylstilbene are disclosed (von Rolf H. Sieber, Liebigs Ann. Ch.
em.730, 31-46 (1969)). Further, some epoxy resins having a stilbene skeleton exhibit a liquid crystal structure. When a compound having a liquid crystallinity is polymerized in a liquid crystal state with a small amount of a catalyst, a crosslinked product retaining the liquid crystal structure as it is is obtained. It has been reported that alignment of liquid crystal domains occurs by obtaining and polymerizing under an electric field under specific conditions (Proceedings of the 3rd Next Generation Industrial Fundamental Technology Symposium P182 (1985)).
Of these, epoxidized products of 4,4'-dihydroxy-α-cyanostilbene are exemplified as compounds exhibiting liquid crystallinity. In addition, an epoxy resin exhibiting liquid crystallinity or having a rod-shaped portion has been proposed in order to improve mechanical properties (Japanese Patent Laid-Open No. 2-275872). As the hydroxyl group-containing compound that is epoxidized in this patent, 4,4'-dihydroxy-α-methylstilbene, 4,4'-dihydroxystilbene, 4,4'-dihydroxy-3,3 ', 5,5'-tetrabromo Examples include stilbene and 4,4′-dihydro-3,3 ′, 5,5′-tetramethylstilbene. As described above, the stilbene-based epoxy resin has been proposed for many applications and developments.

[0003]

However, since the stilbene type epoxy resin generally has a high melting point and a low solubility in a solvent, its usage is limited. For example, 4,4 '
-Dihydroxystilbene, 4,4'-dihydroxy-3,3'-dimethylstilbene, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylstilbene glycidyl ether compound melting point is 208 ~ respectively It was high at 215 ° C, 150 ° C, 151 ° C, and there was a problem that uniform mixing with an epoxy curing agent or uniform kneading with other components was difficult. An object of the present invention is to provide a stilbene-based epoxy resin having a low melting point and good solubility in a solvent, and a method for producing the same.

[0004]

[Means for Solving the Problems] In view of such circumstances,
As a result of intensive studies, the present inventors have completed the present invention. That is, the present invention is as follows. [1] General formula (1)

Embedded image (Here, R _{1 to} R ₈ each independently represent a chain or cyclic alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom. Two aryl groups bonded to a carbon-carbon double bond are Are not the same as each other) and have a melting point of 15
A stilbene-based epoxy resin having a temperature of 0 ° C. or lower.

[2] In the general formula (1), R ₁ is t-
The stilbene-based epoxy resin according to the above [1], which is a butyl group.

[3] In the general formula (1), R ₁ is t-
The stilbene-based epoxy resin according to [1] above, which is a butyl group and R _{5 to} R ₈ are other than a t-butyl group.

[4] In the general formula (1), t-of R ₁
The stilbene-based epoxy resin according to the above [2] or [3], wherein the butyl group is bonded to the ortho position with respect to the bonding position of the oxygen atom.

[5] One or more of the stilbene-based epoxy resins represented by the general formula (1) described in [1] above and the general formula (2).

Embedded image (Wherein R _{9 to} R ₁₂ each independently represents a chain or cyclic alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom), and is bonded to a carbon-carbon double bond. An epoxy resin mixture having one or two or more stilbene type epoxy resins in which the two aryl groups are the same as each other and having a melting point of 150 ° C. or less.

[6] The epoxy resin mixture according to the above [5], wherein R ₁ is a t-butyl group in the stilbene type epoxy resin represented by the general formula (1).

[7] In the general formula (1), R ₁ is t-
The epoxy resin mixture according to the above [5] or [6], which is a butyl group and R _{5 to} R ₈ are other than a t-butyl group.

[8] In the general formula (1), R ₁ is t-
[5], [6] above which is a butyl group and is substituted at the ortho position with respect to the substitution position of the oxygen atom in the aryl group.
Alternatively, the epoxy resin mixture described in [7].

[9] The epoxy resin mixture as described in [5], [6], [7] or [8], which has a melt viscosity at 150 ° C. of 1 poise or less.

[10] The presence of a basic substance in a 1,1-bis (hydroxyphenyl) -2-chloroethane derivative obtained by reacting two or more phenols with chloroacetaldehyde in the presence of an acidic substance. A process for producing an epoxy resin or a mixture thereof, which comprises subjecting a dihydroxystilbene derivative to a dihydroxystilbene derivative under the following conditions and then reacting the dihydroxystilbene derivative with epihalohydrin in the presence of a basic substance.

[11] Two or more phenols selected from the group consisting of 2,6-xylenol, 2,4-xylenol, 3-methyl-6-t-butylphenol and 2-methyl-6-t-butylphenol. Above [10]
A method for producing the described epoxy resin or a mixture thereof.

[12] The method for producing an epoxy resin or a mixture thereof according to the above [10], wherein the phenol is a mixture of 2,6-xylenol and 3-methyl-6-t-butylphenol.

The general formula (1) or (2) in the present invention
Substituent R of the epoxy resin represented by ₁~ R₁₂Specifically
For example, methyl group, ethyl group, propyl group
Group, butyl group, amyl group, hexyl group, cyclohexyl
Group (including each isomer), chlorine atom, bromine atom, etc.
I can do it. Above all, the low melt viscosity of products and the availability of raw materials
Methyl, ethyl, propyl, butyl for ease of use
Is preferred.

Specific examples of stilbene-based phenols in which two aryl groups bonded to a carbon-carbon double bond are not the same as each other, which is a raw material of the epoxy resin represented by the general formula (1) in the present invention, Is 3-t-butyl-4,4'-
Dihydroxy-3'-methylstilbene, 3-t-butyl-4,4'-
Dihydroxy-5,3'-dimethylstilbene, 3-t-butyl-
4,4'-dihydroxy-3 ', 6-dimethylstilbene, 3-t-butyl-4,4'-dihydroxy-5-ethyl-3'-methylstilbene, 3-t-butyl-4,4'-dihydroxy -3'-methyl-5-propylstilbene, 3-t-butyl-4,4'-dihydroxy-5-butyl-3'-methylstilbene, 3-t-butyl-4,4'-dihydroxy-5-amyl -3'-methylstilbene, 3-t-butyl-4,4 '
-Dihydroxy-5-hexyl-3'-methylstilbene, 3-t-
Butyl-4,4'-dihydroxy-5-cyclohexyl-3'-methylstilbene, 3-t-butyl-4,4'-dihydroxy-3 ', 5,5'
-Trimethylstilbene, 3-t-butyl-2,4'-dihydroxy-3 ', 5', 6-trimethylstilbene, 3-t-butyl-4,4'-
Dihydroxy-3 ', 5', 6-trimethylstilbene, 3-t-butyl-4,4'-dihydroxy-3 ', 5, -dimethyl-5'-propylstilbene, 3-t-butyl-4,4' -Dihydroxy-3 ', 6, -dimethyl-5'-propylstilbene etc. (including isomers with different substitution positions) can be exemplified, but 3-t-butyl is used in terms of ease of synthesis, performance, and raw material price. -4,4'-dihydroxy-3 ', 5,
5'-trimethylstilbene, 3-t-butyl-2,4'-dihydroxy-3 ', 5', 6-trimethylstilbene, 3-t-butyl-4,4 '
-Dihydroxy-3 ', 5', 6-trimethylstilbene is particularly preferred.

Specific examples of stilbene-based phenols, which are raw materials for the epoxy resin represented by the general formula (2), include:
4,4'-dihydroxy-3,3'-dimethylstilbene, 3,3'-diethyl-4,4'-dihydroxystilbene, 4,4'-dihydroxy-3,3'-dipropylstilbene, 3,3 ' -Jiamil-4,4 '
-Dihydroxystilbene, 3,3'-dihexyl-4,4'-dihydroxystilbene, 3,3'-dicyclohexyl-4,4'-dihydroxystilbene, 2,2'-dihydroxy-3,3 ', 5,5' -
Tetramethylstilbene, 4,4'-dihydroxy-3,3 ', 5,
5'-tetramethylstilbene, 4,4'-dihydroxy-3,3'-
Di-t-butylstilbene, 4,4'-dihydroxy-3,3'-di-t
-Butyl-5,5'-dimethylstilbene, 4,4'-dihydroxy
-3,3'-di-t-butyl-6,6'-dimethylstilbene, 2,2'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, 2,4 '-Dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene,4,4'-dihydroxy-3,3',5,5'-tetra-t
-Butylstilbene, etc. (including isomers with different substitution positions) can be exemplified. Among them, 2,2'-dihydroxy-3,3 ', 5,5' from the viewpoint of easiness of synthesis, performance, and raw material price. -Tetramethylstilbene, 4,4'-dihydroxy-3,3 ', 5,5'-tetramethylstilbene, 4,4'-dihydroxy-3,3'-di-t-butyl-5,5'-dimethyl Stilbene, 4,4'-dihydroxy-3,
3'-di-t-butyl-6,6'-dimethylstilbene, 2,2'-dihydroxy-3,3'-di-t-butyl-6,6'-dimethylstilbene, 2,4'-dihydroxy- Particularly preferred is 3,3'-di-t-butyl-6,6'-dimethylstilbene.

In the present invention, the phenols used as a starting material for the stilbene type epoxy resin are as follows. As those containing a t-butyl group, 3-methyl-6-t-butylphenol, 2-methyl-6-t-butylphenol, 2-t-butylphenol, 2-
Ethyl-6-t-butylphenol, 2-propyl-6-t-butylphenol, 2,6-di-t-butylphenol, 2-isobutyl-6-t-butylphenol, 2-amyl-6-t-butylphenol, 2- Amyl-6-t-butylphenol, 2-hexyl-6-
Examples include t-butylphenol and 2-cyclohexyl-6-t-butylphenol, but 3-methyl-6-t-butylphenol and 2-methyl-6 from the viewpoint of the melting point of the final product, availability, and price. Particularly preferred is -t-butylphenol.
Also, as those not containing t-butyl group, cresol,
Examples include xylenol, trimethylphenol, tetramethylphenol, methylethylphenol, methylpropylphenol, methylisobutylphenol, methylhexylphenol, methylcyclohexylphenol and the like (including each isomer). Of these, xylenol is particularly preferable in terms of performance and price balance.

In the present invention, examples of the chloroacetaldehydes used as a starting material for the stilbene type epoxy resin include chloroacetaldehyde, an aqueous solution of chloroacetaldehyde, acetals of chloroacetaldehyde, and a trioxane type trimer of chloroacetaldehyde.

The amount of chloroacetaldehyde to be used is 0.8 to 1.4 times mol, preferably 1 to 0, based on the total molar amount of phenols. If it is less than this range, unreacted phenols are likely to remain in the product, and if it exceeds this range, the product tends to have a high molecular weight.

The reaction between chloroacetaldehydes and phenols is usually carried out in the presence of an acidic substance, and examples of such substances include fuming sulfuric acid, concentrated sulfuric acid, an aqueous sulfuric acid solution,
Examples include concentrated hydrochloric acid, hydrogen chloride gas, aqueous hydrochloric acid, inorganic acids such as trifluorosulfonic acid, organic acids such as p-toluenesulfonic acid, chloroacetic acid, trichloroacetic acid, trifluoroacetic acid, heteropolyacids, acidic ion exchange resins, and the like. However, concentrated sulfuric acid is preferable in that a highly pure product can be easily obtained. The amount used is 0.1 to chloroacetaldehydes.
The molar ratio is 10 times, preferably 0.5 to 2 times. If it is less than this range, the reaction proceeds slowly, and if it is used beyond this range, a certain effect or more cannot be obtained.

As the reaction solvent, hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, ethers such as dioxane and tetrahydrofuran,
Examples thereof include alcohols such as methanol and propanol, aprotic polar solvents such as dimethyl sulfoxide, dimethylacetamide and dimethylformamide, glycols such as ethylene glycol and propylene glycol, and acidic solvents such as acetic acid, with acetic acid being preferred. These solvents may be used alone or in combination of two or more.

The amount of the solvent used is 0.1 to 20 times by weight, preferably 0.5 to 10 times by weight, based on the phenols and chloroacetaldehydes. If it is below this range, stirring will be difficult due to the crystals precipitated by the reaction, and if it exceeds this range, the product yield per reaction will decrease, which is economically disadvantageous.

In the reaction, phenols and chloroacetaldehydes are dissolved in a solvent and then an acidic substance is dropped, or phenols and acidic substances are first charged in a reaction vessel and then chloroacetaldehydes are dropped. You may. The dropping time is usually 0.5 to 10 hours. After the dropping, the reaction is performed for 3 to 24 hours. The temperature is -30
It is carried out at -60 ° C, preferably -10-40 ° C. Below this temperature, the reaction progresses slowly, and above this range, the production of impurities becomes remarkable. After the reaction, the precipitated crystals are filtered off,
After washing with water, it is dried under reduced pressure. Thus, the 1,1-bis (hydroxyphenyl) -2-chloroethane derivative which is an intermediate of the epoxy resin of the present invention is obtained.

Next, 1,1-bis (hydroxyphenyl) -2
-Dehydrochlorination / rearrangement reaction of chloroethane derivative. It can be easily carried out by dissolving this compound in a solvent and dropping a basic substance such as an aqueous solution of caustic soda. Examples of the solvent to be used include hydrocarbons such as toluene and xylene, halogenated hydrocarbons such as chlorobenzene, ethers such as dioxane and tetrahydrofuran, alcohols such as methanol and propanol, dimethyl sulfoxide, dimethylacetamide and dimethylformamide. Examples thereof include aprotic polar solvents, glycols such as ethylene glycol and propylene glycol, acidic solvents such as acetic acid, and alcohols such as methanol and propanol are preferable. These solvents may be used alone or in combination of two or more.

The amount of the solvent used is 0.1 to 20 relative to the 1,1-bis (hydroxyphenyl) -2-chloroethane derivative.
Weight times, preferably 0.5 to 10 times by weight are preferable. If it is below this range, stirring will be difficult due to the salt precipitated during the reaction, and if it exceeds this range, the product yield per reaction will be reduced, which is economically disadvantageous.

As the basic substance used in the reaction, powders of caustic soda, caustic potash and the like, pellets and aqueous solutions thereof are preferred, of which aqueous solutions of caustic soda are preferred in view of handling and cost. The amount used is 1 to 5 times, preferably 1 to 2 times the mol of the 1,1-bis (hydroxyphenyl) -2-chloroethane derivative. If it is below this range, unreacted substances remain, and if it is used beyond this range, the effect of a certain level or more cannot be obtained.

The reaction is 1,1-bis (hydroxyphenyl)
After dissolving the -2-chloroethane derivative in a solvent,
After dropping the basic substance or charging the phenols and acidic substances into the reaction vessel first, the 1,1-bis (hydroxyphenyl) -2-chloroethane derivative as a powder or as a solution or slurry Drop in the state. Usually, the dropping time is preferably 0.5 hours to 10 hours. 3 after dropping
It is preferable to carry out the reaction for -24 hours. The temperature is preferably -20 to 150 ° C, more preferably 20 to 100 ° C. When the temperature is lower than this temperature, the reaction progresses slowly, and even if the reaction is carried out beyond this range, a certain effect or more cannot be obtained.

After the reaction, the reaction system is neutralized and the solvent is recovered. After collecting the solvent, the reaction mixture is easily crystallized by adding water into the reaction vessel. This is collected by filtration, washed with water, and dried under reduced pressure. Thus, a bisphenol compound having a stilbene skeleton, which is an intermediate of the epoxy resin of the present invention, is obtained.

The stilbene type epoxy resin of the present invention can be obtained by a known method of converting the stilbene type bisphenol obtained as described above into a glycidyl ether. That is, this is a method of reacting bisphenol and epihalohydrin in the presence of an alkali such as caustic soda. Particularly, when a high-purity product is obtained, the method disclosed in JP-A-60-315
As in No. 17, a reaction using an aprotic solvent or a solvent such as dioxane is preferable.

In the present invention, the mixture of the epoxy resin represented by the general formula (1) and the epoxy resin represented by the general formula (2) may be separately synthesized and mixed to prepare. It can also be obtained by separately synthesizing up to the middle of the steps up to the epoxidation, mixing at that stage, and then performing the reaction of the remaining steps.

[0033]

EXAMPLES Examples of the present invention will be described below, but the present invention is not limited to these examples. In the examples, the epoxy equivalent is defined as the molecular weight of the epoxy resin per epoxy group.

Reference Example 1 (1) Synthesis of 1,1-bis (hydroxyphenyl) -2-chloroethane derivative-1 In a 2-liter four-necked flask equipped with a thermometer, a stirrer and a condenser, 2,6-xylenol ( Hereinafter, abbreviated as 26XY.) 244.4 g (2.0 mol), 43.8% aqueous chloroacetaldehyde solution 193.8 g (1.0 mo)
l) and 376 g of acetic acid, and stirred and dissolved.
Cooled down. Next, 122 g (1.2 mol) of concentrated sulfuric acid
Was added dropwise to acetic acid (84 g) over 3 hours at 5 ° C., and then the reaction system was kept warm at 25 ° C. for 6 hours and stirred at room temperature overnight. The temperature of the system was cooled to 5 ° C., and the precipitated crystals were separated by filtration. The crystals were washed six times with 500 g of water, and then vacuum dried at 40 ° C. for 8 hours to obtain 264 g (yield: 86.6%) of colorless crystals (referred to as XYCE). Gel permeation chromatography (hereinafter abbreviated as GPC. 2
Purity of 98.3).
%, A broad absorption due to hydroxyl group was confirmed at around 3500 cm ^-1 by infrared absorption spectrum. In addition, a fragment having a molecular weight of 304 was observed from the mass spectrum.

(2) Synthesis of stilbene-type bisphenol-1 A liter four-necked flask equipped with a thermometer, a stirrer and a condenser was charged with 225.6 g of XYCE obtained in (1) and 451.2 g of methanol, and under a nitrogen stream, Stir to dissolve. 91.9 g of a 48.3% aqueous sodium hydroxide solution was added dropwise at an internal temperature of 30 ° C. for 1 hour. Next, the mixture was reacted for 3 hours while heating and refluxing methanol. After the reaction, XYCE as a raw material had completely disappeared by high performance liquid chromatography (hereinafter abbreviated as LC). After cooling to 60 ° C., concentrated hydrochloric acid 37.
5 g was added for neutralization, and methanol was distilled off. Subsequently, 1000 g of warm water was added, and the precipitated crystals were collected by filtration. The crystals were washed with water and vacuum dried at 80 ° C. for 8 hours to obtain yellow crystals 19
2 g (96.7%) was obtained (referred to as XYSB). GPC
Is 98.1%, and 3 according to infrared absorption spectrum.
Broad absorption by a hydroxyl group was confirmed at around 400 cm ^-1 . In addition, a fragment having a molecular weight of 268 was observed from the mass spectrum.

(3) Synthesis of Epoxy-1 100 g of raw material phenol (XYSB) obtained in (2)
The thermometer, stirrer, dropping funnel, condenser with separation tube
Into a reaction vessel marked with, and add epichlorohydrin 48
5.6 g, dissolved in 242.8 g of 1,4-dioxane
Was. While maintaining the inside of the reaction system at 140 torr, a temperature of 62
At 4 ° C., 61.71 g of 48.3% caustic soda was added in 5 hours.
It was dropped continuously. During this time, keep the temperature at 62 ° C
Liquefied epichlorohydrin and water,
The reaction was carried out while returning the layers to the reaction system. After the reaction
And unreacted epichlorohydrin and 1,4-dioxane
Was removed by vacuum concentration, and the by-product salt and glycidyl ether were removed.
Dissolved in 800 g of methyl isobutyl ketone,
And dimethyl sulfoxide were removed by washing with water. afterwards
Methyl isobutyl ketone at 160 ° C, 10 torr
Evaporation under reduced pressure gave 122.2 g (86.2%) of the desired product.
(Named XYCC-E). GPC (by differential refractometer
Purity by detection) is 93.0%, melting point of this is 15
The epoxy equivalent was 198 g / eq at 1 ° C. Infrared absorption
As a result of absorption spectrum measurement, absorption by the phenolic hydroxyl group
Loss disappears, 1240 cm due to epoxy ^-1, 915c
m^-1It was confirmed to have absorption of.

Reference Example 2 (1) Synthesis of 1,1-bis (hydroxyphenyl) -2-chloroethane derivative-2 In the case of Reference Example 1 (1), 26XY244.4 g (2.0
mol) instead of 3-methyl-6-t-butylphenol (hereinafter abbreviated as 3M6B) 328.5 g (2.0 m)
ol) was used in the same manner as described above, and the light purple crystals were washed with 31
7 g (81.5%) was obtained (designated as XMCE-100).
Purity by GPC (detected by ultraviolet rays at 254 nm) was 87.7%, and infrared absorption spectrum confirmed wide absorption by hydroxyl groups at around 3500 cm ^-1 . In addition, a fragment having a molecular weight of 389 could be observed by mass spectrometry.

(2) Synthesis of stilbene bisphenol-2 Reference example 1 In the case of (2), reference example 2 was used instead of XYCE.
The same experiment was carried out using the XMCE-100 obtained in (1), and 134 g (94.8%) of pale yellow crystals were obtained (X
MSB-100). Purity by GPC is 93.5
%, An infrared absorption spectrum confirmed a wide absorption due to a hydroxyl group near 3100 cm ⁻¹ . In addition, a fragment having a molecular weight of 352 could be observed by mass spectrometry.

(3) Synthesis of Epoxy-2 XMSB-instead of XYSB in Reference Example 1 (3)
Other than using 100, the same operation was carried out and epoxidation was carried out in the same manner to obtain 54.7 g (36.2%) of the desired product (X
MCC-100E). The purity by GPC (detected by a differential refractometer) was 95.2%. The melting point of this product is 220 to 224 ° C, and the epoxy equivalent is 230.
g / eq. As a result of infrared absorption spectrum measurement, it was confirmed that the absorption due to the phenolic hydroxyl group disappeared and that the epoxy had absorptions at 1230 and 920 cm ⁻¹ .

Example 1 (1) Synthesis of 1,1-bis (hydroxyphenyl) -2-chloroethane derivative-3 In the case of Reference Example 1 (1), 26XY244.4 g (2.0
mol) instead of 26XY195.5g (1.6mo)
1) and 65.7 g (0.4 mol) of 3M6B were used in the same manner, and 271 g (84.1 g) of pale purple crystals were obtained.
%) Obtained (referred to as XMCE-20). GPC (254n
m, detected by ultraviolet rays) and the infrared absorption spectrum confirmed broad absorption by hydroxyl groups at around 3450 and 3550 cm ^-1 . In addition, fragments having molecular weights of 346 and 304 were observed by mass spectrometry. In addition, X of Reference Example 4 was analyzed by LC.
MCE-100 was not detected.

(2) Synthesis of Stilbene Bisphenol-3 Reference Example 1 In the case of (2), Example 1 was used instead of XYCE.
The same experiment was performed using 144.8 g of XMCE-20 obtained in (1), and 124 g (96.6%) of yellow crystals were obtained.
(Referred to as XMSB-20). GPC (254 nm
Of 97.1%, and a broad absorption due to hydroxyl group was confirmed at around 3400 cm ^-1 by infrared absorption spectrum. In addition, fragments having molecular weights of 310 and 268 were observed by mass spectrometry. In addition, XMSB-10 of Reference Example 5 was analyzed by LC.
0 was not detected.

(3) Epoxy synthesis-3 In the case of Reference Example 1 (3), the above (2) was used instead of XYSB.
The same operation was performed except that 99.7 g of the XMSB-20 obtained in the above was used to obtain 131 g (94%) of the desired product (XM
CC-20E). Purity by GPC (detected by a differential refractometer) was 93.6%, and that of a stilbene-based epoxy compound having 26XY and 3M6B in a molecule was 39.6%. This had a melting point of 110 to 130 ° C. and an epoxy equivalent of 208 g / eq. As a result of infrared absorption spectrum measurement, absorption by the phenolic hydroxyl group disappeared, and it was confirmed that the epoxy resin had absorptions of 1240 and 920 cm ^-1 .

Example 2 (1) Synthesis of 1,1-bis (hydroxyphenyl) -2-chloroethane derivative-4 In the case of Reference Example 1 (1), 26XY244.4 g (2.0
mol instead of 26XY171.1 g (1.4 mo
l) and 3M6B 98.6 g (0.6 mol) g were used in the same manner as above, and 253 g (76.7 g) of light purple crystals were obtained.
%) Obtained (designated as XMCE-30). GPC (254n
The purity was 96.0% as detected by ultraviolet light of m), and the infrared absorption spectrum confirmed wide absorption by hydroxyl groups at around 3450 and 3550 cm ^-1 . In addition, fragments having molecular weights of 346 and 304 were observed by mass spectrometry. In addition, X of Reference Example 4 was analyzed by LC.
MCE-100 was not detected.

(2) Synthesis of stilbene bisphenol-4 In the case of Reference Example 1 (2), the same experiment was carried out using 122.1 g of XMCE-30 obtained in (1) above instead of XYCE. , Yellow crystals 108g (99.4%)
Was obtained (designated as XMSB-30). GPC (254 nm
The purity was 93.3% (detected by ultraviolet light), and the infrared absorption spectrum confirmed wide absorption at 3400 cm ^-1 due to the hydroxyl group. In addition, fragments having molecular weights of 310 and 268 were observed by mass spectrometry. In addition, the XMSB of Reference Example 2 (2) was analyzed by LC.
-100 was not detected.

(3) Synthesis of Epoxy-4 In the case of Reference Example 1 (3), the above (2) was used instead of XYSB.
The same operation was performed except that 95.4 g of XMSB-30 obtained in 1. was used to obtain 118 g (89.5%) of the desired product (referred to as XMCC-30E). Purity by GPC (detected by differential refractometer) is 86.6%, 26XY and 3M6
The stilbene type epoxy compound having B in the molecule is 53.
2%. This product was semi-solid at room temperature and had an epoxy equivalent of 200 g / eq. Melt viscosity is 150
It was 0.16 poise at ° C. As a result of the infrared absorption spectrum measurement, it was confirmed that the absorption due to the phenolic hydroxyl group disappeared and that the absorptions due to the epoxy were 1260 and 910 cm ⁻¹ .

Example 3 (1) Synthesis of 1,1-bis (hydroxyphenyl) -2-chloroethane derivative-5 In the case of Reference Example 1 (1), 26XY244.4 g (2.0
mol instead of 26XY122.2 g (1.0 mo
l) and 3M6B164.3 g (1.0 mol) g were used in the same manner, and 321 g (92.
5%) was obtained (designated as XMCE-50). GPC (254
The purity was 90.7% by detection with ultraviolet rays of nm), and the infrared absorption spectrum confirmed wide absorption by hydroxyl groups at around 3450 and 3550 cm ⁻¹ . In addition, by mass spectrometry, molecular weights of 346 and 304 and a trace amount of 389 fragment were observed.

(2) Synthesis of stilbene bisphenol-5 In the case of Reference Example 1 (2), the same experiment was conducted using 114.7 g of XMCE-50 obtained in (1) above instead of XYCE. , Light brown crystals 98.5 g (95.8)
%) Was obtained (designated as XMSB-50). GPC (254
The purity was 96.5% by detection with ultraviolet light of nm), and the stilbene compound having 26XY and 3M6B in the molecule was 86.4%. 3 according to infrared absorption spectrum
Wide absorption due to hydroxyl groups was confirmed near 400 cm ^-1 . In addition, the molecular weight of 310,
268 and trace 352 fragments could be observed.

(3) Purification of stilbene bisphenol XMSB-50 obtained in Example 3 (2) was recrystallized from toluene. The crystals were washed with cyclohexane and dried under reduced pressure to give brown fine crystals. Purity by high performance liquid chromatography (hereinafter abbreviated as LC) is 99.1%,
The retention time of LC of stilbene bisphenol having 26XY and 3M6B in the molecule obtained in Example 3 (2) was completely the same. 3500 cm by infrared absorption spectrum
^Wide absorption due to hydroxyl groups was confirmed around ^-1 . Also,
By mass spectrometry, a fragment with a molecular weight of 310 could be observed. Melting point 175 to 179 ° C. ¹ H-NMR δ: 1.43 ppm (s, t-butyl group, 9H) 2.27 ppm (s, Ar—CH ₃ , 6H) 2.33 ppm (s, Ar—CH ₃ , 3H) 4.77 ppm (brs, hydroxyl group, 2H) 6.5-7.5 ppm (m, Ar-H, -CH = CH-, 6H)

(4) Synthesis of epoxy-5 In the case of Reference Example 1 (3), the above (2) was used instead of XYSB.
The same operation was performed except that 99.7 g of the XMSB-50 obtained in 1. was used and 131 g (94%) of the desired product was obtained (XM
CC-50E). Purity by GPC (detected by differential refractometer) is 93.5%, 26XY residue and 3M6B
There are 8 stilbene-based epoxy compounds that have a residue in the molecule.
0.5%. This product had a melting point of 45 ° C., an epoxy equivalent of 226 g / eq and a melt viscosity of 0.2 poise at 150 ° C. As a result of the infrared absorption spectrum measurement, it was confirmed that the absorption due to the phenolic hydroxyl group disappeared and the absorption due to the epoxy was 1260 and the absorption at 920 cm ^-1 .

(5) Synthesis of Epoxy-6 In the case of Reference Example 1 (3), Example 3 was used instead of XYSB.
The same except that 38.8 g of the recrystallized product obtained in (3) was used.
To 50.2 g (95%) of a pale yellow viscous liquid.
%)Obtained. Holds 26XY and 3M6B in the molecule by LC
The purity of the stilbene type epoxy compound is 94.2%.
Was. As a result of infrared absorption spectrum measurement, phenolic water
Absorption by acid groups disappears, absorption by epoxy 126
0,910 cm ^-1It was confirmed to have absorption of.・¹H-NMR δ: 1.42 ppm (s, t-butyl group, 9H) 2.32 ppm (s, Ar-CH_Three, 6H) 2.38 ppm (s, Ar-CH_Three3H) 2.7 to 3.0 ppm (m, epoxy-CH_Two4H) 3.4 ppm (m, epoxy-CH, 2H) 3.7-4.3 ppm (m, -OCH_Two4H) 6.6 to 7.5 ppm (m, Ar-H, -CH = CH-, 6H).

Example 4 (1) Synthesis of 1,1-bis (hydroxyphenyl) -2-chloroethane derivative-6 In the case of Reference Example 1 (1), 26XY244.4 g (2.0
mol instead of 26XY91.7g (0.75mo)
1) and 3M6B164.3 g (1.25 mol) were used in the same manner, and 315 g (88.
0%) was obtained (designated as XMCE-62.5). GPC (2
Purity by detection with 54 nm UV light) is 94.4
%, 3450 and 3550 cm by infrared absorption spectrum
^Wide absorption due to hydroxyl groups was confirmed around ^-1 . Also,
By mass spectrometry, the molecular weights of 346, 389, 3
04 fragments could be observed.

(2) Synthesis of stilbene bisphenol
-6 In the case of Reference Example 1 (2), the above is used instead of XYCE.
121.1 g of XMCE-62.5 obtained in (1)
The same experiment was carried out using 103 g (94.
7%) was obtained (designated as XMSB-62.5). GPC
The purity according to (detected by ultraviolet rays at 254 nm) is 92.
0%, 3500 cm according to infrared absorption spectrum ^-1In the vicinity
Wide absorption due to hydroxyl groups was confirmed. Mass spectrometry
According to the spectrum, the molecular weight of 310, 268, 352
I was able to observe the lagment.

(3) Synthesis of Epoxy-7 In the case of Reference Example 1 (3), Example 4 was used instead of XYSB.
The same operation was performed except that 80.3 g of XMSB-62.5 obtained in (2) was used, and 95.2 g (87.
9%) was obtained (designated as XMCC-62.5E). GPC
Purity by (detected by differential refractometer) is 85.8%,
The stilbene type epoxy compound having 26XY and 3M6B in the molecule was 71.0%. The melting point of this product is 10
5 to 125 ° C., epoxy equivalent is 230 g / eq,
The melt viscosity at 150 ° C. was 0.4 poise. As a result of infrared absorption spectrum measurement, the absorption due to the phenolic hydroxyl group disappeared, and the absorption due to the epoxy 1260, 915 cm ^-1
It was confirmed to have absorption of.

Example 5, Solubility Test of Epoxy Resin in Solvents Epoxy resins obtained in Examples 1, 2, 3, 4 or Reference Examples 1 and 2 (XMCC-20E and XMCC-3, respectively).
0E, XMCC-50E, XMCC-62.5E, XM
80 parts by weight of methyl isobutyl ketone was added to 20 parts by weight of CC-100E, XYCC-E), and the solubility when heated to 80 ° C. was examined. Further, 10 parts by weight of each of the epoxy resins obtained in Reference Examples 1 and 2 was added to 80 parts by weight of methyl isobutyl ketone, and the solubility was similarly examined. Table 1 shows the results. When dissolved, it is indicated by ◯, and when not dissolved, by x. In addition, the melting points of the respective resins are also shown.

[0055]

[Table 1]

[0056]

INDUSTRIAL APPLICABILITY The stilbene-type epoxy compound having different aryl groups or the epoxy resin mixture containing the same according to the present invention has a lower temperature than the stilbene-type epoxy resin having equal aryl groups or the epoxy resin mixture containing the same. Melting point. Therefore, these resins and the like have improved workability and moldability as compared to conventional products, and when molding is performed using these, shortening the time of the commercialization process, etc.
Excellent in terms of economy and productivity. Further, when the epoxy resin or the like of the present invention is used, the range of application is expanded compared to the conventional one.
The melting point of the epoxy resin or the like of the present invention can be largely changed by changing the substituent of the aryl group, and for example, it can be widely applied from 150 ° C. to liquid at room temperature, and flexibly according to the purpose and application. Can respond. Further, the epoxy resin and the like of the present invention have improved solubility in a solvent as compared with conventional ones, and can be used for applications such as varnish and paint. As described above, the epoxy resin or the like of the present invention is useful as an adhesive, a paint, an electric / electronic material such as an insulating material or a laminated board, and particularly for sealing an electronic component.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hiroshi Nakamura 6 Kitahara, Tsukuba-shi, Ibaraki Prefecture Sumitomo Chemical Co., Ltd. (72) Inventor Shigeki Naito 6 Kitahara, Tsukuba-shi, Ibaraki Sumitomo Chemical Co., Ltd.

Claims (12)

[Claims] 1. A compound of the general formula (1) (Here, R _{1 to} R ₈ each independently represent a chain or cyclic alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom. Two aryl groups bonded to a carbon-carbon double bond are Are not the same as each other) and have a melting point of 15
A stilbene-based epoxy resin having a temperature of 0 ° C. or lower. 2. The stilbene type epoxy resin according to claim ₁ , wherein R ₁ in the general formula (1) is a t-butyl group. 3. In the general formula (1), R ₁ is t-butyl group and R _{5 to} R ₈ are other than t-butyl group.
The stilbene-based epoxy resin described. 4. The stilbene type epoxy resin according to claim 2, wherein in the general formula (1), the t-butyl group of R ₁ is bonded to the ortho position with respect to the bonding position of the oxygen atom. 5. A stilbene-based epoxy resin represented by the general formula (1) according to claim 1 or a combination of two or more stilbene-based epoxy resins represented by the general formula (2): (Wherein R _{9 to} R ₁₂ each independently represents a chain or cyclic alkyl group having 1 to 6 carbon atoms, a hydrogen atom or a halogen atom), and is bonded to a carbon-carbon double bond. An epoxy resin mixture having one or two or more stilbene type epoxy resins in which the two aryl groups are the same as each other and having a melting point of 150 ° C. or less. 6. The epoxy resin mixture according to claim 5, wherein R ₁ in the general formula (1) is a t-butyl group. 7. The epoxy resin mixture according to claim ₅ , wherein in the general formula (1), R ₁ is a t-butyl group and R _{5 to} R ₈ are other than the t-butyl group. 8. The epoxy according to claim 5, 6 or 7, wherein in the general formula (1), R ₁ is a t-butyl group, and the aryl group is substituted at the ortho position with respect to the substitution position of the oxygen atom. Resin mixture. 9. The epoxy resin mixture according to claim 5, 6, 7 or 8 having a melt viscosity at 150 ° C. of 1 poise or less. 10. A 1,1-bis (hydroxyphenyl) -2-chloroethane derivative obtained by reacting two or more phenols and chloroacetaldehydes in the presence of an acidic substance in the presence of a basic substance. A method for producing an epoxy resin or a mixture thereof, which comprises subjecting the compound to a dehydrochlorination reaction to give a dihydroxystilbene derivative, and then reacting the dihydroxystilbene derivative with epihalohydrin in the presence of a basic substance. 11. A phenol is 2,6-xylenol,
The method for producing an epoxy resin or a mixture thereof according to claim 10, which is two or more selected from the group consisting of 2,4-xylenol, 3-methyl-6-t-butylphenol, and 2-methyl-6-t-butylphenol. 12. The method for producing an epoxy resin or a mixture thereof according to claim 10, wherein the phenol is a mixture of 2,6-xylenol and 3-methyl-6-t-butylphenol.