JPH10130371A - Adamantanes, thermoplastic resin and thermosetting resin composition containing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a new bis(hydroixyphenyl)adamantane useful as a new polymer material excellent in terms of heat resistance, thermal conductivity, refractive index, electric characteristics, etc., and its raw material. SOLUTION: This compound is shown by the formula (X is H or glycidyl; R is an alkyl, an aryl, a halogen, hydroxyl group, glycidyloxy, etc.; with the proviso that when X is H, R is not glycidyloxy and when X is glycidyl, R is not hydroxyl group; (n) is 0-4) such as 2,2-bis(4'-hydroxyphenyl)adamantane. The compound is preferably obtained by reacting 2-adamantanone with a phenol compound such as phenol in the presence of an acid catalyst such as sulfuric acid at 30-180 deg.C. The compound in which X is glycidyl is obtained by reacting the compound of the formula in which X is hydrogen with an epithalohydrin such as epichlorohydrin in the presence of a caustic alkali, etc.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD The present invention relates to bis (hydroxyphenyl) adamantanes, bis (glycidyloxyphenyl) adamantanes, and a composition comprising these as a constituent,
It relates to a thermoplastic resin and a thermosetting resin.

[0002]

2. Description of the Related Art A polymer compound having an adamantane skeleton has good heat resistance.
Polyesters and polycarbonates using polyesters are known.

[0003]

SUMMARY OF THE INVENTION The present invention relates to heat resistance,
It is an object of the present invention to provide a novel polymer material excellent in thermal conductivity, refractive index, electrical characteristics, and the like, and a raw material thereof.

[0004]

That is, the present invention provides (1) bis (hydroxyphenyl) adamantane represented by the following formula (1):

[0005]

Embedded image

R independently represents an alkyl group, an alkylene group, an aralkyl group, an aryl group, a halogen, an alkoxy group, a hydroxyl group or a glycidyloxy group. n
Is an integer of 0 to 4 and represents the number of substituents R. Where X
When R is a hydrogen atom, R represents a hydroxyl group, and when X is a glycidyl group, R represents a glycidyloxy group. (2) Epoxy compound in which X is a glycidyl group in formula (1) (3) Epoxy resin composition using a compound in which X is a hydrogen atom in formula (1) as a curing agent (4) X in formula (1) X is a hydrogen atom and X
(5) An epoxy resin composition containing the compound in which X is a glycidyl group in the formula (1) and / or the epoxy resin described in (4) and a curing agent (6) A composition for sealing electronic components, comprising a compound in which X is a glycidyl group in the formula (1) and / or the epoxy resin, a curing agent, a curing catalyst, and an inorganic filler according to claim (4). An electronic component sealing composition comprising the composition described in (3) and an inorganic filler.

[0007]

DESCRIPTION OF THE PREFERRED EMBODIMENTS The present invention will be described below in detail. Specific examples of the compound in which X is a hydrogen atom in the formula (1) obtained in the present invention include 2,2-bis (4′-hydroxyphenyl) adamantane and 2,2-bis (2′-hydroxyphenyl) Adamantane, 2,2-bis (3 '
4'-dihydroxyphenyl) adamantane, 2,2-
Bis (2′4′-dihydroxyphenyl) adamantane, 2,2-bis (3 ′, 5′-dimethyl-4′-hydroxyphenyl) adamantane, 2,2-bis (3′-
Bromo-4′-hydroxyphenyl) adamantane,
2,2-bis (2'-methyl-4'-hydroxyphenyl) adamantane, 2,2-bis (3'-methyl-4 '
-Hydroxyphenyl) adamantane, 2,2-bis (3'-t-butyl-4'-hydroxyphenyl) adamantane, 2,2-bis (3'-t-butyl-6'-methyl-4'-hydroxyphenyl Adamantane, 2,
Specific examples of 2-bis (4′-hydroxy-3′-phenylphenyl) adamantane and the compound in which X in the above formula (1) is a glycidyl group include 2,2-bis (4′-glycidyloxyphenyl) Adamantane,
2,2-bis (2'-glycidyloxyphenyl) adamantane, 2,2-bis (3'4'-diglycidyloxyphenyl) adamantane, 2,2-bis (2'4'-
Diglycidyloxyphenyl) adamantane, 2,2-
Bis (3 ′, 5′-dimethyl-4′-glycidyloxyphenyl) adamantane, 2,2-bis (3′-bromo-4′-glycidyloxyphenyl) adamantane,
2,2-bis (2′-methyl-4′-glycidyloxyphenyl) adamantane, 2,2-bis (3′-methyl-4′-glycidyloxyphenyl) adamantane,
2,2-bis (3′-t-butyl-4′-glycidyloxyphenyl) adamantane, 2,2-bis (3′-t
-Butyl-6'-methyl-4'-glycidyloxyphenyl) adamantane, 2,2-bis (4'-glycidyloxy-3'-phenylphenyl) adamantane, and the like, but are not limited to these specific examples. Not something.

In the above formula (1), the compound in which X is a hydrogen atom can be used as a raw material for esters, polyurethanes, polycarbonates and the like and can be suitably used as a curing agent for epoxy resins. Epoxy resins that can be used at this time include, for example, cresol novolak type epoxy resin, phenol novolak type epoxy resin, bisphenol type epoxy resin, 3,3'5,5 '
Epoxidized tetramethylbiphenol, epoxidized naphthalene group, and trisphenol-based epoxy resin. In addition, a sealing agent containing an inorganic filler such as silica, alumina, or titanium aluminum and the above composition can be used for sealing electronic components. As the curing agent, it can be used in combination with other generally known curing agents such as polyhydric phenol compounds, acid anhydrides and amines.

An epoxy resin composed of an epoxy compound of the formula (1) wherein X is a glycidyl group, an epoxy compound of the formula (2) and a compound of the formula (1) wherein X is a hydrogen atom can be cured by combining with a curing agent. It can be a composition. As the curing agent used at this time,
Phenol novolac, cresol novolak, aralkylene phenol resins known under the trade names of Xyloc, naphthalene diol, bisphenols, biphenols, dicyclopentadiene phenol resin, etc. Phenols, methylnadic acid, phthalic anhydride,
Acid anhydrides such as tetrahydrophthalic anhydride, diaminodiphenylmethane, diaminodiphenylsulfone, ethylenediamine, amines such as triethylenetetramine,
Amides such as dicyandiamide can be used. The amount used is not particularly limited, but is preferably equivalent to the epoxy resin. In this case, it is preferable to use an imidazole-based, phosphine-based, or tertiary amine-based curing catalyst.

In order to obtain the above composition, a cresol novolak type epoxy resin, a phenol novolak type epoxy resin, a bisphenol type epoxy resin, 3,3 ′
Epoxidized 5,5′-tetramethylbiphenol,
An epoxidized product containing a naphthalene group, a trisphenol-based epoxy resin, or the like can be used in combination. There is a remarkable effect in improving the heat resistance.

In order to use the above composition as a composition for sealing electronic parts, it is desirable to fill an inorganic filler.
As the inorganic filler used at this time, silica, alumina, titanium aluminum or the like having a spherical, crushed, or the like shape and having an average particle size of 0.1 to 100 μm can be used. The content is suitably 60 to 95% of the whole composition, and particularly preferably about 75 to 90%.

The method for producing the compound of the above formula (1) will be described. It can be obtained by reacting 2-adamantanone with a phenol compound in the presence of an acid catalyst. Phenol compounds used in this case include phenol, cresols, xylenols, bromophenols, and dibromophenol.
, Chlorophenols, alkylphenols, dihydroxybenzenes, bisphenols, biphenols
Can be used. The amount of the phenol compound used is 2
-At least twice as much as adamantanone, preferably 2 to 10
It is preferably used in a molar excess of twice. As the acid catalyst,
Hydrochloric acid, sulfuric acid, phosphoric acid, polyphosphoric acid, hydrofluoric acid, toluenesulfonic acid, methanesulfonic acid, trifluoroacetic acid, aluminum chloride, iron chloride, boron trifluoride, and the like can be used. The amount used is from 0.01% by weight to 20% by weight of 2-adamantanone. In particular, it is not significantly affected by the amount of the acid catalyst used. In addition, a gas phase reaction can be performed using a solid acid catalyst. The reaction temperature is usually 10 to 200
° C, preferably 30 to 180 ° C.

After completion of the reaction, the acid catalyst is removed by neutralization or washing with water. Excess phenols are removed by distillation or dissolved in a solvent. The produced target product can be purified by recrystallization or the like.

In the formula (1), the compound in which X is a glycidyl group can be prepared by a conventional method, using a compound of formula (1) in which X is a hydrogen atom, such as epichlorohydrin, using caustic alkali or alkali carbonate. By reacting with epihalohydrin. In the formula (1), X is a hydrogen atom and an epihalohydrin usually in a ratio of 1: 1 to 1:
5 At this time, a high molecular compound is also slightly generated (5 to 10%). This corresponds to the above-described epoxy resin composed of a compound in which X is a hydrogen atom and a compound in which X is a glycidyl group in the formula (1). Examples of the caustic alkali include caustic soda, caustic potash, lithium hydroxide, and the like, and examples of the alkali carbonate include soda carbonate, potash carbonate, baking soda, and the like. It is preferable that the used amount is equivalent to the hydroxyl group or slightly excessive. The amount of epihalohydrin used is preferably equivalent to the hydroxyl group to 15 times equivalent.

At this time, alcohols such as methanol, ethanol, isopropanol, butanol and methoxyethanol, ethers such as dioxane, diglyme, dibutyl ether and THF, Dimethylformamide,
An aprotic polar solvent such as dimethylsulfoxide and dimethylimidazolidinone, and a ketone-based solvent such as acetone, methyl ethyl ketone and methyl isobutyl ketone can be used. The amount used is 0.05 to 50 times, preferably 0.1 to 20 times the weight of epichlorohydrin. It is also possible to use a phase transfer catalyst.

The reaction temperature is preferably from 10 to 120 ° C.,
90 ° C. is particularly preferred. In the formula (1), while the compound in which X is a hydrogen atom, epihalohydrin, the above-mentioned organic solvent, and the phase transfer catalyst are optionally stirred, the above-mentioned alkaline substance is gradually added as it is or as an aqueous solution. desirable. It is preferable that water in the system is driven out by azeotropic dehydration. The reaction time can be from 1 to 10 hours. After the completion of the reaction, the used organic solvent and epichlorohydrin are recovered, and a salt of a by-product precipitated is separated by a method such as filtration. Or, it is removed by washing with water. At this time, a solvent can be newly added. In this case,
Aromatic hydrocarbons, ketone solvents, ether solvents, and the like that are not soluble in water are preferred.

After removing the salts, the desired product can be precipitated and removed by distilling off the solvent, adding a poor solvent, cooling or the like.

EXAMPLES The present invention will be described in more detail with reference to the following examples, but the present invention is not limited to these examples.

Example 1 In a 500 ml, four-necked flask, 5-adamantanone was added.
0 g, 150 g of phenol and 150 ml of concentrated hydrochloric acid were added thereto, and the mixture was heated to 80 ° C. and reacted for 16 hours. After completion of the reaction, the lower layer was withdrawn, leaving the upper layer. 200m of toluene here
l was added. The formed precipitate was separated by filtration, washed with acetone, washed with water, and dried. 25.3 g of 2,2-bis (4 ′
White crystals of (-hydroxyphenyl) adamantane were obtained. Its melting point was 321 ° C. 13C-NM
The R spectrum was as shown in FIG.

Example 2 In a 100 ml, four-necked flask, 14 g of 2,2-bis (4'-hydroxyphenyl) adamantane, 32.4 g of epichlorohydrin, 40 g of dimethyl sulfoxide,
20 g of methyl isobutyl ketone and 0.4 g of water were charged and heated to 45 ° C. Here, flaky caustic soda;
5 g were added in small portions over 1.5 hours. After completion of the addition, the reaction temperature was raised to 65 ° C, and the reaction was carried out at 65 to 75 ° C for 4 hours. After the completion of the reaction, the mixture was cooled, and 50 ml of water and 50 g of methylisobutyl ketone were added thereto. After removing the aqueous layer, some insolubles were removed by filtration, and methyl isobutyl ketone was distilled off. 17.1 g of 2,2-bis (4′-glycidyloxyphenyl) adamantane was obtained as white crystals. The melting point of the target product was 160 ° C. The epoxy equivalent was 217, which almost coincided with the theoretical value of 216.
FIG. 2 shows the 1 H-NMR spectrum. The Abbe refractive index of this product was 1.6 at 25 ° C.

[0020]

Example 3 The epoxy compound obtained in Example 2 was replaced with 1
g, 0.45 g of phenol-novolak (softening point: 83 ° C., hydroxyl equivalent) and 0.03 g of triphenylphosphine.
After taking 1 g and mixing well at 180 ° C., the mixture was reacted at 180 ° C. for 5 hours to obtain a cured product. This was pulverized and subjected to DSC measurement, and Tg was determined from the intermediate point between the start and end of the endotherm. T
g was 185 ° C.

[0021]

According to the present invention, 2,2-bis (hydroxyphenyl) adamantane and 2,2-bis (glycidyloxyphenyl) adamantane are newly provided. These are polycarbonates, polyesters,
It can be used for polyurethane, epoxy compounds or resins, and especially epoxy compounds or resins are useful as compositions for electronic materials.

[Brief description of the drawings]

FIG. 1 is a 13 C-NMR spectrum of 2,2-bis (4′-hydroxyphenyl) adamantane obtained in Example 1.

FIG. 2 is a 1H-NMR spectrum of 2,2-bis (4′-glycidyloxyphenyl) adamantane obtained in Example 2.

Claims (7)

[Claims] A bis (hydroxyphenyl) adamantane represented by the following formula (1): (Wherein X represents a hydrogen atom or a glycidyl group, provided that X is
Is a hydrogen atom, R does not contain a glycidyloxy group,
When X is a glycidyl group, R does not include a hydroxyl group. R is
Each independently represents an alkyl group, an alkylene group, an aralkyl group, an aryl group, a halogen, an alkoxy group, a hydroxyl group or a glycidyloxy group. n is an integer of 0 to 4 and represents the number of substituents R. ) 2. The epoxy compound according to claim 1, wherein X in the formula (1) is a glycidyl group. 3. An epoxy resin composition using a compound of the formula (1) wherein X is a hydrogen atom as a curing agent. 4. An epoxy resin comprising a compound of the formula (1) wherein X is a hydrogen atom and a compound wherein X is a glycidyl group. 5. An epoxy resin composition comprising the compound of the formula (1) wherein X is a glycidyl group, and / or the epoxy resin according to claim 4 and a curing agent. 6. A composition for sealing electronic components, comprising a compound in which X is a glycidyl group in the formula (1) and / or the epoxy resin, curing agent, curing catalyst and inorganic filler according to claim 4. 7. The composition according to claim 3, wherein the composition comprises an inorganic filler.
COMPOSITION FOR SEALING ELECTRONIC COMPONENTS CONTAINING