JPH06329741A - Resin, epoxy resin, its production, resin composition and cured product of said composition - Google Patents

Abstract

PURPOSE:To obtain a resin or an epoxy resin useful as a high-reliability sealing material excellent in heat resistance and humidity resistance by condensing through dehydration dimethylolated cumylphenol with a naphthol compound in the presence of an acid catalyst and optionally glycidyletherifying the product. CONSTITUTION:A resin of formula I useful as an epoxy resin curing agent is obtained by condensing through dehydration dimethylolated cumylphenol of formula IV with a naphthol compound or a phenolic compound having substituents other than hydrogen atoms in the presence of an acid catalyst. In formula I, X is for example a group of formula II; X1 is for example a group of formula III; n is 0-20; m is 1 or 2; and R1 is a hydrogen atom, a halogen atom, 1-4C alkyl or aryl. This resin is optionally reacted with an epihalohydrin in the presence of an alkali metal hydroxide to obtain an epoxy resin.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin, an epoxy resin, a method for producing the same, a resin composition and a cured product thereof which are useful for highly reliable sealing / sealing of electronic parts, bonding, and plastic lenses.

[0002]

2. Description of the Related Art Thermosetting resins are widely used in the fields of electric and electronic parts due to their excellent electrical properties, heat resistance, adhesiveness, moldability and the like.

In recent years, particularly with the development of electric and electronic fields, further improvement of various characteristics such as heat resistance, moisture resistance, adhesion, low stress, transparency, and improvement of refractive index has been demanded. Many proposals have been made on epoxy resins, epoxy curing agents and compositions thereof in order to improve the properties. However, it cannot be said to be sufficient, for example, generation of cracks due to thermal shock after water absorption and moisture absorption, and increase in resin melt viscosity when trying to improve heat resistance.

[0004]

DISCLOSURE OF THE INVENTION The present invention has a high refractive index, an extremely small amount of hydrolyzable chlorine, and a cured product thereof having excellent heat resistance and moisture resistance. The present invention provides a useful resin, a method for producing the same, a resin composition containing the same, and a cured product thereof.

[0005]

Means for Solving the Problems The inventors of the present invention have completed the present invention by finding out a resin and a manufacturing method that can achieve the above objects, as a result of earnest research on a method for imparting and improving the above-mentioned characteristics. is there. That is, the present invention includes (1) and formula (1)

[0006]

[Chemical 8]

(X in the formula (1) is the formula (A) or the formula (B)
To

[0008]

[Chemical 9]

X ₁ is the formula (A1) or the formula (B1)

[0010]

[Chemical 10]

And n is 0 to 20. Furthermore, m in the formula (A), the formula (B), the formula (A1), and the formula (B1),
q and 1 respectively represent 1 or 2, R ₁ , R ₂ , R ₃ ,
R _4's each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group,
When q is 1, R ₂ , R ₃ and R ₄ are not hydrogen atoms at the same time. ) Resin (2), Formula (2)

[0012]

[Chemical 11]

(Y in the formula (2) is the formula (C) or the formula (D))
To

[0014]

[Chemical 12]

Y ₁ is the formula (C1) or the formula (D1)

[0016]

[Chemical 13]

And n is 0 to 20. Further, m in the formula (C), the formula (D), the formula (C1), and the formula (D1),
q and 1 respectively represent 1 or 2, R ₁ , R ₂ , R ₃ ,
R _4's each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group,
When q is 1, R ₂ , R ₃ and R ₄ are not hydrogen atoms at the same time. Further, G represents a glycidyl group, that is, the following formula (G). ) Epoxy resin represented by

[0018]

[Chemical 14]

(3), equation (3)

[0020]

[Chemical 15]

The cumylphenol dimethylol compound represented by and a naphthol compound or a phenol compound having a substituent other than a hydrogen atom are dehydrated and condensed in the presence of an acid catalyst, and if necessary, an alkali metal hydroxide is added. A method for producing a resin represented by the above formula (1) or an epoxy resin represented by the above formula (2), characterized by reacting with epihalohydrin in the presence of

An epoxy resin composition containing (4) an epoxy resin, a curing agent and, if necessary, a curing accelerator, contains the resin represented by the above formula (1) as a curing agent,
And / or an epoxy resin composition containing the epoxy resin represented by the above formula (2) as the epoxy resin,
(5) A cured product of the epoxy resin composition according to (4) above.

The present invention will be described in detail below. Formula (1)
In (2) and (2), n represents an average value and takes a value of 0 to 20, preferably a value of 0 to 7, and particularly preferably a value of 0 to 4. R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. Examples of the halogen atom include a bromine atom and a chlorine atom. Examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group and t-butyl group, and examples of the aryl group include phenyl group.

The resin represented by the above formula (1) has the above formula (3) easily obtained by reacting cumylphenol and formaldehyde in the presence of an alkali metal hydroxide by a conventionally known method. It is synthesized by subjecting the represented cumylphenol dimethylol compound and a naphthol compound or a phenol compound having a substituent other than a hydrogen atom to a dehydration condensation reaction in the presence of an acid catalyst.

Further, if necessary, the resin represented by the above formula (1) is glycidyl etherified by a conventionally known method, that is, the resin represented by the above formula (1) and epihalohydrin are treated with alkali metal water. By reacting in the presence of an oxide, the epoxy resin represented by the above formula (2) can be obtained.

As the cumylphenol dimethylol compound represented by the above formula (3), 2,6-dimethylol-4-cumylphenol is preferably used because of its stability and easiness of reaction. Examples of the phenol compound having a substituent other than a hydrogen atom, which can be reacted with these cumylphenol dimethylol compounds, include o-cresol and m.
-Cresol, p-cresol, 2,4-xylenol, 2,6-xylenol, 2,3,6-trimethylphenol, 2,3,5-trimethylphenol, o-ethylphenol, o-chlorophenol, o-tret
-Butylphenol, o-tert-butyl-4-methylphenol, p-tret-butylphenol, catechol, resorcinol, hydroquinone, 2,5-dimethylhydroquinone, 2,6-dimethylhydroquinone, 2,4,6-trimethylhydroquinone, etc. Examples of the naphthol compound include 1-naphthol and 2
-Naphthol, 2-methyl 1-naphthol, 1,4-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like can be mentioned, but they are not limited to these compounds.

When a dehydration condensation reaction is carried out between a cumylphenol dimethylol compound and these phenol compounds or naphthol compounds, the amount of the phenol compound or naphthol compound used is preferably 1 with respect to 1 mol of the cumylphenol dimethylol compound. It is used in the range of 0.5 to 16 mol, particularly preferably 2 to 6 mol. If the amount of the phenol compound or naphthol compound used is small, the compound is easily polymerized or decomposed to generate an aldehyde, and if the amount used is too large, the cost for recovery increases, which is disadvantageous.

As the acid catalyst used in the dehydration condensation reaction, hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, oxalic acid, paratoluenesulfonic acid, boron trifluoride, zinc chloride or the like can be used. Particularly, hydrochloric acid, paratoluenesulfonic acid, oxalic acid and the like are preferably used, but two or more kinds can be used in combination. The amount of these acid catalysts used is not particularly limited, but is usually 0.0 with respect to the amount of cumylphenol dimethylol compound used.
It can be selected in the range of 01 to 0.1 times.
When these acid catalysts are added to the reaction system, they can be diluted with an appropriate solvent or gradually added dropwise.

The dehydration condensation reaction in the presence of the acid catalyst is preferably carried out in the range of 20 to 130 ° C., particularly preferably in the range of 40 to 100 ° C., and the reaction time is usually 1 to 20 hours. The range can be selected. Further, this reaction is preferably carried out in the presence of a suitable solvent such as methanol, toluene, methyl isobutyl ketone and the like. Further, the condensation reaction solution thus obtained is repeatedly washed with water until the inside of the system becomes neutral, and after water is separated and drained, the solvent and unreacted materials are removed under heating and reduced pressure, thereby being represented by the formula (1). A resin is obtained.

Next, the epoxy resin represented by the formula (2) of the present invention can be obtained by reacting the resin represented by the formula (1) with epihalohydrin. This reaction can be carried out according to a conventionally known method for obtaining a polyglycidyl ether from a novolak type phenol resin and epihalohydrin. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a dissolved mixture of a resin represented by the formula (1) and an excess of epihalohydrin such as epichlorohydrin, or 20 to 120 while being added.
React at a temperature between ° C. At this time, an aqueous solution of the alkali metal hydroxide may be used, and in that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and the water is continuously added under reduced pressure or normal pressure. Alternatively, a method in which epihalohydrin is distilled off, liquid separation is performed, water is removed, and epihalohydrin is continuously returned to the reaction system may be used.

Further, it can be obtained by adding a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride as a catalyst to a dissolved mixture of resin and epihalohydrin and reacting at 50 ° C to 150 ° C. Alternatively, a solid or aqueous solution of an alkali metal hydroxide may be added to the halohydrin etherified product, and the mixture may be reacted again at a temperature of 20 to 120 ° C. for dehydrohalogenation (ring closure).

Usually, the amount of epihalohydrin used in these reactions is 1 to 20 mol, preferably 2 to 10 mol, based on 1 equivalent of hydroxyl group of the resin of the formula (1) as a raw material. The amount of the alkali metal hydroxide used is 0.8 to 1.5 mol, preferably 0.9 to 1.1 mol, per 1 equivalent of the hydroxyl group of the resin of the formula (1) which is the raw material. Furthermore, in order to allow the reaction to proceed smoothly, it is preferable to carry out the reaction by adding an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide in addition to alcohols such as methanol and ethanol.

After washing the reaction products of these epoxidation reactions with or without washing with water, the mixture is heated to 150 to 2 under reduced pressure.
The epoxy resin of the formula (2) of the present invention can be obtained by removing epihalohydrin and other added solvents at 20 ° C. and a pressure of 15 mmHg or less. Further, in order to obtain an epoxy resin having less hydrolyzable halogen, the recovered epoxy resin is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is prepared. It is also possible to secure the ring closure by carrying out the second step reaction by adding. In this case, the amount of the alkali metal hydroxide used is preferably 0.01 to 0.2 mol, particularly preferably 0.05 to 0.1 mol, relative to 1 equivalent of the hydroxyl group of the resin of the formula (1) used for the epoxidation.
It is a mole. The reaction temperature is preferably 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

After the completion of the second-step reaction, the produced salt is removed by filtration, washing with water and the like, and the solvent such as toluene and methyl isobutyl ketone is distilled off under reduced pressure with heating, whereby the amount of hydrolyzable halogen of the present invention is small. An epoxy resin of formula (2) is obtained.

The epoxy resin composition of the present invention will be described below. In the epoxy resin composition of the above (4), the resin represented by the formula (1) (hereinafter referred to as the resin of the present invention) can be used alone or in combination with other curing agents. When used in combination, the proportion of the resin of the present invention in the total curing agent is preferably 20% by weight or more, and particularly 30
It is preferably at least wt%.

Other curing agents that can be used in combination with the resin of the present invention include, for example, polyamine type curing agents such as aliphatic polyamine, aromatic polyamine and polyamide polyamine, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride and the like. Examples thereof include acid anhydride curing agents, phenolic novolacs, phenolic curing agents such as cresol novolacs, Lewis acids such as boron trifluoride or salts thereof, and curing agents such as dicyandiamides, but are not limited thereto. is not. These may be used alone or in combination of two or more.

In the epoxy resin composition of the above (4), the epoxy resin represented by the formula (2) (hereinafter referred to as the epoxy resin of the present invention) is used alone or in combination with other epoxy resins. You can When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 20% by weight or more, and particularly preferably 30% by weight or more.

Other epoxy resins which can be used in combination with the epoxy resin of the present invention include novolac type epoxy resin, bisphenol F type epoxy resin, bisphenol A type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin and biphenol type epoxy resin. Examples of the epoxy resin include novolac type epoxy resin, which is advantageous from the viewpoint of heat resistance. As the novolac type epoxy resin, for example, phenol novolac type epoxy resin,
Examples thereof include cresol novolac type epoxy resin, naphthol novolac type epoxy resin, and brominated phenol novolac type epoxy resin. Other epoxy resins that can be used in combination are not limited to these, and these may be used alone or in combination of two or more kinds.

In the epoxy resin composition of the above (4), when the resin of the present invention is used as the curing agent, the above-mentioned other epoxy resin or the epoxy resin of the present invention can be used as the epoxy resin.

In the epoxy resin composition (4), when the epoxy resin of the present invention is used as the epoxy resin, the above-mentioned other curing agent or the resin of the present invention may be used as the curing agent. I can.

In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably such that the functional group of the curing agent is 0.5 to 1.5 equivalents relative to 1 equivalent of the epoxy groups of the epoxy resin. It is preferably an amount of 0.6 to 1.2 equivalents.

If necessary, a curing accelerator can be used in the epoxy resin composition of the present invention. Examples of the curing accelerator include imidazole compounds, tertiary amine compounds, triphenylphosphine compounds and the like, but are not limited to these, and any of them can be used as a curing accelerator for ordinary epoxy resins. Can be used. These may be used alone or in combination of two or more. The amount of the curing accelerator used is preferably 0.01 to 15 parts by weight, more preferably 0.1 to 5 parts by weight, based on 100 parts by weight of the epoxy resin.

If desired, known additives can be added to the epoxy resin composition of the present invention. Examples of the additives include inorganic fillers such as silica, alumina, talc and glass fibers, surface treatment agents such as silane coupling agents, flame retardants, release agents, pigments and the like.

The epoxy resin composition of the present invention is obtained by uniformly mixing the components, and is usually 130 to 180.
Pre-cure in the range of 30-300 seconds at a temperature of ℃, 1
By post-curing in the range of 50 to 220 ° C. for 2 to 10 hours, a sufficient curing reaction proceeds to obtain the cured product of the present invention. It is also possible to uniformly disperse or dissolve the components of the epoxy resin composition in a solvent or the like, and then remove the solvent and cure.

Since the resin of the present invention and the epoxy resin of the present invention contain a hydrophobic group in the skeleton and have a low softening point and a low melt viscosity, they have good workability in transfer molding and the like. Further, since it has a characteristic of having a large refractive index, it can be used as a material for plastic lenses and the like.
Furthermore, the resin of the present invention obtained as described above, and /
Alternatively, the cured product of the epoxy resin composition containing the epoxy resin of the present invention has the property of having moisture resistance without impairing heat resistance. Therefore, the resin of the present invention and the epoxy resin of the present invention can be used as an epoxy resin curing agent or as an epoxy resin in a wide range of fields where high refractive index, moisture resistance and the like are required. Specifically, it is useful as a compounding component for various electrical / electronic materials such as various sealing / sealing materials, composite materials, laminated plates, insulating materials, etc., and can also be used for molding materials, coating materials, optical materials, etc. It is not limited to.

[0046]

EXAMPLES The present invention will be described below with reference to examples. In addition, the refractive index in the examples is a value obtained by calculation from a value of a resin and a 50% by weight solution of an epoxy resin in tetrahydrofuran at 25 ° C. by an Abbe refractometer, and the softening point is JIS K2425.
(Ring and ball method) Hydrolyzable chlorine is 1N-KOH to ethanol in dioxane for 30 minutes, and when decomposed under reflux, chlorine content ppm, hydroxyl group equivalent and epoxy equivalent determined by titration indicate g / eq. The present invention is not limited to these examples.

Example 1 A flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer was equipped with 400 parts by weight of water and sodium hydroxide (purity: 99%).
Granules) 42.6 parts by weight were charged, the alkali content was dissolved under nitrogen purging, and 212 parts by weight (1 mol) of 4-cumylphenol was added under stirring at 50 ° C. Although the inside of the system became homogeneous and transparent, the reaction was further carried out at a temperature of 50 ° C. for 1 hour. Then formalin (35% by weight pure) 18
2 parts by weight (2.12 mol) were added, paying attention to the exotherm. After completion of the addition, the mixture was reacted at 60 ° C for 2 hours, 300 parts by weight of water was added, and the temperature in the system was further cooled to 30 ° C.
600 parts by weight of methyl isobutyl ketone were added. Next, 105 parts by weight of an aqueous hydrochloric acid solution (pure content 35% by weight) was added while paying attention to heat generation and neutralization, and the aqueous phase was discarded. Furthermore, it was washed twice with 300 parts by weight of water, and methyl isobutyl ketone (hereinafter referred to as MIBK) containing 2,6-dihydroxymethyl-4-cumylphenol (hereinafter referred to as dimethylol compound).
A solution was obtained.

Then, a MIB containing the above dimethylol compound
To the K solution, 460 parts by weight (4.2 mol) of o-cresol (purity 99% by weight) and 2 parts by weight of paratoluenesulfonic acid were added, and the mixture was added at 40 ° C. for 1 hour, 60 ° C. for 1 hour, and 80 ° C. for 2 hours.
The dehydration condensation reaction was carried out for a time. After completion of the reaction, the reaction mixture was transferred to a separating funnel and washed with water repeatedly to return to neutral. Then 180 from the oil layer using a rotary evaporator
℃, 5mmHg heating, MIBK under reduced pressure, and unreacted o
-Cresol was removed to obtain 425 parts by weight of a resin (A) of the present invention which was a pale yellow, transparent and solid at room temperature.

The softening point of the obtained resin (A) is 81.6.
ICI viscosity at ℃, 150 ℃ is 1.4ps,
The refractive index was 1.611 and the hydroxyl equivalent was 155.
Further, using this resin (A) as a solvent, tetrahydrofuran (TH
When F) was used and analyzed by the following GPC analyzer, the molecular weight distribution curve shown in FIG. 1 was obtained.

GPC device Liquid feed pump: L-6000 (manufactured by Hitachi Ltd.) Column: KF-803 (1 unit) + KF-802.5 (2 units) + KF-802 (1 unit) (Showa Denko) Column temperature : 40 ° C. Solvent: Tetrahydrofuran 1 ml / min Detector: RI SE-61 (Showa Denko) Data processing: CR-4A (Shimadzu)

From the calibration curve obtained by using standard polystyrene under these analytical conditions, the molecular weight of the composition of the main peak corresponds to the retention time of the tetranuclear body having four benzene rings, which is considered to be the main tetranuclear body. Sort the peak components,
Mass spectrum (FAB-MS) analysis gave M ⁺ 453. From this fact and the above molecular weight distribution curve, it was confirmed that this resin (A) was a resin (n = 0.3) represented by the following formula (4).

[0052]

[Chemical 16]

Example 2 2,6-xylenol was used in place of o-cresol in 30%.
Reaction was carried out in the same manner as in Example 1 except that 5 parts by weight (2.5 mol) was used to obtain 402 parts by weight of the resin (B) of the present invention which was a pale yellow, transparent and solid at room temperature.

The resin (B) thus obtained has a softening point of 68.2.
The ICI viscosity at 60 ° C and 150 ° C is 0.6 ps,
The refractive index was 1.607 and the hydroxyl equivalent was 162.
Further, this resin (B) was analyzed by the same GPC apparatus as in Example 1 to obtain the molecular weight distribution curve shown in FIG. In addition, the main peak component is collected and a mass spectrum (FAB-
Analysis by MS) gave M ⁺ 481.
From this fact and the molecular weight distribution curve, it was confirmed that this resin (B) was a resin (n = 0.1) represented by the following formula (5).

[0055]

[Chemical 17]

Example 3 The same as Example 1 except that 600 parts by weight (4.0 mol) of o-tert-butylphenol was used instead of o-cresol, and the reaction was further continued at 95 ° C. for 2 hours at the end of the dehydration condensation reaction. The same reaction was carried out to obtain 492 parts by weight of a resin (C) of the present invention which was light yellow, transparent and solid at room temperature.

The resin (C) thus obtained has a softening point of 85.5.
ICI viscosity at ℃, 150 ℃ is 1.0 ps,
The refractive index was 1.601 and the hydroxyl equivalent was 212.
Further, this resin (C) was analyzed by the same GPC apparatus as in Example 1 to obtain the molecular weight distribution curve shown in FIG. In addition, the main peak component is collected and a mass spectrum (FAB-
Analysis by MS) gave M ⁺ 537.
From this fact and the molecular weight distribution curve, it was confirmed that this resin (C) was a resin (n = 0.3) represented by the following formula (6).

[0058]

[Chemical 18]

Example 4 Instead of o-cresol, 6 o-phenylphenol was used.
80 parts by weight (4.0 mol) was used, and the reaction was carried out in the same manner as in Example 1 except that the dehydration condensation reaction was further reacted at 90 ° C. for 2 hours at the end, and the resin of the present invention was pale yellow, transparent and solid at room temperature. (D) 530 parts by weight was obtained.

The softening point of the obtained resin (D) is 91.2.
ICI viscosity at ℃, 150 ℃ is 2.7ps,
The refractive index was 1.639 and the hydroxyl equivalent was 197.
Further, this resin (D) was analyzed by the same GPC apparatus as in Example 1 to obtain the molecular weight distribution curve shown in FIG. In addition, the main peak component is collected and a mass spectrum (FAB-
Analysis by MS) gave M ⁺ 577.
From this fact and the molecular weight distribution curve, this resin has the following formula (7).
It was confirmed that the resin was represented by (n = 0.3).

[0061]

[Chemical 19]

Example 5 The reaction was carried out in the same manner as in Example 1 except that 440 parts by weight (4.0 mol) of resorcinol was used instead of o-cresol, and the resin of the present invention (E ) 42
3 parts by weight were obtained.

The softening point of the obtained resin (E) is 93.3.
ICI viscosity at ℃, 150 ℃ is 6.4 ps,
The refractive index was 1.631 and the hydroxyl equivalent was 118.
Further, this resin (E) was analyzed by the same GPC apparatus as in Example 1 to obtain the molecular weight distribution curve shown in FIG. In addition, the main peak component is collected and a mass spectrum (FAB-
Analysis by MS) gave M ⁺ 457.
From this fact and the molecular weight distribution curve, this resin has the following formula (8).
It was confirmed that the resin was represented by (n = 0.1).

[0064]

[Chemical 20]

Example 6 The reaction of Example 1 was repeated except that 864 parts by weight (6.0 mol) of 1-naphthol was used instead of o-cresol, and the resin of the present invention was yellow, transparent and solid at room temperature. (F) 52
6 parts by weight were obtained.

The softening point of the obtained resin (F) is 95.2.
ICI viscosity at 300C and 150C is 3.5 ps,
The refractive index was 1.651 and the hydroxyl equivalent was 177.
Further, this resin (F) was analyzed by the same GPC apparatus as in Example 1 to obtain a molecular weight distribution curve shown in FIG. In addition, the main peak component is collected and a mass spectrum (FAB-
Analysis by MS) gave M ⁺ 525.
From this fact and the molecular weight distribution curve, this resin has the following formula (9).
It was confirmed that the resin was represented by (n = 0.2).

[0067]

[Chemical 21]

Example 7 The reaction of Example 1 was repeated except that 360 parts by weight (2.5 mol) of 2-naphthol was used in place of o-cresol, and the resin of the present invention was yellow, transparent and solid at room temperature. (G) 51
3 parts by weight were obtained.

The softening point of the obtained resin (G) was crystallized and could not be measured, but the ICI viscosity at 150 ° C. was 6.0 ps, the refractive index was 1.654, and the hydroxyl equivalent was 179. It was Moreover, about this resin (G), Example 1
The same GPC device was used for analysis, and the molecular weight distribution curve shown in FIG. 7 was obtained. The main peak component was fractionated and analyzed by mass spectrum (FAB-MS) to give M ⁺ 5
25 was obtained. From this fact and the molecular weight distribution curve, it was confirmed that this resin was a resin (n = 0.1) represented by the following formula (10).

[0070]

[Chemical formula 22]

Example 8 The same as Example 1 except that 480 parts by weight (3.0 mol) of 1,6-dihydroxynaphthalene was used in place of o-cresol, and the recovery temperature of unreacted material was 230 ° C. The reaction and operation were carried out to obtain 500 parts by weight of a resin (H) of the present invention which was brown, transparent and solid at room temperature.

The softening point of the obtained resin (H) is 129.6.
The ICI viscosity at 40 ° C. and 150 ° C. was 40 ps or more, the refractive index was 1.649, and the hydroxyl equivalent was 124. The same GPC as in Example 1 was applied to this resin (H).
The analysis was carried out by the apparatus to obtain the molecular weight distribution curve shown in FIG. In addition, the main peak component is collected and the mass spectrum (F
It was analyzed by (AB-MS) to give M ⁺ 557. From this fact and the molecular weight distribution curve, it was confirmed that this resin was a resin (n = 0.7) represented by the following formula (11).

[0073]

[Chemical formula 23]

Example 9 155 parts by weight of the resin (A) obtained in Example 1 was added with 555 parts by weight of epichlorohydrin (6 mol) and 280 parts of DMSO.
After adding 50 parts by weight and dissolving, the mixture was heated to 50 ° C., 42 parts by weight (1.04 mol) of flaky sodium hydroxide (purity 99%) was added over 100 minutes, and then at 60 ° C. for 2 hours and at 70 ° C. The reaction was carried out for 1 hour. After completion of the reaction, washing with water was repeated, the aqueous layer was separated and removed, and excess epichlorohydrin was distilled off from the oil layer under heating and reduced pressure, and 500 parts by weight of methyl isobutyl ketone was added and dissolved in the residue.

Further, this methyl isobutyl ketone solution was heated to 70 ° C., 10 parts by weight of a 30% by weight sodium hydroxide aqueous solution was added, and the mixture was reacted for 1 hour, and then washed with water repeatedly to make the pH neutral. Further, the aqueous layer was separated and removed, and methyl isobutyl ketone was distilled off from the oil layer under heating and reduced pressure to give a pale yellow,
203 parts by weight of a transparent and solid epoxy resin (I) of the present invention was obtained.

The softening point of the obtained epoxy resin (I) is 5
The ICI viscosity at 3.7 ° C. and 150 ° C. was 0.6 ps, the refractive index was 1.589, the epoxy equivalent was 221 and the hydrolyzable chlorine was 360 ppm. This resin (I)
Was analyzed by liquid chromatography (GPC, analysis conditions are the same as in Example 1) to obtain a molecular weight distribution curve shown in FIG. The main peak component was fractionated and analyzed by mass spectrum (FAB-MS) to find that M ⁺ 62
1 was obtained. From this fact and the molecular weight distribution curve, this epoxy resin is represented by the following formula (12) (n =
It was confirmed to be 0.5).

[0077]

[Chemical formula 24]

Example 10 The same reaction and operation as in Example 9 were carried out except that 160 parts by weight of the resin (B) was used to obtain 208 parts by weight of a pale yellow, transparent, solid epoxy resin (J) of the present invention. . The obtained epoxy resin (J) has a softening point of I at 45.8 ° C and 150 ° C.
The CI viscosity was 0.9 ps, the refractive index was 1.575, the epoxy equivalent was 235, and the hydrolyzable chlorine was 350 ppm. This resin (J) was analyzed by liquid chromatography (GPC, analysis conditions being the same as in Example 1), and the molecular weight distribution curve shown in FIG. 10 was obtained. Further, the main peak component was collected and analyzed by mass spectrum (FAB-MS) to obtain M ⁺ 649. From this fact and the molecular weight distribution curve, it was confirmed that this epoxy resin was an epoxy resin (n = 0.2) represented by the following formula (13).

[0079]

[Chemical 25]

Example 11 The same reaction and operation as in Example 9 were carried out except that 214 parts by weight of the resin (C) was used to obtain 255 parts by weight of a pale yellow, transparent and solid epoxy resin (K) of the present invention. . The obtained epoxy resin (K) has a softening point of I at 67.3 ° C and 150 ° C.
The CI viscosity was 1.2 ps, the refractive index was 1.573, the epoxy equivalent was 285, and the hydrolyzable chlorine was 345 ppm. This resin (K) was analyzed by liquid chromatography (GPC, analysis conditions being the same as in Example 1), and the molecular weight distribution curve shown in FIG. 11 was obtained. When the main peak component was collected and analyzed by mass spectrum (FAB-MS), M + 705 was obtained. From this fact and the molecular weight distribution curve, it was confirmed that this epoxy resin was an epoxy resin (n = 0.3) represented by the following formula (14).

[0081]

[Chemical formula 26]

Example 12 The same reaction and operation as in Example 9 except that 197 parts by weight of the resin (D) were used to obtain 239 parts by weight of a pale yellow, transparent, solid epoxy resin (L) of the present invention. . The obtained epoxy resin (L) has a softening point of I at 69.8 ° C and 150 ° C.
The CI viscosity was 1.7 ps, the refractive index was 1.609, the epoxy equivalent was 270, and the hydrolyzable chlorine was 380 ppm. This resin (L) was analyzed by liquid chromatography (GPC, analysis conditions being the same as in Example 1), and the molecular weight distribution curve shown in FIG. 12 was obtained. The main peak component was collected and analyzed by mass spectrum (FAB-MS) to obtain M ⁺ 745. From this fact and the molecular weight distribution curve, it was confirmed that this epoxy resin was an epoxy resin (n = 0.4) represented by the following formula (15).

[0083]

[Chemical 27]

Example 13 The same reaction and operation as in Example 9 was carried out except that 108 parts by weight of the resin (E) was used to obtain 156 parts by weight of a pale yellow, transparent, solid epoxy resin (M) of the present invention. . The resulting epoxy resin (M) has a softening point of I at 61.3 ° C and 150 ° C.
The CI viscosity was 3.0 ps, the refractive index was 1.583, the epoxy equivalent was 183, and the hydrolyzable chlorine was 390 ppm. This resin (M) was analyzed by liquid chromatography (GPC, analysis conditions being the same as in Example 1), and the molecular weight distribution curve shown in FIG. 13 was obtained. The main peak component was fractionated and analyzed by mass spectrum (FAB-MS) to obtain M ⁺ 737. From this fact and the molecular weight distribution curve, it was confirmed that this epoxy resin was an epoxy resin (n = 0.9) represented by the following formula (16).

[0085]

[Chemical 28]

Example 14 The same reaction and operation as in Example 9 were carried out except that 172 parts by weight of the resin (F) was used to obtain 222 parts by weight of a pale yellow, transparent, solid epoxy resin (N) of the present invention. . The softening points of the obtained epoxy resin (N) are 74.8 ° C. and I at 150 ° C.
The CI viscosity was 1.6 ps, the refractive index was 1.627, the epoxy equivalent was 257, and the hydrolyzable chlorine was 320 ppm. This resin (N) was analyzed by liquid chromatography (GPC, analysis conditions being the same as in Example 1), and the molecular weight distribution curve shown in FIG. 14 was obtained. Moreover, when the peak component was fractionated and analyzed by mass spectrum (FAB-MS), M ⁺ 693 was obtained. From this fact and the molecular weight distribution curve, it was confirmed that this epoxy resin was an epoxy resin (n = 0.2) represented by the following formula (17).

[0087]

[Chemical 29]

Example 15 The same reaction and operation as in Example 9 were carried out except that 174 parts by weight of the resin (G) was used to obtain 218 parts by weight of a yellow, transparent and solid epoxy resin (O) of the present invention. The obtained epoxy resin (O) has a softening point of 73.0 ° C. and IC at 150 ° C.
The I viscosity was 2.0 ps, the refractive index was 1.629, the epoxy equivalent was 266, and the hydrolyzable chlorine was 330 ppm. This resin (O) was analyzed by liquid chromatography (GPC, analysis conditions being the same as in Example 1), and the molecular weight distribution curve shown in FIG. 15 was obtained. The main peak component was collected and analyzed by mass spectrum (FAB-MS), and M ⁺ 693 was obtained. From this fact and the molecular weight distribution curve, it was confirmed that this epoxy resin was an epoxy resin (n = 0.3) represented by the following formula (18).

[0089]

[Chemical 30]

Example 16 The same reaction and operation as in Example 9 were carried out except that 117 parts by weight of the resin (H) was used to obtain 165 parts by weight of a brown, transparent and solid epoxy resin (P) of the present invention. The resulting epoxy resin (P) has a softening point of 85.3 ° C and IC at 150 ° C.
The I viscosity was 9.4 ps, the refractive index was 1.630, the epoxy equivalent was 187, and the hydrolyzable chlorine was 390 ppm. This resin (P) was analyzed by liquid chromatography (GPC, analysis conditions being the same as in Example 1), and the molecular weight distribution curve shown in FIG. 16 was obtained. The main peak component was collected and analyzed by mass spectrum (FAB-MS), and M ⁺ 837 was obtained. From this fact and the molecular weight distribution curve, it was confirmed that this epoxy resin was an epoxy resin (n = 1.2) represented by the following formula (19).

[0091]

[Chemical 31]

Test Example Resins (A), (B) obtained in Examples 1 to 8 above,
(C), (D), (E), (F), (G), and (H) are used respectively, and as Comparative Example 1, a bisphenol A type resin (resin (X), hydroxyl group equivalent 116, refractive index 1.60
7, melting point 156 [deg.] C., and an epoxy resin (o-cresol novolac type epoxy resin, EOCN-1020 (Nippon Kayaku Co., Ltd.) for 100 parts by weight of these curing agents
Made), epoxy equivalent 200, hydrolyzable chlorine 380pp
m, an ICI viscosity at 150 ° C. of 3.2 ps) and a curing accelerator (triphenylphosphine) were used in amounts shown in Table 1, and a resin molded body was prepared by transfer molding to obtain 160 ° C. × 2 hours + 180 ° C. × 8 hours. It was cured under the following curing conditions. The results of measuring the glass transition temperature and water absorption of the cured product thus obtained are shown in Table 1.

Further, the epoxy resins (I), (J), (K), (L), (M), obtained in Examples 9 to 16 above,
(N), (O) and (P) are used, and as a comparative example 2, a bisphenol A type epoxy resin (epoxy resin (Y), epoxy equivalent 189, hydrolyzable chlorine 560p is used.
pm, refractive index 1.574, ICI viscosity at 150 ° C. is 0.1 ps or less), and these epoxy resins 150
Hardening agent (phenol novolac type resin,
PN-80 (Nippon Kayaku Co., Ltd.), hydroxyl equivalent 106g
/ Mol, ICI viscosity of 1.5 ps at 150 ° C.) and a curing accelerator (triphenylphosphine) in the amounts used shown in Table 2, and a resin molded product is prepared by transfer molding to obtain 160 ° C. × 2 hours + 180 ° C. × 8. It was cured according to the curing condition of time. Table 2 shows the results of measuring the glass transition temperature and water absorption of the thus obtained cured product.

[0094]

Table 1 (1) Resin (Curing agent) (A) (B) (C) (D) (E) Epoxy resin wt part 129 123 123 94 102 169 Curing accelerator wt part 1.3 1.2 1.2 0.0 1.0 1.7 Glass transition temperature * 1 ° C 130 133 136 127 156 Water absorption rate * 2 wt% 1.1 1.1 1.1 0.9 0.9 1.6

[0095]

Table 2 (1) Resin (hardening agent) (F) (G) (H) (X) Epoxy resin wt part 113 112 112 161 173 Curing accelerator wt part 1.1 1.1 1.1 1.6 1. 7 Glass transition temperature * 1 ° C 141 136 156 124 124 Water absorption rate * 2 wt% 0.9 0.9 0.9 1.5 1.3 * 1 TMA Value at temperature rising rate 2 ° C / min * 2 Specimen diameter x thickness 50 mm × 3 mm
Absorption by the Increase in Weight of Boiled Disc after 24 Hours in Boiling Water

[0096]

[Table 3] Table 2 (1) Epoxy resin (I) (J) (K) (L) (M) Curing agent wt part 68 69 56 56 59 89 Curing accelerator wt part 1.5 1.5 1.5 1.5 1 .5 1.5 Glass transition temperature * 1 ° C 131 131 134 134 125 151 Water absorption rate * 2 wt% 1.2 1.2 1.0 1.0 1.0 1.8

[0097]

Table 4 (2) Epoxy resin (N) (O) (P) (Y) Curing agent wt part 62 60 85 85 84 Curing accelerator wt part 1.5 1.5 1.5 1.5 1.5 Glass transition Temperature * 1 ° C 143 139 160 125 Water absorption * 2 wt% 0.9 1.0 1.7 1.4 * 1 Same as Table 1 * 2 Same as Table 1

[0098]

The resin of the present invention and the epoxy resin both have a high refractive index, a small amount of hydrolyzable chlorine and the like, and a high purity.
Since the cured product of the resin composition using the resin or epoxy resin of the present invention as a raw material can obtain excellent heat resistance and moisture resistance, it is used for sealing electronic components, laminating materials, molding materials, etc. Can be done. Further, according to the production method of the present invention, these resins and the epoxy resin which is a glycidyl ether thereof can be easily obtained in high yield.

[Brief description of drawings]

FIG. 1 is a molecular weight distribution curve of the resin (A) obtained in Example 1.

FIG. 2 is a molecular weight distribution curve of the resin (B) obtained in Example 2.

FIG. 3 is a molecular weight distribution curve of the resin (C) obtained in Example 3.

FIG. 4 is a molecular weight distribution curve of the resin (D) obtained in Example 4.

FIG. 5: Molecular weight distribution curve of resin (E) obtained in Example 5

FIG. 6 is a molecular weight distribution curve of the resin (F) obtained in Example 6.

FIG. 7: Molecular weight distribution curve of resin (G) obtained in Example 7

FIG. 8: Molecular weight distribution curve of resin (H) obtained in Example 8

9 is a molecular weight distribution curve of the epoxy resin (I) obtained in Example 9. FIG.

10 is a molecular weight distribution curve of the epoxy resin (J) obtained in Example 10. FIG.

11 is a molecular weight distribution curve of the epoxy resin (K) obtained in Example 11.

FIG. 12: Molecular weight distribution curve of the epoxy resin (L) obtained in Example 12

13 is a molecular weight distribution curve of the epoxy resin (M) obtained in Example 13.

FIG. 14 is a molecular weight distribution curve of the epoxy resin (N) obtained in Example 14.

15 is a molecular weight distribution curve of the epoxy resin (O) obtained in Example 15. FIG.

16 is a molecular weight distribution curve of the epoxy resin (P) obtained in Example 16.

Claims (5)

[Claims] 1. A formula (1): (In the formula (1), X represents the formula (A) or the formula (B): X ₁ is the formula (A1) or the formula (B1) Is shown and n shows 0-20. Further, in the formula (A), the formula (B), the formula (A1) and the formula (B1), m and q respectively represent 1 or 2, and R ₁ , R ₂ , R ₃ and R ₄ are independent of each other. Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. However, when q is 1, R ₂ , R ₃ and R ₄ are not hydrogen atoms at the same time. ) Resin represented by. 2. Formula (2): (In the formula (2), Y represents the formula (C) or the formula (D): Y ₁ is the formula (C1) or the formula (D1) Is shown and n shows 0-20. Further, in the formula (C), the formula (D), the formula (C1), and the formula (D1), m and q each represent 1 or 2, and R ₁ , R ₂ , R ₃ , and R ₄ are independent of each other. Represents a hydrogen atom, a halogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group. However, when q is 1, R ₂ , R ₃ and R ₄ are not hydrogen atoms at the same time. G represents a glycidyl group. ) Epoxy resin represented by. 3. Formula (3): In the presence of an acid catalyst, a dehydration condensation reaction of a cumylphenol dimethylol compound represented by and a naphthol compound or a phenol compound having a substituent other than a hydrogen atom is carried out, and, if necessary, in the presence of an alkali metal hydroxide. A method for producing the resin represented by the formula (1) according to claim 1 or the epoxy resin represented by the formula (2) according to claim 2, which comprises reacting with epihalohydrin. 4. An epoxy resin composition comprising an epoxy resin, a curing agent and optionally a curing accelerator, which contains the resin of claim 1 as a curing agent and / or an epoxy resin of claim 2. An epoxy resin composition comprising a resin. 5. A cured product of the epoxy resin composition according to claim 4.