JP2887213B2 - New compounds, resins, resin compositions and cured products - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a compound, a resin, a resin composition and a cured product thereof useful as a material for encapsulating a highly reliable semiconductor.

[0002]

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

However, in recent years, particularly with the development of the electric and electronic fields, further improvements in various properties such as heat resistance, moisture resistance and adhesion have been demanded. In order to improve these properties, epoxy resins have been used. Although many proposals have been made for epoxy resins and epoxy curing agents and their compositions, they are still insufficient, for example, cracks are easily generated by thermal shock after water absorption and moisture absorption.

[0004]

SUMMARY OF THE INVENTION The present invention is to provide a resin which has a low melt viscosity and which gives a cured product having excellent heat resistance and moisture resistance and is suitable for highly reliable semiconductor encapsulation, and a cured product thereof. It is.

[0005]

Means for Solving the Problems The present inventors have made intensive studies on methods for imparting and improving the above-mentioned properties, and as a result, completed the present invention.

That is, the present invention provides the following equation (1).

[0007]

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Wherein R ₁ , R ₂ , R ₃ , R ₄ , R
_{'1, R'2, R'3} , showing each _R'4 independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, having 1 to 4 carbon atoms. A compound represented by the formula (2):

[0009]

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1-naphthol dimethylol compound represented by the formula (P):

[0011]

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Wherein 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. A resin obtained by reacting one or more of the above in the presence of an acid catalyst and containing 30% by weight or more of the compound of the formula (1);

[0013]

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(Wherein 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). One or more monomethylol compounds and 1-
A resin obtained by reacting naphthol in the presence of an acid catalyst and containing at least 30% by weight of the compound of the formula (1);

[0015]

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(Wherein R ₁ , R ₂ , R ₃ , R ₄ , R
_{'1, R'2, R'3} , showing each _R'4 independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, having 1 to 4 carbon atoms. An epoxy compound represented by
(5) The compound of the formula (1) or the resin of the above (2) or (3) is converted to a compound of the formula (E)

[0017]

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An epoxy resin obtained by reacting with an epihalohydrin represented by the formula (wherein Y represents a halogen atom) and containing at least 30% by weight of an epoxy compound of the formula (4):

(6) In the epoxy resin composition containing an epoxy resin, a curing agent and a curing accelerator, a compound of the formula (4) or the epoxy resin of the above (5) is used as the epoxy resin (A), and / or (B) Formula (1) as a curing agent
An epoxy resin composition using the compound of the above or the resin of the above (2) or (3),

(7) A cured product of the epoxy resin composition of (6).

Hereinafter, the present invention will be described in detail. The compound represented by the above formula (1) or 30% by weight of the compound
The above-mentioned resin contains a 1-naphthol dimethylol compound represented by the above formula (2) and a phenol represented by the formula (P), or a phenol monomethylol compound represented by the above formula (3). All are synthesized by performing a dehydration condensation reaction with 1-naphthol in the presence of an acid catalyst.

Further, the 1-naphthol dimethylol compound represented by the above formula (2) can be obtained by reacting 1-naphthol with formaldehyde in the presence of an alkali metal hydroxide. The phenol monomethylol compound represented by the above formula (3) can be obtained by reacting a phenol with formaldehyde in the presence of an alkali metal hydroxide. The compounds of the formulas (2) and (3) are all known compounds.

Examples of the 1-naphthol dimethylol compound of the formula (2) include 2,4-dimethylol-1-naphthol.

The phenols of the formula (P) include phenol, 2,4-xylenol, 2,6-xylenol,
2,3,6-trimethylphenol, 2-t-butyl-
4-methylphenol, 2,4-dichlorophenol,
2,4-dibromophenol, 2,4,5-trichlorophenol, 6-phenyl-2-chlorophenol, o
-Cresol, m-cresol, p-cresol, o-
Ethylphenol, p-ethylphenol, o-phenylphenol, p-phenylphenol, 2,3,5-
Trimethylphenol, pt-butylphenol, o
-Chlorophenol, o-bromophenol, 4-chloro-3,5-xylenol and the like, but are not limited thereto.

The phenol monomethylol compound of the formula (3) includes a methylol group in place of the hydrogen atom at the 2-, 4- or 6-position of the compound exemplified as the phenol of the formula (P). Attached compounds.

When the dehydration condensation reaction is performed, one of the formula (2)
In the reaction between the naphthol dimethylol compound and the phenol of the formula (P), the phenol is preferably used in an amount of 1 to 20 moles, more preferably 2 to 10 moles, based on 1-naphthol dimethylol. Can be used. In the case of the reaction between the phenol monomethylol compound of the formula (3) and 1-naphthol, it is preferably 0.3 to 1 mol times, particularly preferably 0.4 to 0.1 mol times the phenol monomethylol compound. 1- in the range of 6 mole times
Naphthol can be used. In this reaction, two or more phenols or phenol monomethylolates may be used in combination.

Further, acid catalysts for the dehydration condensation reaction include protonic acids such as hydrochloric acid, nitric acid, sulfuric acid, phosphoric acid, paratoluenesulfonic acid, boron trifluoride, boron trifluoride ether complex, zinc chloride and aluminum chloride. Lewis acid, acetic acid, oxalic acid and the like can be used. Of these, hydrochloric acid, paratoluenesulfonic acid, oxalic acid and the like are preferably used, and the amount of the acid catalyst used is preferably 0.001 to 0.1 mol times with respect to 1-naphthol-dimethylolated product or phenolic monomethylolated product. Is selected.
The dehydration / condensation reaction in the presence of the acid catalyst is usually performed in the range of 0 to 12
The reaction is carried out at 0 ° C., preferably 80 ° C. or less. The reaction time is preferably in the range of 1 to 10 hours.
This reaction can be carried out in the presence of a suitable solvent such as water, methanol, toluene, methyl isobutyl ketone and the like.

The reaction solution obtained by the dehydration condensation reaction is repeatedly washed with water in the presence of an excess solvent such as toluene or methyl isobutyl ketone until the inside of the system becomes neutral. By removing the substance and the solvent, a compound represented by the formula (1) or a resin containing the compound in an amount of 30% by weight or more, preferably 35% by weight or more is obtained.

Next, the epoxy compound of the present invention or the epoxy compound is added in an amount of 30% by weight or more, preferably 35% by weight.
The epoxy resin containing the above can be obtained by reacting the compound of the formula (1) or a resin containing the compound in an amount of 30% by weight or more with epihalohydrin. As epihalohydrin, epichlorohydrin, epibromohydrin and the like are used, but epichlorohydrin is industrially preferable because it is easily available. 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, a solid of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a mixture of a compound of the formula (1) or a resin containing 30% by weight or more of the compound and an excess of epihalohydrin, or , While adding 2
The reaction is carried out at a temperature between 0 ° C and 120 ° C. At this time, the alkali metal hydroxide may be used in the form of an aqueous solution.In this case, the aqueous solution of the alkali metal hydroxide is continuously added and the water and the water are continuously reduced under reduced pressure or normal pressure from the reaction system. A method may be employed in which epichlorohydrin is distilled off, liquid is further separated, water is removed, and epichlorohydrin is continuously returned into the reaction system.

In the above method, the amount of epichlorohydrin used is usually 1 to 20 mol, preferably 2 to 10 mol, per 1 equivalent of the hydroxyl group of the compound or resin. The amount of the alkali metal hydroxide to be used is generally 0.8 to 1.5 mol, preferably 0.9 to 1.1 mol, per equivalent of the hydroxyl group of the compound.
Range of moles. Further, in order to make the reaction proceed smoothly, in addition to alcohols such as methanol and ethanol, dimethyl sulfone and dimethyl sulfoxide (hereinafter referred to as DMS)
It is preferable to add an aprotic polar solvent such as O), and this reaction is usually carried out for 1 to 20 hours.

A quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is added as a catalyst to the compound or a mixture of the resin and an excess of epihalohydrin.
A solid or aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to the halohydrin ether obtained by the reaction in
The reaction can be carried out at a temperature between ° C and the ring closure of the halohydrin ether to give an epoxy compound or epoxy resin. In this case, the amount of the quaternary ammonium salt used is preferably 0.001 to 0.2 mol, particularly preferably 0.005 mol per equivalent of the hydroxyl group of the compound of the formula (1) or a resin containing 30% by weight or more. 〜0.1 mol.

Usually, the first-stage reaction product is washed with water or without heating, without heating, under reduced pressure with heating to remove excess epihalohydrin, and then dissolved again in a solvent such as toluene, methyl isobutyl ketone, and sodium hydroxide. An aqueous solution of an alkali metal hydroxide such as potassium hydroxide is added to carry out a second-stage reaction to ensure ring closure. In this case, the amount of the alkali metal hydroxide to be used is preferably 0.01 to 0.2 mol, particularly preferably 0.05 to 0.1 mol, per equivalent of the hydroxyl group.
1 mole. The reaction temperature is preferably from 50 to 120 ° C, and the reaction time is usually from 0.5 to 2 hours.

After the completion of the second-stage reaction, the formed salt is removed by filtration, washing with water, etc., and further, the solvent such as toluene, methyl isobutyl ketone or the like is distilled off under reduced pressure under heating, whereby the hydrolyzed halogen of the present invention is reduced. An epoxy compound or an epoxy resin can be obtained.

Hereinafter, the epoxy resin composition of the present invention will be described. In the epoxy resin composition of the above (6), the compound of the formula (4) or the epoxy resin of the above (5) (hereinafter referred to as the epoxy resin of the present invention) is used alone or in combination with another epoxy resin. can do. When used in combination, the proportion of the epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more.

Other epoxy resins used in combination with the epoxy resin of the present invention include novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, biphenol A novolak type epoxy resin is particularly advantageous in terms of heat resistance. Specific examples include, but are not limited to, cresol novolak epoxy resins, phenol novolak epoxy resins, brominated phenol novolak epoxy resins, and the like. These may be used alone or in combination of two or more.

In the epoxy resin composition of the above (6), the compound of the formula (1) or the resin of the above (2) or (3) (hereinafter referred to as the novolak type resin of the present invention) may be used alone or in another form. It can be used in combination with a curing agent. When used in combination, the proportion of the total curing agent such as the novolak resin of the present invention is preferably 30% by weight or more, and particularly preferably 40% by weight or more.
% By weight or more is preferred.

Other curing agents used in combination with the novolak resin of the present invention include, for example, polyamine curing agents such as aliphatic polyamines, aromatic polyamines and polyamide polyamines, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride. Acid anhydride-based hardeners such as acids, phenol novolaks, phenol-based hardeners such as cresol novolak, Lewis acids such as boron trifluoride or salts thereof, hardeners such as dicyandiamide, and the like, but are not limited thereto. It is not something to be done. These may be used alone or in combination of two or more.

In the epoxy resin composition of the above (6), when the epoxy resin of the present invention is used as the epoxy resin, the other curing agent or the novolak resin of the present invention may be used as the curing agent. it can.

Further, in the epoxy resin composition,
When the novolak resin of the present invention or the like is used as a curing agent, the other epoxy resin described above, the epoxy resin of the present invention, or the like can be used as the epoxy resin.

In the epoxy resin composition of the present invention, the amount of the curing agent used is preferably 0.5 to 1.5 equivalents, more preferably 0.6 to 1.2 equivalents, per equivalent of the epoxy group of the epoxy resin.
Equivalents are preferred.

Examples of the curing accelerator include imidazole compounds such as 2-methylimidazole and 2-ethylimidazole, tertiary amine compounds such as 2- (dimethylaminomethyl) phenol, and triphenylphosphine compounds. Various known hardener accelerators can be used and are not particularly limited. The amount of the curing accelerator used is preferably in the range of 0.01 to 15 parts by weight, particularly preferably in the range of 0.1 to 10 parts by weight, based on 100 parts by weight of the epoxy resin.

The epoxy resin composition of the present invention may further contain known additives as necessary. Examples of the additives include inorganic fillers such as silica, alumina, talc and glass fiber. Examples include filler surface treatment agents such as silane coupling agents, release agents, and pigments.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the components, and is usually from 130 to 170.
Precuring at a temperature of 30 ° C. for 30 to 300 seconds and post-curing at a temperature of 150 to 200 ° C. for 2 to 8 hours allow a sufficient curing reaction to proceed to obtain the cured product of the present invention. Alternatively, the components of the epoxy resin composition can be uniformly dispersed or dissolved in a solvent or the like, and the solvent can be removed and cured.

The cured product thus obtained has excellent performance having both of the characteristics of low water absorption while maintaining heat resistance. Therefore, the compound or resin of the present invention can be used as an epoxy resin or as a curing agent in a wide range of fields requiring heat resistance and low water absorption. Specifically, it is useful as a compounding component of all electric and electronic materials such as an insulating material, a laminate, and a sealing material. Further, it can be used in the fields of molding materials, coating materials, composite materials and the like.

The effect is doubled by using the epoxy resin of the present invention and the novolak resin of the present invention for both the epoxy resin component and the curing agent component. Furthermore, since the resin of the present invention has a low softening point despite having a naphthol ring, conventional techniques such as transfer molding can be used, and workability is good.

[0047]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.
The softening point in the examples is a value according to JIS K2425 (ring and ball method), and the hydrolyzable chlorine is 1N in dioxane.
-Ppm of chlorine, hydroxyl equivalent and epoxy equivalent when decomposed under reflux with KOH to ethanol for 30 minutes are g / eq
Is shown.

Example 1 (1) Synthesis of Methylol Compound In a flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer, 144 parts by weight (1 mol) of 1-naphthol, 20 wt.
210 parts by weight (1.05 mol) of a% -aqueous sodium hydroxide solution were charged and reacted at 50 ° C. for 30 minutes. Next, after cooling the system to 10 ° C., 68 parts by weight (2.1 mol) of granular paraformaldehyde (92% by weight pure) was added at a stretch, and the mixture was reacted at 10 ° C. for 2 hours. After the completion of the reaction, 100 parts by weight of a 38 wt% -hydrochloric acid aqueous solution was added while paying attention to heat generation, and neutralized. The reaction solution was analyzed by the following liquid chromatography to find that 1-naphthol dimethylol was 93% (area%).

Liquid chromatograph: Hitachi L-6000 Column: Gaschrom Industry Inertsil ODS-2 4.6 id * 250 mm, column temperature 50 ° C. Solvent: water-acetonitrile (1: 1) 0.8 ml / min Detector: RI

(2) Synthesis of Dehydration Condensate 432 parts by weight (4 mol) of o-cresol and 150 parts by weight of methanol were charged into the reaction solution, and the temperature of the system was increased to 40 ° C.
Was adjusted to Further, 5 parts by weight of a 38 wt% hydrochloric acid aqueous solution was added and reacted for 2 hours, and then reacted at 70 ° C. for 2 hours.
After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and 600 parts by weight of methyl isobutyl ketone was added. Thereafter, methyl isobutyl ketone and unreacted o-cresol were removed from the oil layer using a rotary evaporator under heating and reduced pressure, and the mixture was pale yellow at room temperature.
376 parts by weight of the solid resin of the present invention (No. 1) was obtained.

The obtained resin has a softening point of 86 ° C. and 150 ° C.
Was 1.5 ps, and the hydroxyl equivalent (g / eq) was 129. In addition, this resin (No.
1) Using tetrahydrofuran (THF) as a solvent,
When analyzed by the following GPC analyzer, the molecular weight distribution curve shown in FIG. 1 was obtained.

GPC apparatus: Shimadzu Corporation Column: GPC KF-803 (1) + GPC KF-802.5 (2) + GPC KF-802 (1) Solvent: Tetrahydrofuran 1 ml / min Detector: RI

Under these analytical conditions, the molecular weight of the compound at the main peak from the calibration curve using standard polystyrene corresponds to the retention time of a trinuclear compound having one naphthol ring and two benzene rings, and is considered to be the trinuclear compound. The peak component was separated and analyzed by mass spectrum (FAB-MS). As a result, M ⁺ 384 was obtained, and thus it was confirmed that this compound was a trinuclear compound represented by the following formula (5).

[0054]

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From the molecular weight distribution curve, it was found that the content of the compound of the formula (5) in the resin (No. 1) was 56% by weight.

Example 2 (1) Synthesis of Methylolated Compound A flask equipped with a thermometer, a dropping funnel, a cooling tube and a stirrer was charged with 144 parts by weight of 1-naphthol (1 mol), 20 wt.
210 parts by weight (1.05 mol) of a% -aqueous sodium hydroxide solution were charged and reacted at 40 ° C. for 30 minutes. Next, after cooling the system to 10 ° C., 68 parts by weight (2.1 mol) of granular paraformaldehyde (92% by weight pure) was added at a stretch, and the mixture was reacted at 10 ° C. for 2 hours. After the completion of the reaction, 100 parts by weight of a 38 wt% -hydrochloric acid aqueous solution was added while paying attention to heat generation, and neutralized.

(2) Synthesis of Dehydration Condensate 488 parts by weight (4 mol) of 2,6-xylenol and 200 parts by weight of methanol were charged into the reaction solution, and the temperature of the system was reduced to 40 ° C.
Was adjusted to Further, 5 parts by weight of a 38 wt% -hydrochloric acid aqueous solution was added and reacted for 2 hours, and then reacted at 70 ° C. for 2 hours. After completion of the reaction, the reaction mixture was transferred to a separating funnel, and 600 parts by weight of methyl isobutyl ketone was added. Then
The washing was repeatedly returned to neutral. Thereafter, methyl isobutyl ketone and unreacted 2,6-xylenol were removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 400 parts by weight of a pale yellow solid resin of the present invention (No. 2) at room temperature.

The obtained resin has a softening point of 89 ° C. and 150 ° C.
Was 1.8 ps, and the hydroxyl equivalent (g / eq) was 138. This resin (No. 2)
Was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1) to obtain a molecular weight distribution curve shown in FIG. Also, M ⁺ 4 was analyzed by 3 Shi preparative peak component appears nucleus min Mass spectrum (FAB-MS)
By obtaining 12, it was confirmed that this compound was a trinuclear body represented by the following formula (6).

[0059]

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From the molecular weight distribution curve, it was found that the content of the compound of the formula (6) in the resin (No. 2) was 51% by weight.

Example 3 (1) Synthesis of Methylol Compound 144 parts by weight (1.0 mol) of 1-naphthol was added to a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer.
0 wt% -210 parts by weight of aqueous sodium hydroxide solution (1.05%
Mol) was reacted at 40 ° C. for 30 minutes. Then
After cooling the system to 10 ° C., 68 parts by weight (2.1 mol) of granular paraformaldehyde (92% by weight pure) were added at once, and the reaction was carried out at 10 ° C. for 2 hours. After the completion of the reaction, 100 parts by weight of a 38 wt% -hydrochloric acid aqueous solution was added while paying attention to heat generation, and neutralized.

(2) Synthesis of Dehydration Condensate 2,3,6-Trimethylphenol was added to this reaction
4 parts by weight (4 mol) and 300 parts by weight of methyl isobutyl ketone were charged, and the temperature in the system was adjusted to 40 ° C. 38 wt% -hydrochloric acid aqueous solution (3 parts by weight) was added and reacted for 2 hours.
The reaction was carried out at 2 ° C. for 2 hours. After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and 500 parts by weight of methyl isobutyl ketone was added. Then, washing was repeated several times to return to neutral.
Then, methyl isobutyl ketone and unreacted 2,3,6 were removed from the oil layer under heating and reduced pressure using a rotary evaporator.
-The trimethylphenol was removed to obtain 420 parts by weight of a resin (No. 3) of the present invention as a pale yellow solid at room temperature.

The softening point of the obtained resin was 107 ° C. and 150 ° C.
The ICI viscosity at ℃ was 6.4 ps, and the hydroxyl equivalent (g / eq) was 147. This resin (No. 3)
Was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1) to obtain a molecular weight distribution curve shown in FIG. Also, M ⁺ 4 was analyzed by 3 Shi preparative peak component appears nucleus min Mass spectrum (FAB-MS)
By obtaining 40, it was confirmed that this compound was a trinuclear body represented by the following formula (7).

[0064]

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From the molecular weight distribution curve, it was found that the content of the compound of the formula (7) in the resin (No. 3) was 53% by weight.

Example 4 (1) Synthesis of Methylolated Compound A flask equipped with a thermometer, a dropping funnel, a condenser and a stirrer was charged with 244 parts by weight of 2,4-xylenol (2 mol),
A 40 wt% aqueous solution of sodium hydroxide (100 parts by weight (1 mol)) was charged and the system was heated to 40 ° C. and reacted for 30 minutes. Next, granular paraformaldehyde (92% pure) 6
8 parts by weight were added and reacted at 50 ° C. for 1 hour and then at 60 ° C. for 3 hours. After the completion of the reaction, the system was cooled to 10 ° C.
96 parts by weight of an 8 wt% -hydrochloric acid aqueous solution was neutralized by dropping while paying attention to heat generation.

(2) Synthesis of Dehydration Condensate Next, 400 parts by weight of methyl isobutyl ketone and 144 parts by weight (1 mol) of 1-naphthol were charged into this reaction solution, and the system was adjusted to 60 ° C. 10 parts by weight of methyl isobutyl ketone in which 2 parts by weight of an acid was dissolved was added, and reacted for 2 hours, and further reacted at 75 ° C. for 1 hour. After the completion of the reaction, the reaction mixture was transferred to a separating funnel, and 200 parts by weight of methyl isobutyl ketone was added. Next, washing with water was repeated several times to return to neutral. Thereafter, methyl isobutyl ketone and unreacted substances were removed from the oil layer using a rotary evaporator under heating and reduced pressure to obtain 386 parts by weight of a pale yellow, solid resin (No. 4) of the present invention at room temperature.

The softening point of the obtained resin was 84.5 ° C., 15
The ICI viscosity at 0 ° C. was 0.8 ps, and the hydroxyl equivalent (g / eq) was 138. This resin (No.
4) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and the molecular weight distribution curve shown in FIG. 4 was obtained. Further, peak components considered to be trinuclear were fractionated and analyzed by mass spectrum (FAB-MS).
^{By +} 412 is obtained, this compound was confirmed to be 3 nuclei expressed in the following equation (8).

[0069]

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From the molecular weight distribution curve, it was found that the content of the compound of the formula (8) in the resin (No. 4) was 58% by weight.

Example 5 To 129 parts by weight of the resin (No. 1) obtained in Example 1, 555 parts by weight (6 moles) of epichlorohydrin and 280 parts by weight of DMSO were added and dissolved. Then, 42 parts by weight (1.04 mol) of sodium (99% pure) was added over 100 minutes, and the mixture was further reacted at 60 ° C. for 2 hours and at 70 ° C. for 1 hour. After completion of the reaction, washing with water was repeated, the aqueous layer was separated and removed, 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 to the residue to dissolve the residue.

Further, the solution of methyl isobutyl ketone was heated to 70 ° C., and 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution was added. The mixture was reacted for 1 hour, and then washed repeatedly with water 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 obtain 176 parts by weight of the epoxy resin (No. 5) of the present invention.

The obtained epoxy resin has a softening point of 57.5.
° C, the ICI viscosity at 150 ° C is 1.0 ps,
Epoxy equivalent is 190, hydrolyzable chlorine is 310 ppm
Met. This epoxy resin (No. 5) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and a molecular weight distribution curve shown in FIG. 5 was obtained. 3
A peak component considered to be a nucleus is collected and mass spectrum (F
(AB-MS), M ⁺ 552 was obtained. Thus, it was confirmed that this compound was a trinuclear compound represented by the following formula (9).

[0074]

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From the molecular weight distribution curve, it was found that the content of the compound of the formula (9) in the epoxy resin (No. 5) was 50% by weight.

Example 6 An epoxidation reaction was carried out in the same manner as in Example 5 except that 138 parts by weight of the resin (No. 2) obtained in Example 2 was used, and 176 parts by weight of the epoxy resin (No. 6) of the present invention was obtained. Got a part.
The obtained epoxy resin had a softening point of 60.5 ° C., an ICI viscosity of 1.4 ps, an epoxy equivalent of 199, and a hydrolyzable chlorine of 285 ppm. This epoxy resin (No. 6) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and the molecular weight distribution curve shown in FIG. 6 was obtained. Further, a peak component considered to be a trinuclear compound was collected and analyzed by mass spectrum (FAB-MS) to obtain M ⁺ 580. Therefore, this compound was a trinuclear compound represented by the following formula (10). Was confirmed.

[0077]

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From the molecular weight distribution curve, it was found that the content of the compound of the formula (10) in the epoxy resin (No. 6) was 42% by weight.

Example 7 An epoxidation reaction was carried out in the same manner as in Example 5 except that 147 parts by weight of the resin (No. 3) obtained in Example 3 was used, and 183 parts by weight of the epoxy resin (No. 7) of the present invention was obtained. Got a part. The obtained epoxy resin had a softening point of 78 ° C., an ICI viscosity of 4.1 ps, an epoxy equivalent of 207, and hydrolysable chlorine of 340 ppm. This epoxy resin (N
o. 7) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and the molecular weight distribution curve shown in FIG. 7 was obtained. Further, a peak component thought to be a trinuclear compound was collected and analyzed by mass spectrum (FAB-MS) to obtain M ⁺ 608. Thus, the compound was a trinuclear compound represented by the following formula (11). Was confirmed.

[0080]

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From the molecular weight distribution curve, it was found that the content of the compound of the formula (11) in the epoxy resin (No. 7) was 46% by weight.

Example 8 An epoxidation reaction was carried out in the same manner as in Example 5, except that 138 parts by weight of the resin (No. 4) obtained in Example 4 was used.
176 parts by weight of the epoxy resin of the present invention (No. 8) was obtained. The obtained epoxy resin had a softening point of 57 ° C., an ICI viscosity of 0.9 ps, an epoxy equivalent of 204, and hydrolyzable chlorine of 315 ppm. This epoxy resin (No. 8) was analyzed by liquid chromatography (GPC, analysis conditions were the same as in Example 1), and a molecular weight distribution curve shown in FIG. 8 was obtained. Further, a peak component thought to be a trinuclear compound was collected and analyzed by mass spectrum (FAB-MS) to obtain M ⁺ 580. Thus, the compound was a trinuclear compound represented by the following formula (12). Was confirmed.

[0083]

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From the molecular weight distribution curve, it was found that the content of the compound of the formula (12) in the epoxy resin (No. 8) was 48% by weight.

Test Examples 1 to 8 and Comparative Examples 1 and 2 The resins obtained in Examples 1 to 4 were used. As Comparative Example 1, a bisphenol A resin (having a hydroxyl equivalent of 11
6, an ICI viscosity at 150 ° C. of 0.1 ps) and an epoxy resin (o-cresol novolac type epoxy resin, EOCN)
-1020 (manufactured by Nippon Kayaku Co., Ltd.), epoxy equivalent 20
0, an ICI viscosity at 150 ° C. of 3.2 ps) and a curing accelerator (triphenylphosphine) were blended in the amounts shown in Table 2, and a resin molded article was prepared by transfer molding and cured under the curing conditions shown in Table 2. .

Further, the epoxy resin obtained in the above Examples 5 to 8 was used, and a bisphenol A type epoxy resin (epoxy equivalent: 189, ICI viscosity at 150 ° C. 0.1 ps or less) was used as Comparative Example 2. A curing agent (phenol novolak type resin, PN-80 (manufactured by Nippon Kayaku Co., Ltd.), hydroxyl equivalent 106 g / eq, ICI viscosity at 150 ° C. 1.5 ps) with 150 parts by weight of these epoxy resins, and a curing accelerator (Triphenylphosphine) was blended in the amounts shown in Table 3, and a resin molded product was prepared by transfer molding and cured under the curing conditions shown in Table 3.

Tables 2 and 3 show the results of measuring the heat distortion temperature and the water absorption of the cured product thus obtained. The measurement conditions of the heat distortion temperature and the water absorption are as follows.

Heat deformation temperature Condition specified in JIS K7207 Water absorption Test piece Diameter 50 mm (cured product) Thickness 3 mm Disk Condition Weight increase after boiling in water at 100 ° C. for 24 hours (% by weight)

Table 2 Test Example 1 2 3 4 Comparative Example 1 Resin No. 1 No. 2 No. 3 No. 4 Hydroxyl equivalent g / eq 129 138 147 138 138 116 Epoxy resin wt part 155 145 136 145 173 Curing accelerator wt Part 1.6 1.5 1.4 1.5 1.7 Curing conditions 160 ° C * 2 hours + 180 ° C * 8 hours Heat deformation temperature ℃ 150 168 170 140 120 Water absorption wt% 1.1 1.3 1.2 1.0 1.5

Table 3 Test Example 5 6 7 8 Comparative Example 2 Epoxy resin No. 5 No. 6 No. 7 No. 8 Epoxy equivalent g / eq 190 199 207 207 204 189 Curing agent wt part 84 80 77 78 84 Curing accelerator wt part 1.5 1.5 1.5 1.5 1.5 Curing conditions 160 ° C * 2 hours + 180 ° C * 8 hours Heat deformation temperature ° C 161 171 175 149 125 Water absorption wt% 1.2 1.3 1.1 1.1 1.4

[0091]

When the compound, resin or epoxy resin of the present invention is used as a raw material for a cured epoxy resin, the cured product can have excellent heat resistance and moisture resistance, and can be hydrolyzed with chlorine. Since the amount is extremely small, it can be provided as a highly reliable semiconductor sealing resin.

[Brief description of the drawings]

FIG. 1 is a molecular weight distribution curve of a resin (No. 1) obtained in Example 1.

FIG. 2 is a molecular weight distribution curve of a resin (No. 2) obtained in Example 2.

FIG. 3 is a molecular weight distribution curve of a resin (No. 3) obtained in Example 3.

FIG. 4 is a molecular weight distribution curve of a resin (No. 4) obtained in Example 4.

FIG. 5 is an epoxy resin obtained in Example 5 (No. 5).
Molecular weight distribution curve of

FIG. 6 is an epoxy resin obtained in Example 6 (No. 6).
Molecular weight distribution curve of

FIG. 7: Epoxy resin obtained in Example 7 (No. 7)
Molecular weight distribution curve of

FIG. 8: Epoxy resin obtained in Example 8 (No. 8)
Molecular weight distribution curve of

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁶ Identification code FI C08G 59/06 C08G 59/06 59/32 59/32 59/62 59/62 61/12 61/12 H01L 23/29 H01L 23 / 30 R 23/31 (56) References JP-A-3-50223 (JP, A) JP-A-4-279627 (JP, A) (58) Fields investigated (Int. Cl. ⁶ , DB name) C07C 39/12 C07D 303/28 C08G 8/00 C08G 59/00 C08G 61/12 CA (STN) REGISTRY (STN)

Claims (7)

(57) [Claims] (1) Formula (1) (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ′ ₁ , R ′ ₂ , R
_'3, respectively is _R'4 independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, having 1 to 4 carbon atoms. ). (2) Formula (2) 1-naphthol dimethylol compound represented by the formula and a compound represented by the formula (P): (In the formula, R ₁ , R ₂ , R ₃ and R ₄ each independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group having 1 to 4 carbon atoms.) Obtained by reacting two or more kinds in the presence of an acid catalyst,
A resin comprising the compound of claim 1 in an amount of 30% by weight or more. (3) Formula (3) (Wherein 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). A resin obtained by reacting one or two or more kinds of compounds with 1-naphthol in the presence of an acid catalyst and containing at least 30% by weight of the compound of claim 1. (4) Formula (4) (Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ′ ₁ , R ′ ₂ , R
_'3, respectively is _R'4 independently represent a hydrogen atom, a halogen atom, an alkyl group or an aryl group, having 1 to 4 carbon atoms. An epoxy compound represented by). 5. The compound of claim 1 or the resin of claim 2 or 3 is a compound of formula (E) (Wherein Y represents a halogen atom), and obtained by reacting the compound of claim 4 with an epihalohydrin represented by the following formula:
Epoxy resin containing more than weight%. 6. An epoxy resin composition containing an epoxy resin, a curing agent and a curing accelerator, wherein (A) the compound of claim 4 or the resin of claim 5 is used as the epoxy resin, and / or (B) curing. An epoxy resin composition using the compound according to claim 1 or the resin according to claim 2 or 3 as an agent. 7. A cured product of the epoxy resin composition according to claim 6.