JPH03220219A - Phenol novolac compound, resin, resin composition, and cured product - Google Patents

Abstract

PURPOSE:To obtain a phenol novolac compound having a specified structure and giving a cured product with improved heat resistance, reduced water absorption and excellent workability. CONSTITUTION:A compound (A) of formula I (wherein R1 to R3 are each H, 1-4C alkyl, aryl or halogen), e.g. dimethylolated 4-methylphenol, is reacted with 2-15mol, per mol of component A, of a naphthol (B) of formula II (wherein R4 to R9 are each R1), e.g. 1-naphthol, at 20-150 deg.C in the presence of 0.1-30wt.%, based on component A, acid catalyst (C) optionally in a solvent, and component C is removed by, e.g. washing with water. The solvent and excess component B are distilled off in a vacuum, and the product is optionally reacted with an epihalohydrin compound (D) of formula III (wherein X is halogen) in the presence of a basic compound to obtain a phenol novolac epoxy resin containing a compound of formula IV (wherein X is H or a group of formula V).

Description

DETAILED DESCRIPTION OF THE INVENTION [Field of Industrial Application] The present invention relates to compounds, resins, resin compositions, and cured products thereof that are particularly useful as materials for sealing or laminating electronic components.

[Conventional technology] Epoxy resins generally have good adhesive properties, chemical resistance, electrical properties,
Due to its excellent mechanical properties and heat resistance, it is widely used in adhesives, paints, electrical insulation materials, etc. In particular, in the field of electrical and electronic components, conventional epoxy resins are often used as electrical insulating materials. Resin compositions containing epoxy resins and phenol novolac resins as main components are used as sealants for ICs, and cresol novolac epoxy resins are often used as epoxy resins, as they produce cured products with excellent heat resistance. .

[Problems to be Solved by the Invention] The high density and high integration of ICs accompanying the recent development of electronic materials has required particularly higher heat resistance and lower water absorption for sealants. In particular, the harsh conditions of immersion in a solder bath during high-density mounting require high heat resistance and
Demand for lower water absorption rates is increasing. but,
In conventional compositions, when a cresol novolak type epoxy resin, which is commonly used as an epoxy resin, is used, a cured product that has heat resistance and can withstand harsh conditions such as immersion in a solder bath without any problem has not been obtained. Furthermore, a polyphenol prepared by epoxidizing a polyphenol obtained by condensing an aromatic aldehyde having a phenolic hydroxyl group with phenols described in JP-A No. 63-264622 has been proposed to provide a cured product having heat resistance. When it comes to epoxy compounds, the cured products thereof are not as good as the cured products of cresol novolac type epoxy resins in terms of water absorption. Furthermore, JP-A No. 62-20206 proposes a polyglycidyl ether of a condensate of l-naphthol and formaldehyde, which improves the heat resistance of the cured product, but increases the softening point. Alternatively, the melt viscosity increases, which impairs workability.

On the other hand, the phenol novolak resins commonly used as curing agents still have insufficient heat resistance, and although attempts have been made to reduce the amount of low molecular weight substances (binuclear phenol novolacs), Under increasing conditions (e.g. solder bath immersion), satisfactory results have not been achieved. Therefore, there is a need for the development of a resin that provides a cured product with heat resistance and low water absorption, and also has better workability.

[Means for Solving the Problems] As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found that heat resistance and low water absorption of cured products can be achieved by using a compound with a specific structure into which a naphthol ring is introduced. The present invention was completed after discovering that it is possible to simultaneously achieve efficiency reduction and to have good workability.

That is, the present invention provides: (1) Formula (I) R1, R-, , Rs, R'1, R-7, R'8, R'
, each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom) Formula (I[) (4) R,! The compound according to (3) above, wherein is a methyl group and R14 is a hydrogen atom.

(5) Formula (IV) ■1@ (In the formula, R1゜, RII, R52, R'11, R', 2
each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms,
phenyl group or halogen atom).

(3) Formula (III) (wherein, R3゜, R11, I'2+z, R', 1, R'
1. each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom).

(6) Formula (V) Js (wherein, R+s represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom, and R1 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.) compound.

(In the formula, R+s represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom, and R14 represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.)

The compound according to (6) above, wherein R+3 is a methyl group and R1 is a hydrogen atom.

A novolak-type resin comprising the compound described in (1) above.

A phenolic novolac type resin comprising the compound described in (2), (3) or (4) above.

(lO) A phenolic novolac type epoxy resin comprising the compound described in (5), (6) or (7) above.

(11) The resin according to (8), (9) or αω, wherein the content of the compound is 30% by weight or more.

(12) (a) Formula [VI) as epoxy resin (
In the formula, R1, R1, R1, R1, R5, R6, R7, R
,,R,,R-,,R'5,R-,,R″7,R-,
, R- each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom. An epoxy resin composition comprising a phenolic novolac type epoxy resin containing a compound represented by (b) a curing agent.

The epoxy resin composition according to α2 above, wherein the phenolic novolac type epoxy resin is the resin described above αω.

(+4) (Al epoxy resin and fb) Formula as curing agent [ (wherein, R1, R2, R2, R1, R5, R6, R7,
R,,R,,R-,,R-,,R-,,R7,R'8,
An epoxy resin composition comprising a phenolic novolak type resin containing a compound represented by R-, each independently representing a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom. .

(15) The phenolic novolac type fat is the above (9
) The epoxy resin composition described in α4 above, which is the resin described in ).

(16) (a) An epoxy resin composition comprising the phenolic novolak type epoxy resin described in the above uz as an epoxy resin and the phenolic novolac type resin described in the above I as a bl curing agent.

(17) The epoxy resin composition according to the above αω, wherein the phenolic novolak type epoxy resin is the resin described in the above description, and the phenolic novolac type resin is the resin described in the above (9).

(18) The above α2, α3. Q41, α
9. The epoxy resin composition described in ae or αη.

(19) Compound represented by formula [■] 1”IF5 R3 (wherein R1, R7, and R2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom) Corresponding ones of formula [IX] OH (wherein R4, R6, R6, R7, R,, R1 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen The above (8) obtained by reacting with the corresponding naphthols represented by
, (9) or the resin described in αυ.

(20) The above Q4, αS, αe, surface or 0 g epoxy resin composition, wherein the phenolic novolac type resin is the resin obtained in the above α9.

(21) The resin described in (8) above, aIll or aυ, which is obtained by further reacting the resin obtained in the above process with an shrimp halohydrin compound.

(22) The above α, aa, α which is a phenolic novolak type epoxy resin or a resin obtained in the above (21)
Epoxy resin composition of G, 0η or 08.

(23) 0ri, aa, I, α9, ae, tt'n,
A cured product of the epoxy resin composition of aa, w or (22).

It is related to.

The present invention will be explained in detail below.

In the compound of the present invention, examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-brobyl group, isopropyl group, n-butyl group, isobutyl group, S-butyl group, and t-butyl group. Among them, methyl group and t-butyl group are particularly preferred. As the aryl group, phenyl group, 4-
Examples include methylphenyl group and 2-methylphenyl group, with phenyl group being particularly preferred. Examples of the halogen atom include a chlorine atom, a fluorine atom, a bromine atom, an iodine atom, and the like, with a chlorine atom being particularly preferred.

Among the compounds of the present invention and resins containing the same, particularly preferred are compounds represented by formula [II] or formula [V] and resins containing the same.

The compound of the present invention and the resin containing the same can be produced as follows.

That is, it can be produced by dehydrating and condensing a compound represented by formula [■] and a naphthol represented by formula (IX) in the presence of an acid catalyst.

The dimethylol compound represented by the formula [■] is 2-
Methylphenol dimethylol compound, 4-methylphenol dimethylol compound, 2,3-dimethylphenol dimethylol compound, 2,5-dimethylphenol dimethylol compound, 3,4-dimethylphenol dimethylol compound, 2.3.5- Trimethylphenol dimethylol compound, 4-ethylphenol dimethylol compound, 4-n-propylphenol dimethylol compound, 4-i-propylphenol dimethylol compound, 4
-n-butylphenol dimethylol compound, 4-s-
Butylphenol dimethylol compound, 1- to 3-substituted alkylphenol dimethylol compound such as 4-t-butylphenol dimethylol compound, 2-phenylphenol dimethylol compound, 4-phenylphenol dimethylol compound, or 4-fluorophenol dimethylol compounds, halogen-substituted phenol dimethylol compounds such as 4-chlorophenol dimethylol compounds, 4-bromophenol dimethylol compounds, and 2-chloro-3-methylphenol dimethylol compounds, but are limited to these. isn't it.

Moreover, as the naphthols represented by formula (IX),!
-naphthol, 2-naphthol, 1-methyl-2-naphthol, 2-methyl-1-naphthol, etc., and substituents may be introduced at positions 5, 6, 7, and 8 of the naphthol ring.

Among the above, the dimethylol compound is a dimethylol compound of a phenol substituted at the 4-position represented by the formula [X) H (wherein R represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom). preferable. In particular, 4-methylphenol dimethylol compounds are most preferred. Also,
As the naphthols, l-naphthol and 2-methyl-■-naphthol are particularly preferred.

As the acid catalyst, hydrochloric acid, sulfuric acid, phosphoric acid, P-toluenesulfonic acid, oxalic acid, etc. can be used, and it is preferable to use the acid catalyst in an amount of 0.1 to 30% by weight of the compound represented by formula [■]. . Moreover, it is preferable to use naphthols in an amount of 2 to 15 times the mole of the compound represented by formula [■]. The reaction can be carried out without a solvent or in a solvent such as benzene, toluene, methyl isobutyl ketone, or the like. The reaction temperature is 20~
A range of 150°C is preferred. After the reaction is completed, the used catalyst is removed by washing with water, etc., and the solvent and excess naphthol are distilled off under reduced pressure to obtain the desired phenolic novolak type compound represented by formula [■] (in formula [1]). X
is H).

The phenolic novolac type resin obtained in this way preferably contains 30% by weight or more, particularly 35% by weight or more of the compound represented by formula [■] (in formula [I], X represents H). It is preferable to include.

Next, the phenolic novolac type compound represented by the formula [■] obtained in this way or the phenolic novolac type resin containing the compound is added with the formula [XI] (wherein, X represents a halogen atom). By reacting the shrimp halohydrin compound represented by the formula in the presence of a basic compound, a compound represented by the formula [VI] (in the formula [I], X is a borac type eboxo resin) can be easily obtained.

In the formula (X I ), examples of the halogen atom represented by X include Cf, Br, ■, etc., and the formula [X I ]
Specifically, the compounds include epichlorohydrin,
Examples include shrimp bromohydrin and shrimp iodohydrin, and mixtures thereof can also be used, but epichlorohydrin is preferably used industrially.

The reaction between the compound represented by the formula [■] or the phenolic novolac type resin containing this compound and the shrimp halohydrin compound can be carried out by a known method.

For example, a compound represented by the formula [■] or a phenolic novolac type resin containing the same, and an excess molar amount of the shrimp halohydrin compound relative to the hydroxyl equivalent thereof, are combined with tetramethylammonium chloride, tetramethylammonium bromide, triethylammonium The reaction is carried out in the presence of a quaternary ammonium salt such as chloride or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. If a quaternary ammonium salt is used, the ring-opening addition reaction step Since the reaction stops, the above alkali metal hydroxide is then added to cause a ring-closing reaction.

In addition, when reacting by adding an alkali metal hydroxide from the beginning, the ring-opening addition reaction and the ring-closing reaction are performed at once.

The proportion of the shrimp halohydrin compound to be used is generally 1 to 50 moles, preferably 3 to 15 moles, per 1 of the hydroxyl equivalent of the compound represented by formula [■] or the phenolic novolak type resin containing the same.

In addition, in order to facilitate the reaction, alcohols such as methanol, or aprotic polar solvents such as acetone, dimethyl sulfoxide, dimethyl sulfone, and dimethyl formamide can be used. In particular, dimethyl sulfoxide is not recommended. preferable.

The amount of alkali metal hydroxide used is usually 0.8 to 1.5 mol, preferably 0.9 mol per hydroxyl equivalent of the compound represented by formula [■] or the phenolic novolac type resin containing the same. ~1.3 mol, and when a quaternary ammonium salt is used, the amount used is usually within the range of 1 mol of hydroxyl group of the compound represented by formula [■] or the phenolic novolak type resin containing it. o, o o t -t mol, preferably in the range of 0.005 to 0.5 mol.

The reaction temperature is usually 30-130°C, preferably 40-120°C.
It is 0°C.

Furthermore, the reaction can be allowed to proceed while removing water produced in the reaction from the reaction system.

After completion of the reaction, by-produced salts are removed by water washing, filtration, etc., and excess epihalohydrin compound is distilled off, thereby obtaining a phenolic novolac type epoxy resin containing the compound represented by formula [VI].

The phenolic novolac type epoxy resin thus obtained has a compound represented by the formula [VI]) of 30! It is preferable that the content is at least 35% by weight, particularly preferably at least 35% by weight.

The epoxy resin composition of the present invention will be explained below.

In the epoxy resin composition of αL (13, αG, α force, α mark, (22)), the phenolic novolac type epoxy resin of the present invention can be used alone or in combination with other epoxy resins. When used together, the proportion of the phenolic novolac type epoxy resin of the present invention in the total epoxy resin is preferably 30% by weight or more, particularly preferably 50% by weight or more.

Other epoxy resins used in combination with the phenolic novolak epoxy resin of the present invention include bisphenol A epoxy resin, bisphenol F epoxy resin, bisphenol S epoxy resin, ring type epoxy resin, biphenyl type epoxy resin, etc. However, novolac type epoxy resin is particularly advantageous in terms of heat resistance.

Examples include, but are not limited to, cresol novolac type epoxy resins, phenol novolac type epoxy resins, and brominated phenol novolac type epoxy resins.

These may be used alone or in combination of two or more.

In the epoxy resin compositions α4, α9, αe, a7), aε, and (a), the phenolic novolac type resin of the present invention can be used alone or in combination with other curing agents. When used together, the proportion of the phenolic novolac type resin of the present invention in the total curing agent is preferably 30% by weight or more, particularly preferably 50% by weight or more.

Other curing agents used in combination with the phenolic novolak type resin of the present invention include, for example, polyamine curing agents such as aliphatic polyamines, aromatic polyamines, polyamide polyamines, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, etc. Examples include, but are not limited to, acid anhydride curing agents, phenol curing agents such as phenol novolak and cresol novolak, Lewis acids such as boron trifluoride or their salts, and curing agents such as ciscyandiami F. It's not something you can do. These may be used alone or in combination of two or more.

In the epoxy resin composition of -, α9, a8, (2), examples of the (al epoxy resin) include the phenolic novolac type epoxy resin of the present invention as well as the other epoxy resins mentioned above.

In the epoxy resin composition having α-ri, a3.0 step, (22), examples of the tb+ curing agent include the above-mentioned other curing agents in addition to the phenolic novolac type resin of the present invention.

In the epoxy resin composition of the present invention, the amount of the curing agent (b) used is preferably 0.5 to 1.5 equivalents, particularly 0.6 to 1.2 equivalents per equivalent of epoxy groups in the (al epoxy resin).
Equivalent amounts 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 phosphine compounds such as triphenylphosphine. Various curing accelerators can be used, and there are no particular limitations. The amount of the curing accelerator used is preferably in the range of 0.01-15 parts by weight, particularly preferably in the range of 0.1-10 parts by weight, per 100 parts by weight of the epoxy resin (al).

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

The epoxy resin composition of the present invention is obtained by uniformly mixing each component.

The epoxy resin composition of the present invention is usually precured at a temperature of 130 to 170°C for 30 to 300 seconds, and further cured for 150 to 150 seconds.
By post-curing at a temperature of 0 to 200°C for 2 to 8 hours, a sufficient curing reaction proceeds, and the cured product of the present invention can be obtained.

The cured product thus obtained has low water absorption while maintaining heat resistance.

In this way, the compound of formula [■] of the present invention or the phenolic novolac type resin containing the same and/or the compound of formula [VI
] The cured product obtained using the compound or the phenolic novolac type epoxy resin containing the same has excellent performance that combines the two characteristics of high heat resistance and low water absorption.

Therefore, the above compound or resin of the present invention can be used as an epoxy resin in a wide range of fields where heat resistance and low water absorption are required.
Alternatively, it can be used as a curing agent. Specifically, it is used as a compounding component of all electrical and electronic materials such as insulating materials, laminates, and sealing materials. Furthermore, it can be used in fields such as molding materials and composite materials. By using the phenolic novolac type epoxy resin and phenolic novolac type resin of the present invention for both the epoxy resin component and the curing agent component, the effect is doubled. Further, since the resin of the present invention has a low softening point despite having a naphthol ring, conventional methods such as transfer molding can be used.

[Example] The present invention will be explained below with reference to Examples.

Example 1 162 g (1.5 moles) of 4-methylphenol, 90 g (3 moles) of paraformaldehyde, and 100 g of water were charged into 12 flasks equipped with a thermometer, condenser, dropping funnel, and stirrer, and nitrogen was blown into the flasks. I stirred it because it was a bit crowded.

At room temperature, 120 g of a 15% aqueous sodium hydroxide solution (0.45 mol as sodium hydroxide) was slowly added dropwise while being careful not to generate heat so that the liquid temperature did not exceed 50°C.

Thereafter, the mixture was heated to 50°C in a water bath and reacted for 10 hours. At the end of the reaction, add 300ml of water, cool to room temperature, and neutralize with a 10% aqueous hydrochloric acid solution while paying attention to heat generation.
The precipitated crystals were collected by filtration. The filtrate was washed until the pH was 6 to 7, dried under reduced pressure (10 mHg) at 50''C, and white crystals of 4-methylphenol dimethylol compound (A
M) (Compound where R is a methyl group in formula [X]) 202
I got g.

168 g of the thus obtained white crystalline 4-methylphenol dimethylol compound (AM) was charged into a glass container equipped with a thermometer and a stirrer, and 100 g of l-naphthol was added.
8 g and 1,500 g of methyl isobutiketone were added, and the mixture was stirred at room temperature under a nitrogen atmosphere. Then, 1.7 g of p-toluenesulfonic acid was gradually added, being careful not to generate heat, so that the liquid temperature did not exceed 50°C.

After the addition, the mixture was heated to 50°C on an oil bath and reacted for 2 hours, then transferred to a separatory funnel and washed with water. After washing with water until the washing water shows neutrality, the solvent and unreacted substances are removed from the organic layer under reduced pressure to obtain the phenolic novolac type resin (A-1) of the present invention.
370g was obtained. Softening temperature (JIS
K2425 ring and ball method) is the hydroxyl equivalent (g/m
o 1! ) was 138.

Example 2 The product (A-2
) 368g was obtained. The softening temperature of product (A-2) is 11
The hydroxyl equivalent was 137 at 7°C.

Example 3 The product (A-3
) 365g was obtained. The softening temperature of product (A-3) is 11
The hydroxyl equivalent was 137 at 8°C.

Example 4 371 g of product (A-4) was obtained in the same manner as in Example 1 except that 1008 g of 2-naphthol was used instead of 1008 g of l-naphthol. The product (A-4> had a softening temperature of 113°C and a hydroxyl equivalent of 138.

Example 5 222 g (1.5 moles) of 4-t-butylphenol, 90 g (3 moles) of paraformaldehyde, and 100 g of water were placed in a liter equipped with a thermometer, cooling tube, dropping funnel, and stirrer.
I! The mixture was poured into a flask and stirred after blowing in nitrogen. At room temperature, 120 g of 15% sodium hydroxide aqueous solution (
0.45 mol (as sodium hydroxide) was slowly added dropwise to the solution while being careful not to generate heat so that the liquid temperature did not exceed 50°C. Thereafter, the reaction was carried out in a water bath at 50°C for 10 hours. After the reaction was completed, 300 g of water was added, the mixture was cooled to room temperature, and neutralized with a 10% aqueous hydrochloric acid solution while being careful not to generate heat. 5001R1 of chloroform was added to separate the oil layer, washed with a water-methanol solution (water:methanol=80/20 (wt%)), and dried by adding anhydrous sodium sulfate. Subsequently, chloroform was removed under reduced pressure, and 4-t-butylphenol dimethylol compound (
AB) Compound 25 in which R is a t-butyl group in formula [X]
6g (purity 82%) was obtained. The 4-t thus obtained
-Butylphenol dimethylol compound (AB) 254
g was placed in a glass container equipped with a thermometer and a stirrer, and 576 g of 1-naphthol and 1500 rd of methyl isobutyl ketone were added thereto, followed by stirring at room temperature under a nitrogen atmosphere. And p-1 luenesulfonic acid! , 7 g was added gradually, being careful not to generate heat, so that the liquid temperature did not exceed 50°C.

After the addition, the mixture was reacted for 2 hours at 50°C in a hot water bath, and then transferred to a separatory funnel and washed with water. After washing with water until the washing water becomes neutral, the solvent and unreacted substances were removed from the growing layer under reduced pressure, and 414 g of the phenolic novolac type resin (A-5) of the present invention was obtained.
I got it. Softening temperature of product (A-5) (JIS K2
425 ring and ball formula> is the hydroxyl group equivalent (g/mof) at 121°C
was 151.

Example 6゜In Example 5! -420 g of product (A-6) was obtained in the same manner as in Example 5, except that 576 g of 2-naphthol was used instead of naphthol. Product (A-
The softening temperature of 6) was 126°C and the hydroxyl equivalent was 152.

Example 7 193 g (1.5 moles) of 4-chlorophenol, 90 g (3 moles) of paraformaldehyde, and 100 g of water were charged into 11 flasks equipped with a thermometer, condenser, dropping funnel, and stirrer, and nitrogen was blown into the flask. while stirring. At room temperature, 120 g of a 15% aqueous sodium hydroxide solution (0.45 mol as sodium hydroxide) was slowly added dropwise, being careful not to generate heat, so that the liquid temperature did not exceed 50°C. Thereafter, the reaction was carried out in a water bath at 50° C. for 10 hours. After the reaction was completed, 300 g of water was added, the mixture was cooled to room temperature, and neutralized with a 10% aqueous hydrochloric acid solution while being careful not to generate heat. Thereafter, the precipitated crystals were collected by filtration, washed until the pH of the filtrate became 6 to 7, and dried at 50°C under reduced pressure (10 wHg) to form white crystals of 4-chlorophenol dimethylol compound (AC) (formula [ 226 g of a compound in which R is Cf) was obtained. The 4-chlorophenol dimethylol compound (AC
) was placed in a glass container equipped with a thermometer and a stirrer, and 576 g of 1-naphthol and 1,500 g of methyl isobutyl ketone were added thereto, followed by stirring at room temperature under a nitrogen atmosphere. and p-toluenesulfonic acid 1.7
g was added gradually, being careful not to generate heat, so that the liquid temperature did not exceed 50°C. After the addition, the mixture was reacted for 2 hours at 50°C in a hot water bath, and then transferred to a separatory funnel and washed with water. After washing with water until the washing water became neutral, the solvent and unreacted substances were removed from the organic layer under reduced pressure to obtain 388 g of phenolic novolac type resin (A-7) used in the present invention. The softening temperature (JIS K2425 ring and ball system) of the product (A-7) was 118°C, and the hydroxyl equivalent (g/mof) was 142.

Example 8 380 g of product (A-8) was obtained in the same manner as in Example 7 except that 576 g of 2-naphthol was used instead of 1-naphthol. Product (A-8)
The softening temperature was 120°C and the hydroxyl equivalent was 144.

Example 9 255 g (1.5 moles) of 4-phenylphenol, 90 g (3 moles) of paraformaldehyde, and 100 g of water were placed in a lI! equipped with a thermometer, condenser, dropping funnel, and stirrer. The mixture was charged into a flask and stirred while blowing nitrogen. At room temperature, add 120 g of a 15% aqueous sodium hydroxide solution (0.45 mol as sodium hydroxide) while being careful not to generate heat.
The mixture was slowly added dropwise so that the liquid temperature did not exceed 50°C.

Thereafter, the mixture was heated to 50° C. in a water bath and reacted for 200 hours. After the reaction was completed, 300 rIdl of water was added, the mixture was cooled to room temperature, and the mixture was neutralized with a 10% aqueous hydrochloric acid solution while being careful not to generate heat.

Chloroform 500- was added to this to separate the oil layer, washed with a water-methanol aqueous solution [water:methanol=80:20 (wt%)], and dried by adding anhydrous sodium sulfate. Subsequently, chloroform was removed under reduced pressure to obtain 305 g (78% purity) of 4-phenylphenol dimethylol compound (AP) (a compound in which R is a phenyl group in formula [X]) as a yellow viscous liquid.

295 g of the 4-phenylphenol dimethylol compound (AP) thus obtained was placed in a glass container equipped with a thermometer and a stirrer, and 576 g of l-naphthol and 1,500 g of methyl isobutyl ketone were added and stirred at room temperature under a nitrogen atmosphere. . and p-1 luenesulfonic acid 1
, 7 g was added gradually, being careful not to generate heat, so that the liquid temperature did not exceed 50°C.

After the addition, the mixture was heated to 50° C. in an oil bath and reacted for 2 hours, then transferred to a separatory funnel and washed with water. After washing with water until the washing water becomes neutral, the solvent and unreacted substances are removed from the organic layer under reduced pressure, and the phenolic novolac type resin (A-9) 4 of the present invention is prepared.
15g was obtained. Softening temperature of product (A-9) (JISK
2425 ring and ball method) is the hydroxyl equivalent (g
/mol) was 159.

Example 10 420 g of product (A-10) was obtained in the same manner as in Example 9 except that 576 g of 2-naphthol was used instead of 1-naphthol. Product (A-1
0) had a softening temperature of 131°C and a hydroxyl equivalent of 159.

Example It.

168 g of the 4-methylphenol dimethylol compound (compound with R or methyl group in formula (X)) (AM) obtained in Example 1 was charged into a glass container equipped with a thermometer and a stirrer, and further 2-methyl-1 -Naphthol 632
g and 1500 g of methyl isobutyl ketone were added, and the mixture was stirred at room temperature under a nitrogen atmosphere. Then, 1.7 g of p-toluenesulfonic acid was gradually added while being careful not to generate heat so that the liquid temperature did not exceed 50°C.

After the addition, the mixture was heated to 50°C in an oil bath and reacted for 2 hours, and then the solvent and unreacted substances were removed from the organic layer under reduced pressure.
I got g. The product (A-11) had a softening temperature of 107° C. and a hydroxyl equivalent of 1 47 (g/mof).

Analysis Example The products (A-1) to (A-11), which are phenolic novolac type resins of the present invention obtained in Example 1-11, were each subjected to GPC analysis, and the results were expressed by the formula [1[I]. A peak believed to be that of the compound was collected and analyzed by mass spectrometry (FAB-MS). As a result, for products (8-1) to (A-4), M = 420, for products (A-5) and (A-6), M7C3, and for products (A-7) and (A- 8) is M”440 (4
42), M “482 for products (A-9) and (A-10), M = 448 for product (A-11)
were obtained respectively. Therefore, the products (A-1) to (A-11) obtained in Examples 1 to 11 each contain the compound represented by formula [I] in the content as shown in the first column. This was confirmed.

The GPC analysis conditions are as follows.

GPC device: Takasugi Seisakusho (Column: TSK-G-3000XL (
1 bottle) 10TSK-G-2000XL (2 bottles) Solvent: Tetrahydrofuran 1mj/rnin test
Output: UV (254 nm) Application Examples 1-12 The product obtained in Example 1-11 (A-1
) to (A-11) were obtained by blending cresol novolac type epoxy resin or bisphenol A type epoxy resin as the epoxy resin and 2-methylimidazole as the curing accelerator in the proportions shown in Table 2. The composition was roll-kneaded at 70 to 80°C for 15 minutes, cooled, pulverized, made into a doublet, molded using a transfer molding machine, and precured at 160°C for 2 hours to form a 180°
Cured product (test piece) after 8 hours of post-curing at ``C''
I got it. The glass transition temperature (Tg), heat distortion temperature (HDT) and water absorption of this cured product were measured under the following conditions.

Glass transition temperature thermomechanical side fixed fit (TMA), vacuum science and technology ■TM -
7000 Temperature increase rate 2°C/min Heat distortion temperature Conditions specified in JIS K7207 Water absorption rate Conditions Weight increase (% by weight) after boiling in water at 100°C for 50 hours Note that the cresol of the epoxy resin used Novolac type epoxy resin and bisphenol A type epoxy resin are as follows.

Cresol novolac type epoxy resin EOCN1020 (manufactured by Nippon Kayaku ■) Epoxy equivalent (g/mof) 200 Softening temperature 65°C Bisphenol A type epoxy resin Evomic R-301 (manufactured by Mitsui Petrochemical Epoxy ■) Epoxy equivalent (g/mol 470 Softening temperature Softening source 8℃ The evaluation results of the cured products are shown in Table 2.

Comparative Application Examples 1-2 The cured products were evaluated in the same manner as in Application Examples 1 and 12, except that a commercially available curing agent, epoxy resin, and curing accelerator were blended in the proportions shown in Table 2.

The evaluation results are shown in Table 2.

The commercially available curing agents blended are as follows.

Phenol novolac resin (manufactured by Nippon Kayaku ■) Hydroxyl equivalent (g/moI) 106 Softening source degree 85°C Example 12 The reaction was carried out in a reactor equipped with a thermometer, a stirring device, a dropping funnel, and a produced water separation device. Product obtained in Example 1 (A-1)
(Hydroxy group equivalent (g/mol) 138) 138
After charging 460 g of epichlorohydrin and purging with nitrogen, 85 g of a 48% aqueous sodium hydroxide solution was added dropwise over 5 hours. During the dropwise addition, the reaction temperature was 60°C and the pressure was 10°C.
Under conditions of 0 to 150 wHg, the produced water and the water in the aqueous sodium hydroxide solution were continuously removed from the reaction system by azeotropy with epichlorohydrin, and epichlorohydrin was returned to the system.

Then, after recovering excess unreacted epichlorohydrin under reduced pressure, 500% of methyl isobutyl ketone was added and
The mixture was washed with 0 d of water until the aqueous layer became neutral. Methyl isobutyl ketone was removed from the methyl isobutyl ketone phase under reduced pressure, and then 400 g of methyl isobutyl ketone was added again.
was added and redissolved.

20 g of 2% sodium hydroxide solution was added to the obtained methyl isobutyl ketone solution, and the mixture was reacted at a reaction temperature of 70° C. for 2 hours.

After the reaction was completed, washing was repeated with water until the aqueous layer became neutral.

Then, methyl isobutyl ketone was removed from the methyl isobutyl ketone phase under reduced pressure to obtain a pale yellow solid (B-1) 1
70g was obtained. Softening temperature (JIS
K2425) has an epoxy equivalent (g/mol) at 75°C.
) was 213.

In addition, the product (B-1) was subjected to GPC in the same manner as in the above analysis example.
As a result of analysis, the content of the phenolic novolak type epoxy compound represented by formula [V] in the product (B-1) was 57% by weight.

Since M=588 was obtained in the mass spectrum (FAB-MS) of the product (B-1), it was confirmed that the compound having the following structure was contained in the above content.

Example 13 The product (A-1) obtained in Example 1 (hydroxyl equivalent (
After charging 138 g/mo I 138), 460 g of epichlorohydrin, and 230 g of dimethyl sulfoxide and purging with nitrogen, 40 g of sodium hydroxide was gradually added in a water bath at 30°C. Be careful of fever 30
The reaction was carried out at 70°C for 5 hours, at 50°C for 2 hours, and then at 70°C for 1 hour. Then, water was added to wash the mixture until the aqueous layer became neutral. Thereafter, epichlorohydrin and dimethyl sulfoxide were removed from the oil layer under reduced pressure. Thereafter, 400 g of methyl isobutyl ketone was added and redissolved. 20 g of 20% sodium hydroxide solution was added to the obtained methyl isobutyl ketone solution, and the mixture was reacted at a reaction temperature of 70° C. for 2 hours. After the reaction was completed, washing with water was repeated and methyl isobutyl ketone was removed from the methyl isobutyl ketone layer under reduced pressure to obtain 167 g of a yellow solid (B-2). The product (B-
The softening temperature of 2) was 77°C, and the epoxy equivalent (g/mol) was 212. Also, as a result of the same GPC analysis as in Example 12, the product (B-2) was expressed by the formula [V]. The content of the phenolic novolac type epoxy compound was 59% by weight.The mass spectrum of the product (B-2) (F
AB-MS) and M = 588. This confirmed that the compound having the structural formula shown in Example 12 was included in the above content.

Example 14 The product (A-1) obtained in Example 2 was replaced with the product (A-1).
-2) (Hydroxy group equivalent (g/mol) 137)
The reaction was carried out in the same manner as in Example 12, except that 137 g was used, and 172 g of product (B-3) was obtained. The product (B-
The softening temperature of 3> is 89℃ and the epoxy equivalent (g/m
o I! ) was 215. Further, as a result of the same analysis as in Example 12, the content of the phenolic novolak type epoxy compound represented by formula [V] in the product (B-3) was 37% by weight. The mass spectrum (FAB-MS) of the product (B-3') revealed that h588 was obtained, indicating that the compound having the structural formula shown in Example 12 was
It was confirmed that the compound was contained in the above content.

Example 15 The product (A-1) obtained in Example 3 was replaced with the product (A-1).
-3) (Hydroxyl equivalent (g/no 1) 137) 137
The reaction was carried out in the same manner as in Example 12, except that g was used, and 170 g of product (B-4) was obtained. The product (B-4), which is a phenolic novolac type resin of the present invention, had a softening temperature of 92°C and an epoxy equivalent (g/mof) of 212.

As a result of the same analysis as in Example 12, the content of the phenolic novolac type evoquin compound represented by formula [V] in the product (B-4) was 32% by weight. Product (B-4
), it was confirmed that the compound having the structural formula shown in Example 12 was a compound contained in the above content.

Example 16 The product (A-1) obtained in Example 4 was used instead of the product (A-1).
-4) (Hydroxyl group equivalent (g/no l) 138) 138g
The reaction was carried out in the same manner as in Example 12 except that 169 g of product (B-5) was obtained.

The softening temperature of the product (B-5), which is a phenolic novolac type epoxy resin of the present invention, is 76°C and the epoxy equivalent (
g/mof) was 214. As a result of the same analysis as in Example 12, the content of the phenolic novolak type epoxy compound represented by formula [V] in the product (B-5) was 55
% by weight. Mass spectrum of product (B-5) (
FAB-MS), M'''588 was obtained,
It was confirmed that the compound having the structural formula shown in Example 12 (however, the bonding position of the epoxy group to the naphthalene nucleus is the 2-position) was a compound contained in the above content.

Example 17 Product (A-1) obtained in Example 5 was replaced with product (A-1).
-5) (hydroxyl equivalent (g/mof) 151) The reaction was carried out in the same manner as in Example 12 except that 151 g of the product (hydroxyl group equivalent (g/mof) 151) was used to obtain 186 g of product (B-6). The softening temperature of the product (B-6), which is a phenolic novolac type epoxy resin of the present invention, is 89°C and the epoxy equivalent (g / mol)
was 240. Further, as a result of the same analysis as in Example 12, the content of the phenolic novolac type epoxy compound represented by formula [V] in the product (B-6) was 35% by weight. Mass spectrum of product (B-6) (FAB-
By obtaining M'628 by MS), it was confirmed that the compound having the following structure was contained in the above content.

Example 18 The product (A-1) obtained in Example 6 was replaced with the product (A-1).
-6) (Hydroxy group equivalent (g/mol) 152)
The reaction was carried out in the same manner as in Example 12, except that 152 g was used, and 188 g of product (B-7) was obtained. The product (B-
7) The softening temperature is 92 °C and the epoxy equivalent (g/m
o l ) was 238. Furthermore, as a result of the same analysis as in Example 12, the content of the phenolic novolak type epoxy compound represented by formula [V] in the product (B-7) was 38
% by weight. Mass spectrum of product (B-7) (
FAB-MS), M''628 was obtained, resulting in a compound having the structural formula shown in Example 17 (however, the bonding position of the epoxy group to the naphthalene nucleus is the 2-position).
was confirmed to be a compound contained in the above content.

Example 19 Product (A-1) obtained in Example 7 was substituted for product (A-1).
7) (Hydroxyl group equivalent (g/m o 1) 142) 1
The reaction was carried out in the same manner as in Example 12, except that 42 g was used, and 176 g of product (B-8) was obtained. The product (B-8) which is a phenolic novolac type epoxy resin of the present invention
) has a softening temperature of 95°C and an epoxy equivalent (g/moA')
was 230. Further, as a result of the same analysis as in Example 12, the content of the phenolic novolak type epoxy compound represented by formula [V] in the product (B-8) was 37% by weight. Mass spectrum of product (B-8) (FAB-
Since M2O3 and 6!0 were obtained by MS), it was confirmed that the compound having the following structure was contained in the above content.

Example 20 The product (A-1) obtained in Example 8 was replaced with the product (A-1).
-8) (Hydroxy group equivalent (g/m o 1) 144)
The reaction was carried out in the same manner as in Example 12 except that 144 g was used to obtain 180 g of product (B-9). The product (B-
The softening temperature of 9) is 96°C and the epoxy equivalent (g/mof)
was 232. Further, as a result of the same analysis as in Example 12, the content of the phenolic novolac type epoxy compound represented by formula [V] in the product (B-9) was 38% by weight. Mass spectrum of product (B-9) (FAB-
MS), M゛608 and 610 were obtained,
It was confirmed that the compound having the structural formula shown in Example 19 (however, the bonding position of the epoxy group to the naphthalene nucleus is the 2-position) was a compound contained in the above content.

Example 21 Product (A-1) obtained in Example 9 was replaced with product (A-1).
-9) (The reaction was carried out in the same manner as in Example 12 except that 159 g of hydroxyl group equivalent (g/moI ratio 159) was used to obtain 194 g of product (B-10). Phenolic novolac type epoxy resin of the present invention The softening temperature of the product (B-10) is 95 °C and the epoxy equivalent (g/m).

The average was 233. As a result of the same analysis as in Example 12,
The content of the phenolic novolac type epoxy compound represented by formula [V] in the product (B-10) was 42% by weight. Mass spectrum (FAB) of product (B-10)
-MS), M = 650 was obtained, confirming that the compound having the following structure was contained in the above content.

Example 22 Product obtained in Example 1O instead of product (A-1) (
A-10) (Hydroxyl group equivalent (g/m).

f) The reaction was carried out in the same manner as in Example 12 except that 159 g of 159) was used to obtain 190 g of product (B-11). The product (B-11), which is a phenolic novolac type epoxy resin of the present invention, has a softening temperature of 97°C and an epoxy equivalent (g/m).

I was 230. Further, as a result of the same analysis as in Example 12, the content of the phenolic novolac type epoxy compound represented by formula [V] in the product (B-11) was 43% by weight. Mass spectrum of product (B-11) (
FAB-MS), a compound having the structural formula shown in Example 21 was obtained (however, the bonding position of the epoxy group to the naphthalene nucleus was at the 2-position).

) was confirmed to be a compound contained in the above content.

Example 23 Instead of product (A-1), the product obtained in Example 11 (
A-11) (Hydroxyl group equivalent (g/m).

! Example 13 except that 4') 147) 1.47 g was used.
The reaction was carried out in the same manner as above to obtain 179 g of product (B-12). The product (B-12), which is a phenolic novolak type epoxy resin of the present invention, has a softening temperature of 83°C and an epoxy equivalent (g/m).

i> was 218. Further, as a result of the same analysis as in Example 12, the content of the phenolic novolak type epoxy compound represented by formula [V] in the product (B-12) was 52% by weight. Mass spectrum of product (B-12) (
By obtaining M''616 by FAB-MS), it was confirmed that the compound having the following structure was contained at the above content.

Application Examples 13-26 The products obtained in Examples 1-11 (A
-1) to (A-11) as a curing agent, Examples 12 to 23
The products (B-1) to (B-12) obtained in (B-1) to (B-12) were used as an epoxy resin, and 2-methylimidazole was used as a curing accelerator, and these were blended in the proportions shown in Table 3. The test was conducted in the same manner as in 12. The evaluation results of the cured products are shown in Table 3.

Application Comparative Examples 3 and 4 A phenol novolac resin (H-1) was used as a curing agent, a cresol novolak type epoxy resin (EOCN 1020) was used as an epoxy resin, or an aromatic aldehyde and phenol were combined in the proportions shown in Table 3. polyepoxy compound of polyphenol obtained by (EPPN502)
using 2-methylimidazole as a curing accelerator,
Tests were conducted in the same manner as in Application Example 1-12, and the cured products were evaluated.

The evaluation results are shown in Table 3.

In addition, the above (H-1), (EOCN 1020), (EP
PN502) is as follows.

H-1: Nippon Yamayaku ■, phenol novolac resin Softening temperature 85°C Hydroxyl equivalent (g/IIIoi) 106EOCN-1
020: Made by Nippon Kayaku ■, cresol novolac type epoxy resin Softening temperature 65°C EPPN502 Epoxy equivalent (g / mol> 200 = Made by Nippon Kayaku ■, polyepoxy compound Softening temperature 70''C Epoxy equivalent (g 7m01') 168 Application Examples 27-36 Phenol novolak (Nippon Kajimi Co., Ltd., softening temperature 85°C, hydroxyl equivalent (g/mol) + 0) in the proportions shown in Table 4
5) and examples! Products (B-1'), (B-3), (B-5) to (B-12) obtained in 2.14 and 16-23
) and 2-methylimidazole, and the following tests were conducted in the same manner as in Application Examples 1 to 12, and the evaluation results of the obtained cured products are shown in Table 4.

Application Comparative Examples 5 and 6 Products (B-1), (B-3), (B-5) to (B-1
In place of 2), the product (D-1) obtained in the following Reference Example 1 or the following commercially available 0-cresol novolac type epoxy resin EOCN1020 was used in the proportions shown in Table 4, and the rest were the same as in the applied examples. Tests were conducted in the same manner as in Examples 27-36.

The results are shown in Table 4.

EOCN-1020: Nippon Kajimi Co., Ltd., epoxy equivalent (g
/mol ratio 200, softening salinity 65°C Reference example 1° 1-naphthol 1 in a glass container equipped with a thermometer and a stirrer
44 g, water 20g 1 oxalic acid 1.6g, 11
Heat to 0°C to melt, and add formalin aqueous solution (37
%) was added dropwise over 30 minutes. Next, 90
The mixture was heated at the same temperature for a minute, and then the temperature was raised to 150°C, and the reaction was continued for an additional 120 minutes. Then, take out the reactant,
It was crushed, washed with hot water, and dried. The hydroxyl equivalent of the obtained novolak naphthol resin (g/m o I!
) is 156, the softening temperature is 175°C, and the average molecular weight by GPC analysis is 730 (the naphthol component in the molecule is 4.7 on average).
).

The product (
Polyglycidyl ether (D-1) 195 was obtained by carrying out the same operation as in Example 12 except that it was used instead of A-1).
I got g. The softening temperature of polyglycidyl ether (D-1) is +20'C and the epoxy equivalent (g/mof) is 270
Met.

〔Effect of the invention〕

The resin containing the compound of the present invention has a low softening temperature and low melt viscosity, so it is easy to handle and has excellent workability.
The cured product obtained using this resin has a high glass transition temperature and heat distortion temperature, which are indicators of heat resistance, and can have a lower water absorption rate than cured products obtained from conventional resins.

Therefore, the resin containing the compound of the present invention can meet the recent demands for heat resistance and low water absorption, and can be used in a wide range of fields, specifically as sealing materials, molding materials, and laminated materials for electronic components. Used as a material for 1. Extremely useful.

Claims (23)

[Claims] (1) Formula [ I ] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [ I ] (In the formula, X represents H or ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼, R_1, R_2, R_3, R_4, R_5 ,R_6,R
_7, R_8, R_9, R'_4, R'_5, R'_6
, R'_7, R'_8, and R'_9 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom). (2) Formula [II] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [II] (In the formula, R_1_0, R_1_1, R_1_2, R'_
1_1 and R'_1_2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom). (3) Formula [III] ▲ Numerical formulas, chemical formulas, tables, etc. 1 to 4 alkyl groups). (4) The compound according to claim 3, wherein R_1_3 is a methyl group and R_1_4 is a hydrogen atom. (5) Formula [IV] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [IV] (In the formula, R_1_0, R_1_1, R_1_2, R'_
1_1 and R'_1_2 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom. (6) Formula [V] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [V] (In the formula, R_1_3 represents an alkyl group having 1 to 4 carbon atoms, a phenyl group, or a halogen atom, and R_1_4 represents a hydrogen atom or a carbon number 1 to 4 alkyl groups). (7) The compound according to claim 6, wherein R_1_3 is a methyl group and R_1_4 is a hydrogen atom. (8) A novolak-type resin comprising the compound according to claim 1. (9) A phenolic novolac type resin comprising the compound according to claim 2, 3 or 4. (10) A phenolic novolac type epoxy resin comprising the compound according to claim 5, 6 or 7. (11) The resin according to claim 8, 9 or 10, wherein the content of the compound is 30% by weight or more. (12) (a) Formula as epoxy resin [VI] ▲ Formula,
There are chemical formulas, tables, etc. ▼ [IV] (In the formula, R_1, R_
2, R_3, R_4, R_5, R_6, R_7, R_8
, R_9, R'_4, R'_5, R'_6, R'_7,
R'_8 and R'_9 are each independently a hydrogen atom, carbon number 1
-4 alkyl group, aryl group or halogen atom. ) A phenolic novolac type epoxy resin containing a compound represented by (b)
An epoxy resin composition comprising a curing agent. (13) The epoxy resin composition according to claim 12, wherein the phenolic novolac type epoxy resin is the resin according to claim 10. (14) Formula for (a) epoxy resin and (b) curing agent [VII] ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ [VII] (In the formula, R_1, R_2, R_3, R_4, R_1_5
, R_6, R_7, R_8, R_9, R'_4, R'_
5, R'_6, R'_7, R'_8, and R'_9 each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom). An epoxy resin composition comprising a phenolic novolac type resin. (15) The epoxy resin composition according to claim 14, wherein the phenolic novolac type resin is the resin according to claim 9. (16) An epoxy resin composition comprising (a) the phenolic novolac type epoxy resin according to claim 12 as an epoxy resin, and (b) the phenolic novolac type resin according to claim 14 as a curing agent. thing. (17) The epoxy resin composition according to claim 16, wherein the phenolic novolac type epoxy resin is the resin according to claim 10, and the phenolic novolac type resin is the resin according to claim 9. (18) Claims 12, 13, 14, 1 containing a curing accelerator
5, 16 or 17. The epoxy resin composition according to item 5, 16 or 17. (19) Formula [VIII] ▲ Numerical formulas, chemical formulas, tables, etc. are available ▼ [VIII] (In the formula, R_1, R_2, R_3 are each independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen ▼There are mathematical formulas, chemical formulas, tables, etc.▼[IX] (In the formula, R_4, R_5, R_6, R_7, R_8, R
_9 each independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom). Resin according to 11. (20) The epoxy resin composition according to claim 14, 15, 16, 17 or 18, wherein the phenolic novolac type resin is the resin obtained according to claim 19. (21) Claim 8, 10 or 1 obtained by further reacting the resin obtained in Claim 19 with an epihalohydrin compound.
Resin according to 1. (22) Claims 12, 13, 16, wherein the phenolic novolac type epoxy resin is the resin obtained in Claim 21;
Epoxy resin composition of No. 17 or 18. (23) Claims 12, 13, 14, 15, 16, 17,
Cured product of the epoxy resin composition of No. 18, 20 or 22.