JPH04304225A - New compound, resin, resin composition, and cured article - Google Patents

Abstract

PURPOSE:To prepare a resin compsn. having both a high thermal resistance and low water absorption properties by using a resin having a specific structural formula. CONSTITUTION:A dimethylol compd. of formula I or II (wherein R is 1-4C alkyl, aryl, or halogen) is condensed with dihydroxynaphthalene of formula III in the presence of an acid catalyst to give a resin of formula IV (wherein A is a group of formula V or VI; X is H or a group of formula VII; and n is 0-10). An epoxy resin which comprises the resin of formula IV wherein X is the group of formula VII, a curative which comprises the resin of formula IV wherein X is H, and an accelerator are compounded to give a resin compsn.

Description

Description: FIELD OF THE INVENTION The present invention relates to compounds, resins, resin compositions, and cured products thereof useful as materials for sealing or laminating electronic components. [0002] Conventionally, resin compositions containing epoxy resins, phenol novolac resins, and curing accelerators as main components have been widely used in the field of encapsulants for electrical and electronic components, particularly ICs. However, the recent trend toward higher density and higher integration in ICs has required encapsulants to have high heat resistance and low water absorption. In particular, the harsh conditions of immersion in a solder bath during high-density mounting of ICs are increasingly demanding higher heat resistance and lower water absorption for cured products. However, cresol novolac type epoxy resins, which are generally used as epoxy resins in conventional compositions, are insufficient in terms of heat resistance against the harsh conditions of immersion in a solder bath. In addition, in the polyepoxy compound, which is obtained by epoxidizing a polyphenol obtained by condensing an aromatic aldehyde having a phenolic hydroxyl group and phenols, as described in JP-A No. 63-264622, which has been proposed as having heat resistance, the cured product is Although it has been recognized that the heat resistance has improved, it has the disadvantage of increasing the softening point or melt viscosity, impairing workability.
Also, it is not as good as cresol novolak type epoxy resin in terms of water absorption. On the other hand, the phenol novolac resins commonly used as curing agents are still insufficient in terms of heat resistance, and although attempts have been made to reduce the amount of low molecular weight substances (binuclear phenol novolaks), Under increasingly severe conditions (eg 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. SUMMARY OF THE INVENTION The present invention provides a resin composition that can withstand these increasingly severe conditions and provides a cured product with high heat resistance and low water absorption, and a cured product thereof. It provides: [Means for Solving the Problems] As a result of intensive studies aimed at developing a resin composition that has the above-mentioned two contradictory properties, high heat resistance and low water absorption, the present inventors found that naphthol The inventors have discovered that the above object can be achieved by using a compound having a specific structure into which a ring has been introduced, and have completed the present invention. That is, the present invention provides formula (1) [1] 000
9 [Chemical formula 17] [0010] (wherein A is the formula [A1] [Chemical formula 18] [Chemical formula 18] [Chemical formula 18] [0012] or the formula [A2] [Chemical formula 19] [Chemical formula 19] [0014], R is carbon an alkyl group, aryl group or halogen atom of numbers 1 to 4, X is H or the formula [XE] 0
##STR20## where n takes a value of 0 to 10. ), (2) formula [2] [0018] (wherein R is an alkyl group having 1 to 4 carbon atoms,
Indicates an aryl group or a halogen atom. ), (3) a compound represented by formula [3] [0020], (4) a compound represented by formula [4] 00
21] Compound represented by [Chemical formula 23] [0022], (5) formula [5] 00
23] Compound represented by [Chemical formula 24] [0024], (6) formula [6] 00
25] [0026] (wherein R is an alkyl group having 1 to 4 carbon atoms,
Indicates an aryl group or a halogen atom. ), (7) an epoxy compound represented by formula [7], (8) an epoxy compound represented by formula [8]
] [0029] Epoxy compound represented by [Chemical formula 27] [0030], (9) formula [9
] [0031] Epoxy compound represented by [Chemical formula 28] [0032], formula (10) [
10] [0033] [0034] (wherein, R represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom) or the formula [11
] A dimethylol compound represented by the formula [12] [Chemical formula 30] [0036] (wherein R has the same meaning as above) and a dihydroxy compound represented by the formula [12] [Chemical formula 31] [0038] It is obtained by reacting with naphthalene, and in the formula [1] of (1) above, n=O
A resin in which X is H in the formula [1] of the above (1), which contains 30% by weight or more of a compound where X=H;
] [0040] [0041] (In the formula, Y represents a halogen atom) obtained by reacting with an epihalohydrin compound represented by (1) contains 30% by weight or more of a compound representing the formula [XE] of (1) above;
) in the formula [1], where X represents the formula [XE] in the above (1); (12) an epoxy resin composition containing an epoxy resin, a curing agent, and a curing accelerator; As, in the formula [1] of the above (1), using a resin in which X represents the formula [XE] of the above (1) or the resin of the above (11), and/or (B) as a curing agent, the above (1) (13) A cured product of the epoxy resin composition of (12) above, using a resin in which X is H in formula [1] or the resin of (10) above. . The present invention will be explained in detail below. The resin of the present invention is represented by the above formula [1], and in the formula [1], n
Those containing 30% by weight or more of the compound with =0 are preferred, and those containing 35% by weight or more are particularly preferred. The number of n in the above formula [1] is 0 to 10, preferably 0 to 5, particularly preferably 0 to 2. If the value of n is too high, the viscosity will increase and workability will be impaired. In R, examples of the alkyl group having 1 to 4 carbon atoms include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, s-butyl group, and t-butyl group. Methyl group is preferred. Examples of the aryl group include a phenyl group, 4-methylphenyl group, and 2-methylphenyl group. Examples of the halogen atom include chlorine atom, fluorine atom, bromine atom, and iodine atom, with chlorine atom and bromine atom being particularly preferred. Among the compounds and resins of the present invention, particularly preferred are compounds represented by formulas [4], [5], [8], or [9] and resins containing the same. In particular, the resins (10) and (11) above have a high content of the compound where n=0 in formula [1], and have a sharp molecular weight distribution, so they have a low melt viscosity and are easy to work with despite having naphthol rings. It can provide cured products with excellent properties, high heat resistance, and low water absorption. The compounds and resins of the present invention can be produced, for example, as follows. That is, a dimethylol compound represented by formula [10] or [11] and formula [1]
2] and dihydroxynaphthalene in the presence of an acid catalyst. Formula [10
] As the dimethylol compound represented by 4,6-dimethylol-2-methylphenol, 2,6-dimethylol-4-methylphenol, 2,6-dimethylol-
4-ethylphenol, 2,6-dimethylol-4-n
-butylphenol, 2,6-dimethylol-4-se
c-butylphenol, 2,6-dimethylol-4-t
ert-butylphenol, 2,6-dimethylol-4
-Chlorophenol, 2,6-dimethylol-4-bromophenol, 2,6-dimethylol-4-phenylphenol, etc., especially 4,6-dimethylol-2-methylphenol, 2,6-dimethylol- 4
-Methylphenol is preferred. [0048] As the dimethylol compound represented by formula [11], a binuclear dimethylol compound of orthocresol, which is a compound represented by formula [14] [Chemical formula 33] used. formula[
12], the dihydroxynaphthalene represented by 1
, 2-dihydroxynaphthalene, 1,3-dihydroxynaphthalene, 1,4-dihydroxynaphthalene, 1,5
-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 1,7-dihydroxynaphthalene, 1,8-dihydroxynaphthalene, 2,3-dihydroxynaphthalene, 2,4-dihydroxynaphthalene, 2,5-dihydroxynaphthalene, 2,6- dihydroxynaphthalene,
Examples include 2,7-dihydroxynaphthalene and 2,8-dihydroxynaphthalene, with 1,6-dihydroxynaphthalene and 1,4-dihydroxynaphthalene being particularly preferred. These may be used alone or in combination of two or more. As the acid catalyst, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, p-toluenesulfonic acid, etc. can be used. Preferably, 30% by weight is used. In addition, dihydroxynaphthalene has the formula [10] or [1
It is preferable to use 2 to 10 times the mole of the dimethylol compound represented by [1]. 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 preferably in the range of 20 to 150°C. After the reaction is completed, the used catalyst is removed by washing with water, etc., unreacted substances are removed by solvent extraction, and the solvent is removed under reduced pressure to obtain the desired resin (formula [1]
(in which X represents H) is obtained. The resin thus obtained preferably contains 30% by weight or more, particularly preferably 35% by weight or more of the compound of formula [1] where X=H and n=0. Next, the formula [1] obtained in this way
By reacting the epihalohydrin compound represented by the formula [13] with the resin in which X=H in the presence of a basic compound, a resin in which X represents the formula [XE] in the formula [1] can be easily obtained. In the above formula [13], examples of the halogen atom represented by Y include Cl, Br, I, etc., and examples of the compound of formula [13] include epichlorohydrin, epibromohydrin, epiiodohydrin, etc. Phosphorus, etc. can be used, and mixtures thereof can also be used, but epichlorohydrin is preferably used industrially. In the formula [1], the reaction between the resin where X=H and the epihalohydrin compound can be carried out by a known method. For example, a resin of formula [1] where X=H and an excess molar amount of an epihalohydrin compound relative to its hydroxyl equivalent are mixed with tetramethylammonium chloride, tetramethylammonium bromide, triethylammonium chloride, etc. The reaction is carried out in the presence of a quaternary ammonium salt or an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. If a quaternary ammonium salt is used, the reaction will stop at the stage of the ring-opening addition reaction. Next, the above-mentioned alkali metal hydroxide is added to carry out the ring-closing reaction. In addition, when the alkali metal hydroxide is added from the beginning and the reaction is carried out, the ring-opening addition reaction and the ring-closing reaction are carried out at once. Usage ratio of the epihalohydrin compound is usually in the range of 1 to 50 mol, preferably 3 to 15 mol, per equivalent of the hydroxyl group of the resin where X=H in formula [1]. For this purpose, alcohols such as methanol, or aprotic polar solvents such as acetone, dioxane, dimethyl sulfoxide, dimethyl sulfone, dimethyl formamide, etc. can be used, and it is particularly preferable to use dimethyl sulfoxide. The amount of oxide used is determined by the formula [1
], usually 0 for 1 hydroxyl equivalent of the resin where X=H
．． The amount is in the range of 8 to 1.5 mol, preferably 0.9 to 1.3 mol, and when a quaternary ammonium salt is used, the amount used is 1
normally 0.001 to 1.0 mol, preferably 0.001 to 1.0 mol, preferably 0.001 to 1.0 mol.
The range is from 0.005 to 0.5 mol. The reaction temperature is usually 30
-130°C, preferably 40-120°C. Furthermore, the reaction can be allowed to proceed while removing water produced in the reaction from the reaction system. After the reaction is completed, the by-produced salt is removed by washing with water, filtration, etc., so that X in the formula [1] becomes the formula [
An epoxy resin exhibiting XE] is obtained. The epoxy resin obtained in this manner preferably contains 30% by weight or more, particularly preferably 35% or more of a compound in which n=0 and X represents the formula [XE] in formula [1]. The epoxy resin composition of the present invention will be explained below. In the epoxy resin composition of the above (12), the resin in which X in the formula [1] of the above (1) represents the formula [XE] or the resin of the above (11) (hereinafter referred to as the epoxy resin of the present invention) is singly Alternatively, it can be used in combination with other epoxy resins. When used together, 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 novolac type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, alicyclic epoxy resin, and biphenyl type. Examples include epoxy resins, but novolak epoxy resins are particularly advantageous in terms of heat resistance. Specific examples include, but are not limited to, cresol novolak epoxy resins, phenol novolak epoxy resins, and brominated phenol novolac epoxy resins. These may be used alone or in combination of two or more. In the epoxy resin composition of the above (12), the resin in which X is H in the formula [1] of the above (1) or the resin of the above (10) (hereinafter referred to as the novolac type resin of the present invention) is used alone. It can be used alone or in combination with other curing agents. When used together, the proportion of the novolac type resin of the present invention in the total curing agent is preferably 30% by weight or more, particularly preferably 40% by weight or more. Other curing agents used in combination with the novolac 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. Acid anhydride curing agents such as, phenolic curing agents such as phenol novolac, cresol novolak, etc.
Examples include, but are not limited to, Lewis acids such as boron trifluoride or their salts, curing agents such as dicyandiamide, and the like. These may be used alone,
Two or more types may be used in combination. In the epoxy resin composition (12) above, when the epoxy resin of the present invention is used as the epoxy resin, the other curing agents mentioned above or the novolac type resin of the present invention can be used as the curing agent. [0064] Furthermore, in the above epoxy resin composition,
When using the novolac type resin of the present invention as a curing agent,
As the epoxy resin, other epoxy resins mentioned above or the epoxy resin of the present invention can be used. In the epoxy resin composition of the present invention, the amount of curing agent used is preferably 0.5 to 1.5 equivalents, particularly 0.6 to 1.2 equivalents per equivalent of epoxy groups in the 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 triphenylphosphine compounds. Various known curing agent 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. [0067] The epoxy resin composition of the present invention may further contain known additives as required. Examples of additives include inorganic fillers such as silica, alumina, talc, and glass fiber; Examples include surface treatment agents for fillers such as silane coupling agents, mold release agents, and pigments. The epoxy resin composition of the present invention is obtained by uniformly mixing each component, and usually has a molecular weight of 130 to 170
By carrying out preliminary curing at a temperature of 150 to 200° C. for 30 to 300 seconds and further post-curing at a temperature of 150 to 200° C. for 2 to 8 hours, a sufficient curing reaction proceeds and the cured product of the present invention is obtained. The cured product thus obtained has excellent performance, having two properties: low water absorption while maintaining heat resistance. Therefore, the above 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 where heat resistance and low water absorption are required. Specifically, it is useful as a compounding component of all electrical and electronic materials such as insulating materials, laminates, and sealing materials. It can also be used in fields such as molding materials and composite materials. By using the epoxy resin of the present invention and the novolak type resin of the present invention as both the epoxy resin component and the curing agent component, the effect is doubled. Furthermore, the resin of the present invention has a low softening point despite having a naphthol ring, so conventional techniques such as transfer molding can be used, and workability is good. [Example] The present invention will be specifically explained below with reference to Examples. Example 1.162 g of 4-methylphenol
(1.5 mol), paraformaldehyde 90 g and water 1
00 ml was placed in a flask equipped with a thermometer, condenser, dropping funnel, and stirrer, and stirred while blowing nitrogen. At room temperature, 120 g of a 15% aqueous sodium hydroxide solution (0.45 mol as sodium hydroxide) was slowly added dropwise to the mixture while being careful not to generate heat so that the temperature of the solution did not exceed 50°C. [0073] Thereafter, it was heated to 50°C in a water bath and heated to 10°C.
Allowed time to react. After the reaction was completed, 300 ml 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, and then the precipitated crystals were collected by filtration. The pH of the filtrate is 6~
7 and dried at 50° C. under reduced pressure (10 mmHg) to obtain 202 g of 2,6-dimethylol-4-methylphenol (AM) as white crystals. White crystals (AM) 168 thus obtained
g was placed in a flask equipped with a thermometer, condenser, and stirrer, and 640 g of 1,6-dihydroxynaphthalene and 1000 ml of methyl isobutyl ketone were added thereto, followed by stirring at room temperature under a nitrogen atmosphere. Then, 1.7 g of p-toluenesulfonic acid was slowly added dropwise while paying attention to heat generation so that the liquid temperature did not exceed 50°C. After the addition, the mixture was heated to 50°C in a water 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, unreacted dihydroxynaphthalene is extracted with a water/methanol solution (water/methanol = 60/40 (wt%)), and then the solvent and unreacted dihydroxynaphthalene are extracted from the organic layer. By removing the reactant under reduced pressure, 430 g of the resin (A-1) of the present invention was obtained. Softening temperature of product (A-1) (JIS K2425
ring and ball method), the hydroxyl equivalent (g/mol) was 88 at 115°C.
Met. Example 2. 438 g of product (A-2) was obtained in the same manner as in Example 1 except that the amount of 1,6-dihydroxynaphthalene used in Example 1 was changed to 400 g. The product (A-2) had a softening temperature of 118°C and a hydroxyl equivalent (g/mol) of 86. Example 3. 426 g of product (A-3) was obtained in the same manner as in Example 1 except that 640 g of 1,4-dihydroxynaphthalene was used instead of 1,6-dihydroxynaphthalene. Product (A
The softening temperature of -3) is 120℃ and the hydroxyl equivalent (g/mol
) was 89. Example 4.4-tert-butylphenol 22
5 g (1.5 moles) of paraformaldehyde, 90 g of paraformaldehyde, and 100 ml of water were placed in a 1-liter flask equipped with a thermometer, condenser, dropping funnel, and stirrer, and stirred while blowing nitrogen. At room temperature, 120 g of 15% aqueous sodium hydroxide solution (0.45 mol as sodium hydroxide)
was slowly added dropwise so that the liquid temperature did not exceed 50° C. while being careful not to generate heat. [0079] Thereafter, it was heated to 50°C in a water bath and heated to 10°C.
Allowed time to react. After the reaction was completed, 300 ml 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. Add 500ml of chloroform to separate the oil layer.
After washing with a water/methanol solution (water/methanol = 80/20 (wt%)), anhydrous sodium sulfate was added to dry. Thereafter, chloroform was removed under reduced pressure to obtain 285 g (purity: 85%) of 2,6-dimethylol-4-t-butylphenol (AB) as a viscous liquid. 2,6-dimethylol 4 thus obtained
- 247 g of t-butylphenol (AB) was charged into a flask equipped with a thermometer, a cooling tube, and a stirrer, and 1,6-
640 g of dihydroxynaphthalene and 1000 ml 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 slowly added dropwise while paying attention to heat generation so that the liquid temperature did not exceed 50°C. After the addition, the mixture was heated to 50°C in a water 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, unreacted dihydroxynaphthalene is extracted with a water/methanol solution (water/methanol = 60/40 (wt%)), and then the solvent and unreacted dihydroxynaphthalene are extracted from the organic layer. By removing the reactant under reduced pressure, 480 g of the resin (A-4) of the present invention was obtained. Softening temperature of product (A-4) (JIS K2425
ring and ball method), the hydroxyl equivalent (g/mol) is 10 at 105°C.
It was 1. Example 5. 476 g of product (A-5) was obtained in the same manner as in Example 4, except that 640 g of 1,4-dihydroxynaphthalene was used instead of 1,6-dihydroxynaphthalene. Product (A
-5) has a softening temperature of 102°C and a hydroxyl equivalent (g/mol
) was 99. Example 6. Product (A-6) was produced in the same manner as in Example 1, except that 189 g of 2,6-dimethylol-4-chlorophenol (AC) was used instead of 2,6-dimethylol-4-methylphenol in Example 1. 46
Obtained 0g. Softening temperature of product (A-6) (JIS
K2425 ring and ball method) is the hydroxyl equivalent (g/
mol) was 93. Example 7. 472 g of product 1 (A-7) was obtained in the same manner as in Example 6 except that 640 g of 1,4-dihydroxynaphthalene was used instead of 1,6-dihydroxynaphthalene. Product (A
-7) has a softening temperature of 117°C and a hydroxyl equivalent (g/mol
) was 95. Example 8. The product ( A-8) 508g was obtained. The softening temperature (JIS K2425 ring and ball method) of the product (A-8) was 125°C, and the hydroxyl equivalent (g/mol) was 104. Example 9. 472 g of product 1 (A-9) was obtained in the same manner as in Example 8 except that 640 g of 1,4-dihydroxynaphthalene was used in place of 1,6-dihydroxynaphthalene. Product (A
-9) has a softening temperature of 128°C and a hydroxyl equivalent (g/mol
) was 105. Example 10. Orthocresol 162g (
1.5 mol), 90 g of paraformaldehyde and 10 g of water
0 ml was placed in a 1 liter flask equipped with a thermometer, condenser, dropping funnel and stirrer, and stirred while blowing nitrogen. At room temperature, 15% sodium hydroxide aqueous solution 5
0 g (0.19 mol as sodium hydroxide) was slowly added dropwise to the solution while paying attention to heat generation so that the temperature of the solution did not exceed 50°C. Thereafter, the mixture was heated to 50° C. in a water bath and reacted for 10 hours. After the reaction is complete, add 300 ml of water, cool to room temperature, and neutralize with 10% aqueous hydrochloric acid solution while being careful not to generate heat.
Thereafter, the precipitated crystals were collected by filtration. The filtrate was washed until the pH became 6 to 7 and dried at 50°C under reduced pressure (10 mmHg) to give 197 g of white crystals (compound of formula [14]) (AO).
I got it. White crystals (AO) 197 thus obtained
1,6-dihydroxynaphthalene and 500 ml of methyl isobutyl ketone were added thereto, and the mixture was stirred at room temperature under a nitrogen atmosphere. and p-toluenesulfonic acid 2
g was slowly added dropwise to the solution 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 a water bath and reacted for 2 hours, and then transferred to a separatory funnel and washed with water. The cleaning water
After washing with water until it becomes neutral, add water/methanol solution (water/
After extracting unreacted dihydroxynaphthalene with methanol = 60/40 (wt%), 388 g of the resin (A-10) of the present invention was obtained by removing the solvent and unreacted substances from the organic layer under reduced pressure. Ta. The softening temperature (JIS K2425 ring and ball method) of the product (A-10) is 96°C
The hydroxyl equivalent (g/mol) was 99. Example 11. In Example 10, 1,6-
Product (A-11) 3 was prepared in the same manner as in Example 10 except that the amount of dihydroxynaphthalene used was 281 g.
93g was obtained. The softening temperature of product (A-11) is 108
The hydroxyl equivalent (g/mol) was 97 at °C. Example 12. In Example 10, 1,6-
385 g of product (A-12) was obtained in the same manner as in Example 10, except that 450 g of 1,4-dihydroxynaphthalene was used instead of dihydroxynaphthalene. The softening temperature of the product (A-12) was 107°C and the hydroxyl equivalent (g
/mol) was 96. Example 13. In Example 12, 1,4-
Product (A-13) 3 was prepared in the same manner as in Example 12 except that the amount of dihydroxynaphthalene used was 281 g.
79g was obtained. The softening temperature of product (A-13) is 110
The hydroxyl equivalent (g/mol) was 99 at °C. Analysis example 1. Regarding products (A-1) to (A-9), which are resins of the present invention obtained in Examples 1 to 9, G
PC analysis was performed, and a peak believed to be that of the compound represented by formula [2] was fractionated, and the mass spectrum (FAB-MS
) was analyzed. As a result, products (A-1) to (
M+ 452 for A-3), product (A-4),
M+ 494 for (A-5), product (A-6)
, M+ 472 and 474 were obtained for (A-7), and M+ 514 was obtained for products (A-8) and (A-9). Similarly, for the products (A-10) to (A-13) obtained in Examples 10 to 13, formula [5]
When a peak believed to be the compound was collected and analyzed by mass spectrometry, M+ 572 was obtained. Therefore, the products (A-1) to (A-13 obtained in Examples 1 to 13)
) contains the formula [2
] or the compound represented by formula [5] was confirmed to be included. [0095] The GPC analysis conditions are as follows. GPC device: Shimadzu Corporation (Column: TSK
-G-3000XL (1 piece) +TSK-G-2000X
L (2 bottles)) Solvent: Tetrahydrofuran 1ml
/min detection: UV (254nm) 0096
Table 1
Compound product represented by usage [2] contained in the product Structural formula
(molecular weight) Content (weight%)
)(A-1) The following formula [15]
(452) 55 (A-2)
The following formula [15] (452)
45(A-3) The following formula [16] (452)
53(A-4) The following formula [17]
(494) 52(A
-5) The following formula [18] (
494) 50 (A-6)
The following formula [19] (472.5)
56(A-7) The following formula [20]
(472.5) 53(A
-8) The following formula [21] (
514) 54(A-9)
The following formula [22] (514)
52 [Formula 34] [Formula 34] [Formula 35] [Formula 36] [Formula 36] [Formula 37] [Formula 38] [Formula 38] [Formula 40] [0104]
Table 2
Compound product represented by formula [5] contained in the product Structural formula
(Molecular weight) Content (weight%) (A
-10) The following formula [23] (5
72) 52 (A-11)
The following formula [23] (572)
43(A-12) The following formula [24]
(572) 53(
A-13) The following formula [24] (
572) 42 embedded image Example 14. The product (A-1) obtained in Example 1 (hydroxyl group equivalent (g/mo
l) 176 g of 88) and 920 g of epichlorohydrin were charged and the mixture was purged with nitrogen, and then 170 g of a 48% aqueous sodium hydroxide solution was added dropwise over 5 hours. During the dropwise addition, the produced water and the water in the aqueous sodium hydroxide solution were continuously removed from the reaction system by azeotropy with epichlorohydrin under conditions of a reaction temperature of 60° C. and a pressure of 100 to 150 mmHg, and epichlorohydrin was returned to the system. [0109] After recovering excess unreacted epichlorohydrin under reduced pressure, 1000 ml of methyl isobutyl ketone was recovered.
ml was added and washed with water until the aqueous layer became neutral. Methyl isobutyl ketone was removed from the organic layer under reduced pressure, and then 400 g of methyl isobutyl ketone was added again and redissolved. 40 g of a 20% aqueous 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, the aqueous layer was washed with water until it became neutral, and methyl isobutyl ketone was removed from the oil layer under reduced pressure to obtain 285 g of a pale yellow solid (B-1). Softening temperature (JI
S K2425) has an epoxy equivalent (g/mo
l) was 149. Example 15. The product obtained in Example 1 (A-1) was placed in a reactor equipped with a thermometer, a stirrer and a dropping funnel.
(Hydroxy group equivalent (g/mol) 88) 176 g, epichlorohydrin 920 g and dimethyl sulfoxide 460 g
After charging and purging with nitrogen, 80 g of sodium hydroxide was gradually added in a 30°C water bath. At 30°C for 5 hours, then at 50°C for 2 hours, then at 70°C, being careful not to generate heat.
The reaction was carried out 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. Next, 400 g of methyl isobutyl ketone was added and redissolved. 40 g of 20% aqueous 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, the aqueous layer was washed with water until it became neutral, and methyl isobutyl ketone was removed from the oil layer under reduced pressure to obtain 280 g of a pale yellow solid (B-2). The softening temperature of the product (B-2), which is the epoxy resin of the present invention, is 90°C and the epoxy equivalent (g/mol) is 148
Met. Example 16. Product (A-2) obtained in Example 2 instead of product (A-1) (hydroxyl equivalent: ■ (g/
The reaction was carried out in the same manner as in Example 14 except that 172 g of mol) 86) was used to obtain 307 g of product (B-3). The product (B-3), which is the epoxy resin of the present invention, had a softening temperature of 86°C and an epoxy equivalent (g/mol) of 149. Example 17. Product (A-3) obtained in Example 3 instead of product (A-1) (hydroxyl equivalent: ■ (g/
The reaction was carried out in the same manner as in Example 14 except that 178 g of the product (mol) 89) was used to obtain 298 g of product (B-4). The product (B-4), which is the epoxy resin of the present invention, had a softening temperature of 91° C. and an epoxy equivalent (g/mol) of 150. Example 18. Product (A-4) obtained in Example 4 instead of product (A-1) (hydroxyl equivalent: ■ (g/
The reaction was carried out in the same manner as in Example 14 except that 202 g of mol) 101) was used to obtain 305 g of product (B-5). The product (B-5), which is the epoxy resin of the present invention, had a softening temperature of 92°C and an epoxy equivalent (g/mol) of 157. Example 19. Product (A-5) obtained in Example 5 instead of product (A-1) (hydroxyl group equivalent: ■ (g/
The reaction was carried out in the same manner as in Example 14 except that 198 g of mol)99) was used to obtain 303 g of product (B-6). The product (B-6), which is the epoxy resin of the present invention, had a softening temperature of 90°C and an epoxy equivalent (g/mol) of 156. Example 20. Product (A-6) obtained in Example 6 instead of product (A-1) (hydroxyl group equivalent: ■ (g/
The reaction was carried out in the same manner as in Example 14 except that 186 g of mol)93) was used to obtain 280 g of product (B-7). Product (B-7), which is an epoxy resin of the present invention, had a softening temperature of 97°C and an epoxy equivalent (g/mol) of 155. Example 21. Product (A-7) obtained in Example 7 instead of product (A-1) (hydroxyl equivalent: ■ (g/
The reaction was carried out in the same manner as in Example 14 except that 190 g of mol)95) was used to obtain 277 g of product (B-8). The softening temperature of the product (B-8), which is the epoxy resin of the present invention, was 96°C and the epoxy equivalent (g/mol) was 158. Example 22. Product (A-8) obtained in Example 8 instead of product (A-1) (hydroxyl group equivalent
The reaction was carried out in the same manner as in Example 14 except that 208 g of mol) 104) was used to obtain 308 g of product (B-9). Product (B-9), which is an epoxy resin of the present invention, had a softening temperature of 99°C and an epoxy equivalent (g/mol) of 163. Example 23. Product (A-9) obtained in Example 9 instead of product (A-1) (hydroxyl group equivalent (g/m
The reaction was carried out in the same manner as in Example 14 except that 210 g of ol) 105) was used to obtain 299 g of product (B-10). The product (B-10), which is the epoxy resin of the present invention, has a softening temperature of 101°C and an epoxy equivalent (g/mol) of 16
It was 4. Example 24. Instead of product (A-1), the product (A-10) obtained in Example 10 (hydroxyl group equivalent (g
The reaction was carried out in the same manner as in Example 14, except that 192 g of the product (B-11) was used, and 294 g of the product (B-11) was obtained. The softening temperature of the product (B-11), which is the epoxy resin of the present invention, is 89°C and the epoxy equivalent (g/mol) is 15.
It was 7. Example 25. Product (A-11) obtained in Example 11 instead of product (A-1) (hydroxyl group equivalent (g
The reaction was carried out in the same manner as in Example 14 except that 194 g of the product (B-12) was used to obtain 290 g of product (B-12). The product (B-12), which is the epoxy resin of the present invention, has a softening temperature of 88°C and an epoxy equivalent (g/mol) of 15
It was 5. Example 26. Product (A-12) obtained in Example 12 instead of product (A-1) (hydroxyl group equivalent (g
The reaction was carried out in the same manner as in Example 14, except that 192 g of the product (B-13) was used, and 292 g of product (B-13) was obtained. The softening temperature of the product (B-13), which is the epoxy resin of the present invention, is 90°C and the epoxy equivalent (g/mol) is 15.
It was 6. Example 27. Product (A-13) obtained in Example 13 instead of product (A-1) (hydroxyl group equivalent (g
The reaction was carried out in the same manner as in Example 14, except that 198 g of the product (B-14) was used, and 294 g of the product (B-14) was obtained. The product (B-14), which is the epoxy resin of the present invention, has a softening temperature of 91°C and an epoxy equivalent (g/mol) of 15
It was 4. Analysis example 2. Products (B-1) to (B-14) obtained in Examples 14 to 27 were subjected to GPC analysis in the same manner as in Analysis Example 1, and the compounds represented by formula [6] or formula [9] were obtained. A peak believed to be was collected and analyzed by mass spectrometry (FAB-MS). the result,
M+ 732 for products (B-1) to (B-4)
, M+774 for products (B-5), (B-6)
, M+ 75 for products (B-7), (B-8)
2 and 754, and M+ 794 for products (B-9) and (B-10), and products (B-11) to (B-1
For 4), M+ 908 was obtained. Therefore, the products (B-1) to (B-14) obtained in Examples 14 to 27
), the formula [6
] or the compound represented by formula [9] was confirmed to be included. [0126]
Table 3
Compound product represented by formula [6] contained in the product Structural formula (molecular weight) Content (
Weight%) (B-1) The following formula [25]
(732) 49(
B-2) The following formula [25]
(732) 48 (B-3)
The following formula [25] (73
2) 38 (B-4)
The following formula [26] (732)
47(B-5) The following formula [27] (774)
45(B-6) The following formula [28]
(774) 44(
B-7) The following formula [29]
(752.5) 48 (B-8)
The following formula [30] (752.5)
46(B-9) The following formula [31] (794)
45(B-10) The following formula [32]
(794) 42 [
embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image embedded image ] [Chemical formula 51]
Table 4
Compound represented by formula [9] contained in the product Product Structural formula
(Molecular weight) Content (weight%) (B-11) Following formula [33]
(908) 46 (B
-12) The following formula [33]
(908) 38 (B-13)
The following formula [34] (908
) 47 (B-14)
The following formula [34] (908)
36 [Chemical formula 52] [Chemical formula 53] [Chemical formula 53] The value (average value) of n (in formula [1]) for the products (A-1) to (B-14) is as follows. It is as follows. Product n value
Product n value
(A-1) 0.5
(B-1) 0.5 (A-2
) 0.8 (
B-2) 0.5 (A-3)
0.6 (B-3)
0.8 (A-4) 0
．． 7 (B-4)
0.6 (A-5) 0.9
(B-5) 0.
7 (A-6) 0.7
(B-6) 0.9
(A-7) 0.8
(B-7) 0.7 (A-
8) 0.6
(B-8) 0.8 (A-9)
0.9 (B-9
) 0.6 (A-10) 0
．． 9 (B-10)
0.9 (A-11) 1.1
(B-11) 0.9
(A-12) 1.0
(B-12) 1.1 (A-1
3) 1.2 (B
-13) 1.0

(B-14) 1.2 Application Examples 1 to 13. Products (A-1) to (A-13) obtained in Examples 1 to 13 were used as curing agents, and cresol novolac type epoxy resin EOCN-10 was used as epoxy resin.
20 and 2-methylimidazole (2MZ) as a curing accelerator, a composition prepared by blending these in the proportions shown in Table 5 was roll-kneaded at 70 to 80°C for 15 minutes. After cooling, this was crushed, made into tablets, molded using a transfer molding machine, and precured at 160°C for 2 hours.
Post-curing was performed at 0° C. for 8 hours to obtain a cured product (test piece). The glass transition temperature (Tg) and water absorption rate of this cured product were measured. The evaluation results of the cured products are shown in Table 5. Application Examples 14-26. A commercially available phenol novolac resin (PN(H-1)) was used as a curing agent, and the products obtained in Examples 14 to 27 (B
Using -1) to (B-14) and 2-methylimidazole (2MZ) as a curing accelerator, these were mixed in the proportions shown in Table 6, and the following tests were carried out in the same manner as in Application Examples 1 to 13. went. The evaluation results of the cured products are shown in Table 6. Application Examples 27-35. The products obtained in Examples 1 to 13 were used as the curing agent, the products obtained in Examples 14 to 27 were used as the epoxy resin, and 2-methylimidazole (2MZ) was used as the curing accelerator.
They were blended in the proportions shown in the table and tested in the same manner as in Application Examples 1 to 13 below. Table 7 shows the evaluation results of the cured products. Application Comparative Examples 1 to 3. Phenol novolac resin (PN■(
H-1)) was cured using a cresol novolak type epoxy resin (EOCN1020), a polyphenol polyepoxy compound obtained by condensing aromatic aldehyde and phenol (EPPN502), and a bisphenol type epoxy resin (Epomic R301) as an epoxy resin. An accelerator was added, and the cured products were evaluated in the same manner as in Application Examples 1 to 13. The evaluation results are shown in Table 8. [0143] The equipment and conditions for measuring the glass transition temperature and water absorption are as follows. Glass transition temperature (℃): Thermomechanical measuring device (
TMA) Shinku Riko Co., Ltd.
TM-7000 Heating rate 2℃/min Water absorption rate (%)
: Test piece diameter
50
(cured product) thickness
3 Disk
condition
20 hours in 100℃ water

Weight gain after boiling

(weight%)
[0144]
Table 5 (1)
Application examples
1 2
3 4
Product (A-1) 88
Product (A-2)
86 Curing agent product (A-3
)
89 Product (A-4)

101
Product (A-5) Product (A-6) Product (A-
7) Epoxy resin EOCN-1020 20
0 200 200 200 Curing accelerator (2MZ) 2.0
2.0 2.0 2.0 Glass transition temperature (℃) 190
188 187 181 Water absorption rate
(%) 0.8
0.9 0.8 0.9 01
45]
Table 5 (2)
Application examples
5 6
7 Product (
A-1) Product (A-2
) Curing agent Product (A-3)
Product (A-4)
Product (A-5) 99
Product (A-6)
93 Product (A-7)
95 epoxy resin EOCN-1020
200 200 200 Curing accelerator (
2MZ) 2.0 2.
0 2.0 Glass transition temperature (℃)
180 183 181 Water absorption rate (%) 0.
9 0.8 0.9 0146]
Table 5 (3)

Application examples
8
9 10
Product (A-8)
104 Product (A-9)
105 hardening agent
Product (A-10)
96
Product (A-11)
Product (A-12)
Product (A-13) Epoxy resin
EOCN-1020 200
200 200 curing accelerator (2MZ)
2.0 2.
0 2.0 Glass transition temperature (℃)
192 188
188 Water absorption rate (%)
0.8 0.8
0.8 0147
Table 5 (4)

Application examples
11
12 13
Product (A-8)
Product (A-9) Curing agent
Product (A-10) Product (A-11) 97
Product (A-12)
96 Product (A-13)
99 epoxy resin EO
CN-1020 200 2
00 200 curing accelerator (2MZ)
2.0 2.
0 2.0 Glass transition temperature (℃)
186 187
186 Water absorption rate (%)
0.9
0.9 0.9 0148]
Table 6 (1)

Application examples
14
15 16 17
Product (B-1)
148
Product (B-3) 149
Product (B-4
)
150 epoxy resin product (B-5)

157
Product (B-6)
Product (B-7)
Product (B-8) Curing agent
PN (H-1) 106 106
106 106 Curing accelerator (2MZ)
1.5 1.5
1.5 1.6 Glass transition temperature (℃)
188 186
182 179 Water absorption rate (%)
0.8
0.8 0.9 0.9 0149]
Table 6 (2)

Application examples
18
19 20
Product (B-1)
Product (B-3)
Product (B-4) Epoxy resin Product (B-5)
Product (B-6) 15
6 Product (B-
7) 155
Product (B-8)

158 Curing agent PN (H-
1) 106 106 1
06 Curing accelerator (2MZ)
1.6 1.6 1.
6 Glass transition temperature (℃)
180 184 182
Water absorption rate (%)
0.9 0.8
0.8 0150
Table 6 (3)

Application examples

21 22 23
Product (B-9)
163
Product (B-10) 16
4 Product (B-
11)
157 Epoxy resin product (B-
12) Product (
B-13) Product (B-14) Curing agent PN
(H-1) 106 106
106 curing accelerator (2MZ)
1.6 1.6
1.6 Glass transition temperature (℃)
186 185
188 Water absorption rate (%)
0.9 0.9
0.8 0151
Table 6 (4)
Application examples
24
25 26
Product (B-9)
Product (B-10)
Product (B-11) Epoxy resin Product (B-12) 155
Product (B-13)
156
Product (B-14)
155 hardening agent
PN (H-1) 10
6 106 106 Curing accelerator (
2MZ) 1.6
1.6 1.6 Glass transition temperature (℃) 187
183 182 Water absorption rate (%)
0
．． 9 0.9 0.9 0152
]
Table 7 (1)

Application examples
27
28 29
Product (B-1)
148 Product (
B-3) 149
Product (B-4)

150 epoxy resin product (B-6)
Product (B-8
)────────────────────────
────────────
Product (A-1) 88
Product (A-2)
86
Product (A-3)
89
Curing agent product (A-5)
Product (A-7)
Product (A-11
) Curing accelerator (2MZ)
1.5 1.5 1.5
Glass transition temperature (℃)
192 193 189 Water absorption rate (%)
0.7 0.7 0
．． 8 0153]
Table 7 (2)

Application examples
30
31 32
Product (B-1)
Product (B-3)
Product (B-4) Epoxy resin Product (B-6) 156
Product (B-8
) 158────────
──────────────────────────
──── Product (A-1) Product (A-2) Product (A-3) Curing agent Product (A-5) 99
Product (A-7)
95
Product (A-11)
97 curing accelerator (2MZ)
1.6
1.6 1.6 Glass transition temperature (℃)
186
188 184 Water absorption rate (%)
0.8
0.9 0.8 0154
Table 7 (3)

Application examples
33
34 35
Product (B-9)
148 Epoxy resin product (B-11)
149
Product (B-13)
150─────
──────────────────────────
────── Product (A-8) 88 Curing agent
Product (A-10)
86 Product (
A-12)
89 Curing accelerator (2MZ)
1.5 1.5
1.5 Glass transition temperature (℃)
194 192
188 Water absorption rate (%)
0.8 0
．． 7 0.7 0155
Table 8

Application comparison example
1
2 3
EOCN-1020
200 epoxy resin EPPN-502
168
Epomic R-301
470 Curing Agent PN- (H-1)
106 106 106 Curing accelerator (2MZ) 2
．． 0 1.7 4.7 Glass transition temperature (℃) 16
2 177 125 Water absorption rate (
%)
1.4 2.0 1.2 [0156] The commercially available resins blended are as follows. PN (H-1): (Nippon Kayaku) Phenol novolak resin Hydroxyl group equivalent (g/mol) 106
Softening temperature 85℃
EOCN-1020: (Nippon Kayaku) Cresol novolac type epoxy resin
Epoxy equivalent (g/mol) 200
Softening temperature
65°C 0157 Efomic R-301: (Mitsui Petrochemical Epoxy) Bisphenol A epoxy resin Epoxy equivalent (g/mol) 470
Softening temperature 68℃EPPN502: (Nippon Kayaku) Polyepoxy compound
Epoxy equivalent (g/mol) 168
Softening temperature
70°C [0158] Effects of the Invention The resin of the present invention has a low softening temperature and is excellent in workability. Moreover, the cured product obtained using this resin has a high glass transition temperature and a high heat distortion temperature, which are indicators of heat resistance, and can have a lower water absorption rate than conventional resins. Therefore, the resin of the present invention can fully meet the recent demands for high heat resistance and low water absorption, and can be used in a wide range of fields, specifically as encapsulating materials for electronic components, molding materials, etc. Extremely useful as a material for lamination.

Claims (13)

[Claims] Claim 1: Formula [1] [Chemical 1] (wherein A is the formula [A1] [Chemical 2] or formula [A2] [Chemical 3], R is an alkyl group having 1 to 4 carbon atoms, A resin represented by an aryl group or a halogen atom; 2. A compound represented by the formula [2] embedded image (wherein R represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom). [Claim 3] Formula [3] [C6] A compound represented by [Claim 4] Formula [4] [Chemical 7] A compound represented by [Claim 5] Formula [5] [Chemical formula 8] A compound represented by 6. An epoxy compound represented by the formula [6] embedded image (wherein R represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom). [Claim 7] Formula [7] [Chemical formula 10] An epoxy compound represented by [Claim 8] Formula [8] [Chemical formula 11] An epoxy compound represented by [Claim 9] Formula [9] [Chemical formula 12] An epoxy compound represented by [Claim 10] Formula [10] [Chemical 13] (wherein, R represents an alkyl group having 1 to 4 carbon atoms, an aryl group, or a halogen atom; or formula [11] [Chemical 14] (wherein, R has the same meaning as above) and dihydroxynaphthalene represented by the formula [12] [Chemical 15], and in the formula [1] of claim 1, where n=O A resin in which X is H in formula [1] according to claim 1, which contains 30% by weight or more of a compound where X=H. Claim 11: The resin of Claim 10 is prepared by formula [13] [Chemical formula 1
6] (In the formula, Y represents a halogen atom) obtained by reacting with an epihalohydrin compound represented by the formula [1
] wherein n=O and X contains 30% by weight or more of a compound representing the formula [XE] of claim 1, wherein in formula [1] of claim 1, X represents the formula [XE] of claim 1. 12. In an epoxy resin composition containing an epoxy resin, a curing agent, and a curing accelerator, (A) as the epoxy resin, in the formula [1] of claim 1, X represents the formula [XE] of claim 1; An epoxy resin composition using a resin or a resin according to claim 11 and/or a resin in which X is H in formula [1] according to claim 1 or a resin according to claim 10 as (B) a curing agent. 13. A cured product of the epoxy resin composition according to claim 12.