JP2005187607A - Phenolic resin, epoxy resin, epoxy resin composition and cured product of the composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an epoxy resin composition(epoxy-based material) of reduced dielectric constant or dielectric dissipation factor required for electrical and electronic epoxy-based materials. <P>SOLUTION: The epoxy resin composition comprises an epoxy resin and a new phenolic compound 190-350 g/eq in hydroxy equivalent that is obtained by reaction between a phenolic hydroxy-bearing aromatic hydrocarbon, an aromatic hydrocarbon having two vinyl groups(b1) and an aromatic hydrocarbon having one vinyl group(b2), wherein the phenolic compound is represented by general formula(1)( wherein, A is the residue of the phenolic hydroxy-bearing aromatic hydrocarbon; R is a 1-6C alkyl; k is an average of 1-3; and m is the number of recurring units, being 1-6 ). In this epoxy resin composition, the weight ratio b2/b1 is 0.1-1.5. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  This invention provides the epoxy resin composition suitable for the material for printed circuit boards excellent in an electrical property, the phenolic compound contained in this, and an epoxy resin.

  Epoxy-based materials are widely used in electrical and electronic materials because excellent insulation, adhesiveness, heat resistance, and moldability can be obtained by thermally curing an epoxy resin curing agent and an epoxy resin. In recent years, in order to cope with an increase in capacity and speed of information processing, there has been a strong demand for reduction of dielectric constant and dielectric loss tangent for electric and electronic materials. However, in the conventional epoxy-based material, the secondary hydroxyl group generated by the curing reaction has a property of increasing the dielectric constant and the dielectric loss tangent, so that the requirement cannot be satisfied. In order to reduce the secondary hydroxyl group in the cured product, it is considered preferable to use a resin having as high a hydroxyl equivalent or epoxy equivalent as possible. Further, considering the maintenance of heat resistance, a modified resin having a novolac skeleton is considered to be effective (see, for example, Patent Document 1). However, there is a limit to the reduction of secondary hydroxyl groups by these existing modified novolak resins, and the effect is insufficient for reducing the dielectric constant and dielectric loss tangent.

JP-A-5-78457 (page 2-4)

  Accordingly, an object of the present invention is to provide an epoxy resin composition (epoxy material) that can reduce the dielectric constant and dielectric loss tangent required for an epoxy material for electrical and electronic applications.

As a result of intensive studies to solve the above problems, the present inventor has obtained the following knowledge.
(1) When an epoxy resin composition containing a phenol having a high hydroxyl equivalent and an epoxy resin having a high epoxy equivalent is used, a cured product having a low dielectric constant and dielectric loss tangent can be obtained.
(2) When an aromatic hydrocarbon having one vinyl group and an aromatic hydrocarbon having two vinyl groups are reacted with a phenol compound, a phenol having a high hydroxyl equivalent can be obtained.
(3) The epoxy resin derived from phenols and epichlorohydrin obtained by the method (2) also has a high epoxy equivalent.
(4) The phenol compound (2) and the epoxy resin (3) are novel compounds.

  The present invention is based on such knowledge. That is, the present invention reacts an aromatic hydrocarbon (a) having a phenolic hydroxyl group, an aromatic hydrocarbon (b) having two vinyl groups, and an aromatic hydrocarbon (b) having one vinyl group. An epoxy resin composition characterized by containing a phenol compound (A1) and an epoxy resin (A2) of a hydroxyl group equivalent of 190 to 350 g / equivalent (hereinafter, g / equivalent is referred to as g / eq), A cured product is provided.

  The present invention also provides a phenol compound having a hydroxyl group equivalent of 190 to 350 g / eq represented by the following general formula (2).

（式中のＲ^１は、下記構造式（３）を表わし、ｎは１〜４の繰り返し単位数を、また、ｄ、ｅ、ｆ、ｇは、それぞれ、独立に、１≦（ｄ＋ｅ）≦６、１≦（ｆ＋ｇ）≦６満足する。）

(Wherein R ¹ represents the following structural formula (3), n represents the number of repeating units of 1 to 4, and d, e, f, and g are each independently 1 ≦ (d + e) ≦ 6, 1 ≦ (f + g) ≦ 6 is satisfied.)

（式中のＲ^２は、メチル基またはエチル基を表す。）

(R ² in the formula represents a methyl group or an ethyl group.)

  The present invention also provides an epoxy resin having an epoxy equivalent of 280 to 550 g / equivalent (hereinafter, g / equivalent is referred to as g / eq) represented by the general formula (4).

（式中のＲ^１、ｎ、ｄ、ｅ、ｆ、ｇは、前記と同一であり、Ｇは、グリシジル基を表す。

(Wherein R ¹ , n, d, e, f, and g are the same as described above, and G represents a glycidyl group).

  According to the epoxy resin composition of the present invention, a cured epoxy resin having a reduced dielectric constant and dielectric loss tangent can be obtained without impairing moisture resistance and solder resistance, which are basic required characteristics of a printed wiring board. can get.

  The phenol compound (A1) used in the epoxy resin composition of the present invention is composed of an aromatic hydrocarbon (a) having a phenolic hydroxyl group, an aromatic hydrocarbon (b2) containing two vinyl groups, and one vinyl group. It is obtained by reacting with the aromatic hydrocarbon (b1) contained, and the hydroxyl equivalent is 190 to 350 g / eq.

  This reaction includes a process in which a hydrogen atom on the aromatic ring of the aromatic hydrocarbon (a) containing a phenolic hydroxyl group is added to the α-position carbon of the vinyl group of the compound (b2) to form a methyl group, and The process of adding a methyl group by adding to the α-position carbon of the vinyl group of the compound (b1) and the β-position carbon of the cleaved vinyl group of the compounds (b2) and (b1) This is done by adding a hydrogen atom on the ring to a position where it has become vacant.

  This addition reaction is performed in the presence of an acid catalyst. Moreover, you may use an organic solvent as needed. The acid catalyst is not particularly limited as long as it is a catalyst usually used for this kind of reaction. For example, hydrochloric acid, sulfuric acid, sulfuric anhydride, p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfone Examples include acid, oxalic acid, formic acid, phosphoric acid, trichloroacetic acid, trifluoroacetic acid and the like. The addition amount of the catalyst is preferably in the range of 0.01 to 10% by weight with respect to the phenols. The organic solvent includes aromatic organic solvents such as benzene, toluene and xylene, ketone organic solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, and alcohols such as methanol, ethanol, isopropyl alcohol and normal butanol. An organic solvent or the like can be used, and it may be selected as appropriate in consideration of properties such as solubility of raw materials and products used, reaction conditions, economy, and the like. The amount of the organic solvent is preferably in the range of 10 to 500% by weight with respect to the total weight of the phenol and the vinyl compound. The reaction conditions are usually from room temperature to 200 ° C., preferably from 50 to 150 ° C., and may be heated and stirred for about 0.5 to 30 hours. After completion of the reaction, neutralize with alkali such as caustic soda and sodium bicarbonate or organic base such as ammonia or triethylamine or deactivate the acid catalyst by washing with water, and then remove excess unreacted components and solvent. Is removed by distillation or the like. The catalyst may be deactivated after removing unreacted components. In that case, after diluting with a hydrophobic organic solvent such as toluene, washing with water may be repeated until neutralization with an alkali or organic base or neutrality.

  Examples of the aromatic hydrocarbon (a) having a phenolic hydroxyl group include phenol, bisphenols such as bisphenol F and bisphenol A, alkylphenols such as cresol and butylphenol, halogenophenols such as bromophenol, resorcin, and catechol. And dihydroxys such as hydroquinone, aromatic hydrocarbons having 3 or more phenolic hydroxyl groups such as novolak, and naphthols such as naphthol and dihydroxynaphthalene. Two or more of these may be used in combination. Among these, bisphenol A is particularly preferable in that it has an excellent balance between performance and cost.

  The aromatic hydrocarbon (b2) containing two vinyl groups is not particularly limited except that it has two vinyl groups. For example, aromatic divinyl such as divinylbenzene, alkyldivinylbenzene, diallyl phthalate, etc. Compounds. Two or more of these may be used in combination. Of these, divinylbenzene is particularly preferable in terms of excellent reactivity and workability.

  In addition, examples of the aromatic hydrocarbon (b1) containing one vinyl group include aromatic monovinyl compounds such as styrene, ethylstyrene, and monobromostyrene, but styrene and ethyl are excellent in reactivity and workability. Styrene is particularly preferred.

  The mixing ratio of the aromatic hydrocarbon (b2) containing two vinyl groups and the aromatic hydrocarbon (b1) containing one vinyl group in the reaction is such that the hydroxyl equivalent of the resulting phenol compound is 190 to 190. If it is 350 g / eq, it will not specifically limit, What is necessary is just to adjust suitably so that the number of desired functional groups (hydroxyl group) per molecule may be obtained. Among these, the weight ratio [(b2) / (b1)] is preferably 0.1 or more because the number of functional groups (hydroxyl groups) per molecule is large and the heat resistance of the cured product is improved. Since gelation or the like hardly occurs during the reaction, 1.5 or less is preferable, and the weight ratio is particularly preferably in the range of 0.2 to 1.3.

  The phenol compound (A1) has, for example, a structure that can be represented by the following general formula (1).

（式中、Ａはフェノール性水酸基を有する芳香族炭化水素を、Ｒは炭素数１〜６のアルキル基を、ｋは、１〜３の平均値を、ｍは１〜６の繰り返し単位数示す。）

(In the formula, A represents an aromatic hydrocarbon having a phenolic hydroxyl group, R represents an alkyl group having 1 to 6 carbon atoms, k represents an average value of 1 to 3, and m represents the number of repeating units of 1 to 6). .)

  Examples of the structure of A in the general formula (1) include phenols, bisphenols such as bisphenol F and bisphenol A, alkylphenols such as cresol and butylphenol, halogenophenols such as bromophenol, resorcin, catechol, and hydroquinone. Aromatic hydrocarbons having a vinyl group from aromatic hydrocarbons having 3 or more phenolic hydroxyl groups such as dihydroxys such as novolac, naphthols such as naphthol and dihydroxynaphthalene [the compounds (b1) and (b2)] And a residue from which a hydrogen atom has been removed. Two or more of these may be used in combination. Among these, those having a bisphenol A skeleton are particularly preferable in terms of excellent balance between performance and cost.

  The epoxy resin (A2) used in the present invention is not particularly limited. For example, the epoxy resin derived from the phenol compound (A1) and epihalohydrin, or other various epoxy resins can be used, and is not particularly limited. It is not something. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy Resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin , Aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolak type epoxy resin, tetrabromo Scan phenol A type epoxy resins, such as brominated phenol novolak type epoxy resins. Moreover, these epoxy resins may be used independently and may mix 2 or more types.

  Among these, the epoxy resin derived from the phenol compound (A1) and epihalohydrin is preferable because the dielectric constant and dielectric loss tangent of the resulting cured product is low, and the epoxy equivalent is particularly in the range of 280 to 550 g / eq. Those are preferred.

  In the epoxy resin composition of this invention, you may use a hardening accelerator further as needed. Various curing accelerators are used, and examples thereof include tertiary amines such as benzyldimethylamine, imidazole, organic acid metal salts, Lewis acids, amine complex salts, and the like. Combinations of more than one species are possible.

Furthermore, the epoxy resin hardening | curing agent mentioned later can also be used together as needed. In this case, the phenol compound (A1) may be contained in an amount of 30 parts by weight or more, particularly 40 parts by weight or more per 100 parts by weight in total of the epoxy resin curing agent used in combination with the phenol compound (A1) as necessary. preferable. As the curing agent for epoxy resin, various curing agents such as amine compounds, acid anhydride compounds, amide compounds and phenol compounds can be used. For example, diaminodiphenylmethane, diethylenetriamine, triethylene Polyamide resin synthesized from tetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid dimer and ethylenediamine, phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, Methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin modified phenol Fatty, dicyclopentadiene phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolac resin, naphthol-phenol co-condensed novolac resin, naphthol-cresol co-condensed novolac resin, biphenyl Examples include, but are not limited to, polyphenol compounds such as modified phenol resins and aminotriazine-modified phenol resins, and modified products thereof, imidazoles, BF ₃ -amine complexes, guanidine derivatives, and the like. .

  In the epoxy resin composition of the present invention, the amount of the curing agent component (the epoxy resin curing agent used in combination with the phenol compound (A1) as necessary) is an epoxy resin epoxy resin because good cured properties can be obtained. The amount of active hydrogen groups in the curing agent component is preferably 0.7 to 1.5 equivalents relative to 1 equivalent of the group.

  An inorganic filler can be used in the epoxy resin composition of the present invention as necessary. Examples thereof include calcium carbonate, barium sulfate, fused silica, crystalline silica, alumina, silicon nitride, and aluminum nitride. The filling rate is preferably higher from the viewpoint of flame retardancy. Moreover, various compounding agents, such as a silane coupling agent, a mold release agent, and a pigment, can be added as needed.

  Moreover, a flame retardant imparting agent can be added as necessary. Various flame retardants can be used, and examples thereof include halogen compounds, phosphorus atom-containing compounds, nitrogen atom-containing compounds, and inorganic flame retardant compounds. Specific examples thereof include halogen compounds such as tetrabromobisphenol A type epoxy resin, phosphorus atom-containing compounds such as red phosphorus and phosphate compounds, nitrogen atom-containing compounds such as melamine, aluminum hydroxide, magnesium hydroxide, boric acid Examples thereof include inorganic flame retardant compounds such as zinc, calcium borate, and boric acid.

  The epoxy resin composition of the present invention can be easily made into a cured product by the same methods as various methods. For example, an epoxy resin composition is obtained by thoroughly mixing an epoxy resin and a compounding agent such as a curing agent and a filler as necessary using an extruder, a kneader, a roll and the like until uniform. The epoxy resin composition is melted and then molded using a casting or transfer molding machine, and further heated at 80 to 200 ° C. for 2 to 10 hours to obtain a cured product. Further, the epoxy resin composition of the present invention can be dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, etc. to be varnished and used as a coating material. Furthermore, a prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper and the like with heat and drying the varnish can be subjected to hot press molding to obtain a cured product. The solvent used here is usually 10 to 70% by weight, preferably 15 to 65% by weight in the mixture of the epoxy resin composition of the present invention and the solvent.

The phenol compound of the present invention is a phenol compound having a hydroxyl group equivalent of 190 to 350 g / eq represented by the general formula (2). Among these, those in which n is 1 to 4 and R ² is an ethyl group are preferable. The phenol compound of this invention is obtained by the method similar to the said phenol compound (A1), for example.

  The epoxy resin of the present invention has an epoxy equivalent of 280 to 550 g / eq represented by the general formula (3), and is obtained, for example, by a reaction from a phenol resin represented by the general formula (2) and an epihalohydrin. Can do.

Various methods can be adopted as a reaction method for obtaining the epoxy resin. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a dissolved mixture of a phenol resin represented by the general formula (2) and an epihalohydrin such as epichlorohydrin or epibromohydrin, or while adding 20 The epoxy resin of this invention is obtained by making it react at -120 degreeC for 1 to 10 hours. The addition amount of epihalohydrin is usually in the range of 0.3 to 20 equivalents relative to 1 equivalent of hydroxyl group in the phenol resin as a raw material. When the epihalohydrin is less than 2.5 equivalents, an epoxy group and an unreacted hydroxyl group are likely to react with each other. Therefore, a group formed by an addition reaction between an epoxy group and an unreacted hydroxyl group (—CH ₂ CR (OH) CH ₂ —, A high molecular weight product containing R: a hydrogen atom or an organic carbon group is obtained. On the other hand, when it is more than 2.5 equivalents, the content of the theoretical structure becomes high. The amount of epihalohydrin may be appropriately adjusted according to desired characteristics.

In the reaction for obtaining the epoxy resin of the present invention, an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and under reduced pressure. Alternatively, water and epihalohydrin may be continuously distilled off under normal pressure, followed by liquid separation, removal of water, and epihalohydrin being continuously returned to the reaction system. Further, it is obtained by adding a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride as a catalyst to the dissolved mixture of the phenol resin and epihalohydrin and reacting at 50 to 150 ° C. for 1 to 5 hours. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the halohydrin etherified product of the phenol resin and reacting again at 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) may be used.

  Furthermore, alcohols such as methanol, ethanol, isopropyl alcohol and butanol, ketones such as acetone and methyl ethyl ketone, ethers such as dioxane, aprotic polar solvents such as dimethyl sulfone and dimethyl sulfoxide, etc. are used in order to facilitate the reaction. It is preferable to carry out the reaction by adding. The amount of the solvent used is usually 5 to 50% by weight, preferably 10 to 30% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, it is 5-100 weight% normally with respect to the quantity of epihalohydrin, Preferably it is 10-60 weight%.

  After the epoxidation reaction product is washed with water or without washing with water, epihalohydrin and other added solvents are removed at 110 to 250 ° C. under a pressure of 10 mmHg or less under reduced pressure. Further, in order to obtain an epoxy resin with less hydrolyzable halogen, the crude epoxy resin obtained after recovering epihalohydrin or the like is dissolved again in a solvent such as toluene or methyl isobutyl ketone, and an alkali such as sodium hydroxide or potassium hydroxide is obtained. An aqueous solution of a metal hydroxide can be added and further reacted to ensure ring closure. In this case, the amount of alkali metal hydroxide used is usually 0.5 to 10 mol, preferably 1.2 to 5.0 mol, per 1 mol of hydrolyzable chlorine remaining in the crude epoxy resin. The reaction temperature is usually 50 to 120 ° C., and the reaction time is usually 0.5 to 3 hours. For the purpose of improving the reaction rate, a phase transfer catalyst such as a quaternary ammonium salt or crown ether may be present. The amount of the phase transfer catalyst used is preferably in the range of 0.1 to 3.0% by weight based on the crude epoxy resin. After completion of the reaction, the produced salt is removed by filtration, washing with water, and the solvent of toluene, methyl isobutyl ketone, etc. is distilled off under heating and reduced pressure to obtain the epoxy resin of the present invention.

EXAMPLES Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, parts and% are based on weight unless otherwise specified.

Example 1
To a 4-neck 3 liter flask equipped with a stirrer, condenser, thermometer and dropping funnel, 530 g of bisphenol A, 530 g of MIBK, and 1 g of paratoluenesulfonic acid as a catalyst were added, and the temperature was raised to 100 ° C. A mixture of 152 g of divinylbenzene, 38 g of ethylstyrene and 210 g of styrene was dropped little by little from the dropping funnel, and the mixture was dropped over about 1 hour while maintaining the temperature at 100 to 110 ° C., and then reacted for 10 hours. After cooling to 80 ° C., 2 g of sodium hydroxide and 500 g of water were added and stirred at 80 ° C. for 30 minutes. After liquid separation and discarding of the aqueous layer, the mixture was heated to 120 ° C. while being distilled and filtered. Furthermore, it heated up to 180 degreeC and refine | purified by vacuum distillation. Taking out from the reaction vessel, 1050 g of a solid phenol compound having a softening point of 83 ° C. and a hydroxyl group equivalent of 220 g / eq was obtained. The infrared absorption spectrum and nuclear magnetic resonance spectrum of the obtained phenol compound are shown in FIGS. 1-1 and 1-2. In addition, n (in General formula (2)) of the obtained phenol compound was 0.7.

Example 2
While performing nitrogen gas purging on a flask equipped with a thermometer, a dropping funnel, a condenser, and a stirrer, 220 g of phenol compound obtained in Example 1 (hydroxyl group 1.0 equivalent), 467 g of epichlorohydrin (6.0 mol), n- 53 g of butanol and 2.3 g of tetraethylbenzylammonium chloride were charged and dissolved. After raising the temperature to 65 ° C., the pressure was reduced to an azeotropic pressure, and 82 parts (1.0 mol) of a 49% aqueous sodium hydroxide solution was added dropwise over 5 hours, and then stirred for 0.5 hours under the same conditions. Continued. During this time, the distillate distilled azeotropically was separated by a Dean-Stark trap, the aqueous layer was removed, and the reaction was carried out while returning the oil layer to the reaction system. Thereafter, unreacted epichlorohydrin was distilled off under reduced pressure. 550 parts of methyl isobutyl ketone and 55 parts of n-butanol were added to the crude epoxy resin thus obtained and dissolved. Further, 15 parts of a 10% aqueous sodium hydroxide solution was added to this solution and reacted at 80 ° C. for 2 hours. Then, washing with 100 g of water was repeated three times until the pH of the washing solution became neutral. Next, the system was dehydrated by azeotropic distillation, and after microfiltration, the solvent was distilled off under reduced pressure to obtain 300 g of an epoxy resin. The resulting epoxy resin had a softening point of 60 ° C. and an epoxy equivalent of 330 g / eq.

Example 3
To a four-necked 3 liter flask equipped with a stirrer, a condenser, a thermometer and a dropping funnel, 530 g of bisphenol A, 1000 g of MIBK, and 1 g of paratoluenesulfonic acid as a catalyst were added, and the temperature was raised to 100 ° C. A mixture of 220 g of divinylbenzene and 180 g of ethylstyrene was dropped little by little from the dropping funnel and dropped over about 1 hour while maintaining the temperature at 100 to 110 ° C., and then reacted for 10 hours. After cooling to 80 ° C., 2 g of sodium hydroxide and 500 g of water were added and stirred at 80 ° C. for 30 minutes. After liquid separation and discarding of the aqueous layer, the mixture was heated to 120 ° C. while being distilled and filtered. Furthermore, it heated up to 180 degreeC and refine | purified by vacuum distillation. The solid phenol compound having a softening point of 105 ° C. and a hydroxyl group equivalent of 220 g / eq was obtained from the reaction vessel. The infrared absorption spectrum and nuclear magnetic resonance spectrum of the obtained phenol compound are shown in FIGS. 2-1 and 2-2. In addition, n (in General formula (2)) of the obtained phenol compound was 2.1.

Example 4
Example 2 was repeated except that the raw material phenol compound was changed to 220 g of the phenol resin obtained in Synthesis Example 3. The obtained epoxy resin was 300 g, the softening point was 60 ° C., and the epoxy equivalent was 330 g / eq.

Synthesis Comparative Example 1
To a 4-neck 3 liter flask equipped with a stirrer, condenser, thermometer and dropping funnel, 530 g of bisphenol A, 530 g of MIBK, and 1 g of paratoluenesulfonic acid as a catalyst were added, and the temperature was raised to 100 ° C. A mixture of 152 g of divinylbenzene and 38 g of ethylstyrene was dropped little by little with a dropping funnel and dropped over about 1 hour while maintaining the temperature at 100 to 110 ° C., followed by reaction for 10 hours. After cooling to 80 ° C., 2 g of sodium hydroxide and 500 g of water were added and stirred at 80 ° C. for 30 minutes. After liquid separation and discarding of the aqueous layer, the mixture was heated to 120 ° C. while being distilled and filtered. Furthermore, it heated up to 180 degreeC and refine | purified by vacuum distillation. Taking out from the reaction vessel, 705 g of a solid modified novolak resin having a softening point of 90 ° C. and a hydroxyl group equivalent of 160 g / eq was obtained.

Synthesis Comparative Example 2
The same procedure as in Example 2 was performed except that the raw material phenol resin was changed to 160 g of the phenol resin obtained in Synthesis Comparative Example 1. The obtained epoxy resin was 210 g, the softening point was 65 ° C., and the epoxy equivalent was 230 g / eq.

Examples 5 and 6 and Comparative Example 1
A resin varnish was prepared according to the formulation shown in Table 1 to obtain an epoxy resin composition. At this time, the curing agent and the epoxy resin were mixed in an equivalent ratio of 1: 1. Moreover, as a hardening accelerator, it was set as the ratio used as 0.1 part with respect to 100 parts of epoxy resins of the main ingredient. Next, each of the mixed solutions was cured under the following conditions to produce a double-sided copper-clad laminate. The obtained double-sided copper-clad laminate was subjected to an etching treatment, and after removing the copper foil, each physical property test was performed under the following conditions. The results are shown in Table 1.
(Laminate production conditions)
Base material: glass cloth (# 7628 type), number of plies: 8, prepreg condition: 160 ° C./3 minutes, copper foil: 35 μm, curing condition: 170 ° C. for 1 hour / 40 kg / cm ² , thickness after molding : 1.5 mm, resin content: 38%

(Measurement conditions for each physical property test)
Glass transition point: by DMA (temperature increase speed 3 ° C / min)
Pre-shear cooker test (PCT): The test piece was processed for a predetermined time in 121 degreeC water vapor | steam.
Moisture resistance and solder resistance test: Evaluation was performed by immersing in a solder bath at 260 ° C. for 20 seconds after PCT treatment. The evaluation was performed by visual judgment on the appearance of the test piece, in particular, the presence or absence of mesuring. Judgment criteria: ○: No abnormality at all, △: Slightly mis-seen, x: Missed

2 is an infrared absorption spectrum of the resinous material obtained in Example 1. It is a nuclear magnetic resonance spectrum of the resinous material obtained in Example 1. 2 is an infrared absorption spectrum of the resinous material obtained in Example 2. 2 is a nuclear magnetic resonance spectrum of the resinous material obtained in Example 2.

Claims (9)

Hydroxyl equivalent weight 190-90 obtained by reacting an aromatic hydrocarbon (a) having a phenolic hydroxyl group, an aromatic hydrocarbon (b1) having two vinyl groups and an aromatic hydrocarbon (b2) having one vinyl group An epoxy resin composition comprising 350 g / equivalent phenol compound (A1) and epoxy resin (A2). The epoxy resin composition according to claim 1, wherein the phenol compound (A1) has a structure represented by the following general formula (1).

(In the formula, A is an aromatic hydrocarbon residue having a phenolic hydroxyl group, R is an alkyl group having 1 to 6 carbon atoms, k is an average value of 1 to 3, and m is a repetition of 1 to 6) Indicates the number of units.) The weight ratio [(b2) / (b1)] of the aromatic hydrocarbon (b2) containing two vinyl groups and the aromatic hydrocarbon (b1) containing one vinyl group is 0.1 to 1.5. The epoxy resin composition according to claim 1. The epoxy resin composition according to claim 3, wherein the aromatic hydrocarbon (a) having two or more phenolic hydroxyl groups is a bisphenol compound. The epoxy resin composition according to claim 4, wherein the compound (b2) having two vinyl groups is divinylbenzene, and the compound (b1) having one vinyl group is ethylstyrene or styrene. The epoxy resin composition according to claim 1, wherein the epoxy resin (A2) is a 280 to 550 g / equivalent epoxy resin derived from the phenol compound (A1) and epichlorohydrin. Hardened | cured material obtained by hardening the epoxy resin composition as described in any one of Claims 1-6. A phenolic compound having a hydroxyl group equivalent of 190 to 350 g / equivalent to the following general formula (2).

(In the formula, R ¹ represents the following structural formula (3), n represents the number of repeating units of 0 to 6, and d, e, f, and g are each independently 1 ≦ (d + e) ≦. 6, 1 ≦ (f + g) ≦ 6 is satisfied.)

(R ² in the formula represents a methyl group or an ethyl group.) An epoxy resin having an epoxy equivalent of 280 to 550 g / equivalent represented by the following general formula (4).

(Wherein R ¹ , n, d, e, f, and g are the same as described above, and G represents a glycidyl group).

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