CN1095728A - Epoxy resins and epoxy resin compositions - Google Patents

Abstract

An epoxy resin prepared by glycidyl etherification of bisphenol (1) and a novolak resin (II) with an epihalohydrin or a methylepihalohydrin in the presence of optionally halogenated bisphenol (III); and an epoxy resin composition prepared by further reacting the thus-obtained epoxy resin with a halogenated bisphenol (III), the product of the present invention is suitable for processing, and after curing, exhibits excellent heat resistance, blister resistance and copper clad laminate adhesion.

Description

The present invention relates to an epoxy resin and an epoxy resin composition comprising said epoxy resin. In particular, the present invention relates to an epoxy resin which exhibits low viscosity when mixed with a curing agent so as to facilitate molding, and which, once cured, has excellent heat resistance and high mechanical strength. The present invention also relates to an epoxy resin composition which exhibits excellent impregnation properties for materials such as glass cloth and which, once cured, exhibits high heat resistance and resistance to blistering so that it can be used Used in the production of printed circuit boards, especially copper-clad epoxy laminates for multilayer printed circuit boards.

A plastic composite material prepared by mixing a plastic material base and a reinforcing agent is widely used in industry because of its excellent heat resistance, weather resistance, chemical resistance, or mechanical strength. Epoxy resins are widely used as binders for plastic composites due to their good dynamic properties, they can also extremely strongly bond reinforcing fibers used as reinforcements, and the resulting composites are easily formable.

Among the plastic composite materials, it is highly expected that the composite material containing epoxy resin and carbon fiber in view of its excellent heat resistance and mechanical strength will become the most prominent application in the aerospace, automobile and other high-tech industries. next-generation structural materials.

However, these composite materials are expected to have higher heat resistance and further improved formability or moldability to enable them to be used as structural materials in these high-tech fields.

In recent years, the range of electronic equipment has greatly expanded, and multilayer printed circuit boards are finding their application not only in computer-related equipment but also in automatic control machines, communication equipment, business equipment, game machines, etc., which are Due to their improved performance, the size has been reduced.

In the computer field, on the other hand, system architecture has undergone marked changes as is often perceived as a downward trend around the workplace where structured distribution systems have become commonplace. Printed circuit boards used in such dispensing systems have not been developed to increase the number of layers of laminated products, and these circuit boards generally include laminated products with 4 to 10 layers. In the field of printed circuit boards, good form factors that enable high-density packaging and reduction in thickness are being investigated.

In order to meet these requirements imposed on printed circuit boards, the base material of printed circuit boards should be more improved in heat resistance and blister resistance.

One of the methods known in the prior art to improve the heat resistance of epoxy resins is to add multifunctional epoxy resins to increase the crosslink density of the resins. Novolak epoxy resins are widely used for this modification due to their inexpensiveness.

However, Novolak epoxy resin has a rather broad molecular weight distribution, and when Novolak epoxy resin is added in a large amount, or when a high molecular weight Novolak epoxy resin is used, the resulting resin has an excessively high viscosity. When such a high-viscosity resin is used as a base for plastic composites, it is difficult to completely impregnate reinforcing fibers with the base resin and shape the resulting plastic composite. In addition, mere addition of a multifunctional epoxy resin cannot satisfy the strict heat resistance requirements imposed on laminated products for printed circuit boards. For example, the improvement of heat resistance by excessive addition of this multifunctional epoxy resin will cause the composition to harden and become brittle, and when the laminated product prepared with this composition is soldered after boiling, delamination often occurs. layer resulting in blistering.

A first object of the present invention is to provide an epoxy resin that is easy to mold, exhibits low viscosity when mixed with a curing agent, and exhibits excellent heat resistance and high mechanical strength once cured.

A second object of the present invention is to provide an epoxy resin composition which exhibits excellent impregnation properties to materials such as glass cloth and which, once cured, exhibits excellent heat resistance and blister resistance, and Adhesion to copper cladding, therefore, it is particularly suitable for the preparation of copper clad epoxy laminates for printed circuit boards, especially laminates for multilayer printed circuit boards.

The inventors of the present invention have conducted sufficient research to achieve the above-mentioned first object, and have found an easily moldable low-viscosity epoxy resin that exhibits excellent heat resistance and high mechanical strength once cured, which Resins can be glycidyl etherified simultaneously with bisphenols and novolak resins by glycidyl etherification of a bisphenol with an epihalohydrin or a methylepihalohydrin in the presence of a novolak resin prepared by chemical reaction.

To achieve the above-mentioned first object of the present invention, the present invention provides an epoxy resin (A), which is obtained by using bisphenol (I) and novolak resin (II) with at least one selected from epihalohydrin and methyl epihalohydrin One of the halogenated alcohols is prepared by glycidyl etherification.

In addition, in order to achieve the above-mentioned second object of the present invention, according to the present invention, an epoxy resin composition mainly containing polyadduct epoxy resin (B) will be provided, and the epoxy resin (B) is Glycidyl etherification of bisphenol (I) and novolak resin (II) with at least one selected from epihalohydrin and methyl epihalohydrin to form epoxy resin (A), and then in an onium salt Or in the presence of a basic catalyst, the epoxy resin (A) is reacted with a halogenated bisphenol (Ⅲ) to produce the polymer resin (B).

Furthermore, in order to achieve the above-mentioned second object of the present invention, according to the present invention, there is also provided an epoxy resin composition mainly containing polymer-added epoxy resin (D), the epoxy resin (D) being bisphenol (I), novolak resin (II), and halogenated bisphenol (III) undergo glycidyl etherification with epihalohydrin or methyl epihalohydrin to form epoxy resin (C), and then in an onium It is prepared by reacting an epoxy resin (A) with a halogenated bisphenol (III) in the presence of a salt or a basic catalyst to produce an added polymer resin (D).

The epoxy resin of the present invention and the epoxy resin composition containing the epoxy resin will be described in detail below.

The epoxy resin (A) of the present invention is produced by using bisphenol (I) and novolak resin (II) as raw materials. The epoxy resin composition of the present invention mainly contains the addition polymer epoxy resin (B) or (D), and epoxy resin (B) or (D) is respectively made of epoxy resin (A) or (C) and halogenated Diphenol (Ⅲ) is prepared by polyaddition reaction, while epoxy resin (A) or (C) is obtained by shrinking bisphenol (I), novolak resin (II), and halogenated bisphenol (Ⅲ) Glyceryl etherification and preparation.

Bisphenol (I)

The bisphenol (I) used as the raw material for preparing epoxy resin (A) or (C) is a compound represented by the general formula (i):

，和-C（CH₃）（C₆H₅）-;R¹单独选自氢原子和含有1至5个碳原子的烃;n是0至4的整数。双酚（Ⅰ）的示范例包括双酚A，双酚F，和双酚AD。其中最优选的是双酚A，它是在上述分子式（ⅰ）中R是异亚丙基，R¹是氢原子的双酚。wherein R is a divalent group selected from -CH ₂ -, -CHCH ₃ -, -C(CH ₃ ) ₂ -, -SO ₂ -,

, and -C(CH ₃ )(C ₆ H ₅ )-; R ¹ is independently selected from hydrogen atoms and hydrocarbons containing 1 to 5 carbon atoms; n is an integer of 0 to 4. Exemplary bisphenols (I) include bisphenol A, bisphenol F, and bisphenol AD. Among them, bisphenol A is most preferred, which is a bisphenol in the above formula (i) in which R is isopropylidene and R ¹ is a hydrogen atom.

Novolak resin (Ⅱ)

The novolak resin (II) used to prepare the epoxy resin (A) or epoxy resin (C) of the present invention (A) or (C) for the preparation of the epoxy resin composition of the present invention) is formaldehyde and the above-mentioned Bisphenol (I) or a condensation product of phenol represented by the following general formula (ii):

wherein ^R1 and ^R2 are each selected from a hydrogen atom and a hydrocarbon containing 1 to 10 carbon atoms. Examples of preferred phenols represented by the general formula (ii) include phenol, o-cresol, p-tert-octylphenol, and p-cresol.

The bisphenol (I) which can be condensed with formaldehyde to form the novolak resin (II) may be a bisphenol represented by the general formula (i). The bisphenol (I) used in the preparation of novolak resin (II) is preferably bisphenol A or bisphenol AD.

The Novolak resin (II) may preferably have a softening point up to 100°C, more preferably a softening point ranging from 30 to 100°C. When bisphenol (II) having a softening point exceeding 110°C is used to prepare an epoxy resin, the resulting epoxy resin is not easily moldable due to its excessively high content of high molecular weight substances, and thus, excessively high viscosity. When the epoxy resin is further reacted with halogenated bisphenol (III) to prepare epoxy resin (B) or (D), the resulting resin will have an excessively high content of high molecular weight substances, resulting in insufficient impregnation into the glass cloth.

The number average molecular weight of the Novolak resin (II) is preferably 300-1000, more preferably 300-700, still more preferably 350-600. Preferably the novolak resin (II) has a molecular weight distribution up to 2, more preferably from 1.1 to 1.8. As the term used in the present invention, molecular weight distribution means the ratio of weight average molecular weight to number average molecular weight, ie Mw/Mn.

Novolak resin (II) can be prepared by reacting the above-mentioned bisphenol and/or phenol with formaldehyde with or without a solvent such as xylene or toluene, and in the presence of an acidic catalyst. Paraformaldehyde can be used instead of formaldehyde. Formaldehyde is used in an amount of 0.2 to 0.8 moles per mole of total bisphenols and/or phenols to optimize softening point and average molecular weight.

When the solvent is used in the above reaction, it is used in a proportion of 20 to 100% by weight per 100% by weight of the total of said bisphenol and/or phenol.

The acidic catalyst used may typically be an inorganic acid such as sulfuric acid, hydrochloric acid, nitric acid, or phosphoric acid; or an organic acid such as p-toluenesulfonic acid or oxalic acid. Among these acids, p-toluenesulfonic acid is preferred due to its high acidity and good miscibility with the reaction matrix. The acidic catalyst is preferably used in a proportion of 0.05 to 2% by weight per 100% by weight of all said bisphenols and/or phenols. More preferably 0.1 to 1% by weight. The use of very small amounts of acidic catalysts can lead to failure of the reaction to produce the desired molecular weight novolak resin (II). The use of an extreme excess of acidic catalyst will result in difficult control of the reaction and lead to excessively high molecular weight of the resulting novolak resin.

The reaction can generally be carried out by heating the reaction mixture to a temperature of 70 to 100°C for 1.5 to 4 hours and then to a temperature of 100 to 120°C for dehydration condensation. The dehydration condensation is either promoted under reduced pressure or by azeotropic reflux in a solvent such as xylene or toluene and removal of the water of condensation. The reaction is preferably continued until no more water of condensation is produced. The reaction is generally carried out for 3 to 5 hours.

After the reaction is complete, a stoichiometric equivalent of the acidic catalyst used is added to the reaction mixture to neutralize the acidic catalyst. Typical base compounds that can be used include sodium hydroxide, potassium hydroxide, and triethanolamine morpholine. Alternatively, neutralization can be carried out by adding an anhydrous solvent to the reaction mixture to form a homogeneous solution, and then washing the solution with an aqueous base solution.

When a solvent is used to produce the novolak resin (II), the used solvent is distilled off to leave the novolak resin.

In novolak resins (II) containing 3 or more functionalities, the polynuclear components may preferably constitute bisphenols (I) and 3 to 50% by weight of the phenolic components in novolak resins (II), more preferably 5 to 40% by weight to provide epoxy resin (A) or bisphenol (I), and novolak resin (II) and halogenated bisphenol (III) to provide epoxy resin (C). When the content of the multi-core component is less than 3% by weight, the glass transition temperature of the resulting epoxy resin after curing will not be sufficiently improved. On the other hand, when the content of the multinuclear component exceeds 50% by weight, the epoxy resin ( B) or (D) would have too high a molecular weight to sufficiently impregnate into the glass cloth.

Halogenated bisphenol (Ⅲ)

The halogenated bisphenol (III) used as a raw material for the preparation of the epoxy resin (C) is preferably brominated bisphenol. Most preferred are tetrabromobisphenol A, tetrabromobisphenol F, and 1,1-bis(3,5-dibromo-4-hydroxyphenyl)ethane.

Glycidylation reaction

Reaction of bisphenol (I) and novolak resin (II) with epihalohydrin or methyl epihalohydrin to generate epoxy resin (A); bisphenol (I), novolak resin (II) and halogenated bisphenol ( iii) The reaction with epihalohydrin or methylepihalohydrin to form epoxy resin (C) can be carried out according to various known methods. However, in order to provide the resulting glycidyl etherified epoxy resin (A) or (C) with reliable quality, it is preferable to carry out the etherification step and the dehydrohalogenation step sequentially. The epihalohydrin is preferably epichlorohydrin, and the methylepihalohydrin is preferably 2-methylepichlorohydrin.

The etherification step can be carried out in the presence of an etherification catalyst, and its dosage is a mixture of bisphenol (I) and novolak resin (II), or a mixture of bisphenol (I), novolak resin (II) and halogenated bisphenol (III) 0.1 to 5% (mol) per 1 equivalent of phenolic hydroxyl group. Typical etherification catalysts include tertiary amines such as trimethylamine, triethylamine, etc.; tertiary phosphines such as triphenylphosphine, tributylphosphine, etc.; quaternary ammonium salts such as tetramethylammonium chloride, tetramethylammonium bromide, Tetraethylammonium, choline hydrochloride, etc.; quaternary phosphonium salts such as tetramethylphosphonium bromide, tetramethylphosphonium iodide, tetraphenylphosphonium bromide, triphenylpropylphosphonium bromide, etc.; tertiary sulfonium salts such as benzyldibutylsulfonium chloride, benzyldimethylsulfonium chloride, etc.; and inorganic bases such as sodium hydroxide, potassium hydroxide and the like. Of these, tetramethylammonium chloride is preferred.

In the etherification step, the reaction is carried out until at least 50 mole percent, preferably at least 70 mole percent, of the phenolic hydroxyl groups are etherified. Generally the reaction is carried out in an inert atmosphere at a temperature of 60-110°C for 1 to 12 hours. The water content in the system is preferably kept at not more than 3.0% by weight.

The next dehydrohalogenation step can be carried out on the reaction product obtained from the etherification step which contains unreacted epihalohydrin. In this reaction, those alkali compounds used in the etherification step, such as alkali metal hydroxides, are preferably used as catalysts. In the dehydrohalogenation step, the general amount of alkali compound used is 0.5 mole or more per 1 equivalent of the phenolic hydroxyl group of novolak resin (II), preferably 0.8 mole or more, preferably up to 1 mole of alkali compound per 1 equivalent of phenolic hydroxyl group. The reaction product is not easy to gel. The reaction is generally carried out at a temperature of 60-100°C for 1-3 hours. When sodium hydroxide is used, the reaction is preferably carried out with removal of by-product water. Removal of water can be achieved by dehydration of the reaction mixture, such as epihalohydrin-water azeotrope, and returning epihalohydrin to the reaction system. After the reaction is completed, the epoxy resin of the present invention can be prepared after post-processing, which refers to, for example, removing unreacted epihalohydrins by vacuum distillation, removing by-product salts by water washing, and may have The workup can be carried out by neutralizing the reaction mixture with a weak acid such as phosphoric acid or sodium dihydrogen phosphate, as well as filtering and drying. In addition, if it is necessary to reduce the amount of hydrolyzable chlorine, a second dehydrohalogenation can be carried out. The ratio of the alkali compound for reducing the amount of hydrolyzable chlorine is 1 to 3 moles per 1 mole of residual hydrolyzable chlorine. Preferably it is 1.2 to 3 moles. The reaction is carried out at a temperature of 60-100°C for about 1-3 hours. The reaction can be performed with or without a solvent. When a solvent is used, preferred are xylene, toluene, methyl ethyl ketone (MEK), and methyl isobutyl ketone.

In the preparation of epoxy resin (A), the weight ratio of used bisphenol (I) and novolak resin (II) is 1-99:99-5, preferably 5-95:95-5, more preferably 10- 90:90-10. When an excess of the novolak component is used, the resulting epoxy resin will have an excessively high content of higher molecular weight species, for example it will not be sufficiently impregnated into the glass cloth during prepreg, and as a result, the resulting laminate will be impact resistant Poor sex. When the proportion of novolak resin (II) is too low, the resulting epoxy resin will not have sufficient heat resistance.

For heat-resistant composite materials, the weight ratio of bisphenol (I) and novolak resin (II) used is 50-90:50:10, preferably 65-90:35-10. When the proportion of novolak resin (II) is too low, the resulting epoxy resin will not have sufficient heat resistance. When the novolak component is used in excess, the resulting epoxy resin will have too high a viscosity and is not easy to shape.

In the production of epoxy resin (C), used bisphenol (I), the weight ratio of novolak resin (II) and halogenated bisphenol (III) is 5-80: 94-5: 1-15, preferably 7 -80:90-10:3-10.

The glycidyl etherified epoxy resin (A) prepared by the above reaction has an epoxy equivalent of 170-220 g/equivalent, and when used for printed circuit boards, it preferably has a softening point as high as 50°C, 170-220 g / equivalent of epoxy equivalent, halide content up to 0.1% (weight). The glycidyl etherified epoxy resin (C) produced by the above reaction has a softening point as high as 40°C, an epoxy equivalent of 170-220 g/equivalent, and a halide content as high as 10% by weight.

Polyaddition reaction

Adding polymer resin (B) and (D) is the main component of epoxy resin composition of the present invention respectively, and resin (B) and (D) are respectively made of epoxy resin (A) and (C) and halogenated bisphenol ( Ⅲ) Manufactured by reaction.

The polyaddition reaction of epoxy resin (A) or (B) and halogenated bisphenol (Ⅲ) is in inert atmosphere with or without the presence of catalysts such as quaternary ammonium salt or quaternary sulfonium salt, (its consumption is 10 -30ppm), realized after 4-15 hours at a temperature of 120°C to 170°C.

The reaction can be carried out in solvents such as toluene, xylene and cyclohexane so that the solids content of the reaction mixture can be as high as 30% by weight.

The halogenated bisphenols (III) usable in the polyaddition reaction may be the same as those used in the glycidyl etherification. Among these halogenated bisphenols (III), brominated bisphenols are preferred, especially tetrabrominated bisphenol A, tetrabrominated bisphenol F, and 1,1-bis(3,5-dibromo-4- hydroxyphenyl) ethane.

In the reaction of epoxy resin (A) and halogenated bisphenol (Ⅲ) to generate polymer epoxy resin (B), the preferred amount ratio of epoxy resin (A) and halogenated bisphenol (Ⅲ) is 74: 26 to 55: 45. In the reaction of epoxy resin (C) and halogenated bisphenol (Ⅲ) to generate polymer epoxy resin (D), the preferred amount ratio of epoxy resin (C) and halogenated bisphenol (Ⅲ) is 90: 10 to 58:42. When an excessive amount of the halogenated bisphenol (III) is used, a high molecular weight substance will be formed in excess, which will result in insufficient impregnation of the resin composition into the cloth when making a prepreg. When the proportion of halogenated bisphenol (III) is too low, the resulting epoxy resin composition will not have sufficient flame retardancy.

The polyaddition reaction can be completed in the presence of general-purpose epoxy resins and/or epoxidized halogenated bisphenols. The epoxidized halogenated bisphenols are obtained by combining the above-mentioned halogenated bisphenols (Ⅲ) with epihalohydrin or methyl epihalide It is prepared by glycidyl etherification reaction of substituted alcohol. When the polyaddition reaction is carried out in the presence of epoxidized halogenated bisphenols. The bisphenol is preferably used in a proportion of 1-15% per 100% by weight of the total content to prevent coloring of the laminate when heated.

The epoxy resin composition of the present invention mainly comprising the polymer-added resin (B) prepared by the reaction of the epoxy resin (A) and the halogenated bisphenol (III) as described above has an epoxy equivalent of 300-500 g/equivalent , the number average molecular weight Mn is 500-1000, the Mn/Mw ratio is 1.7-3.0, the halide content is 15-25% (weight), and the multifunctional component content is 3-40% (weight). It is a viscous product with a narrow molecular weight distribution containing small amounts of low and high molecular weight species.

The epoxy resin composition of the present invention mainly containing the polymer-added resin (D) which is prepared by reacting the epoxy resin (C) with the halogenated bisphenol (III) as described above) has 300-500 g/equivalent The epoxy equivalent, the number average molecular weight Mn is 500-1000, the Mn/Mw ratio is 1.5-2.5, and the halogenated content is 15-25% (weight). And the multifunctional component content is 3-40% by weight. It is a viscous product with a narrow molecular weight distribution containing small amounts of low and high molecular weight species.

When the epoxy resin composition of the present invention is cured with a curing agent such as dicyandiamide or a phenolic novolak resin, the resulting cured product has improved resistance to blistering. And it is about 10°C higher than the glass transition temperature Tg of epoxy resin cured articles prepared with other conventional epoxy resins other than the epoxy resin (A) or (C) of the present invention. The epoxy resin composition of the present invention also exhibits good impregnation properties for glass cloth.

As mentioned above, the glycidyl etherified epoxy resin (A) or (C) is used to prepare the epoxy resin composition of the present invention. In the preparation of the epoxy resin composition of the present invention, the epoxy resin (A) or (C) may be used alone or in combination with another epoxy resin having two or more epoxy groups in one molecule. Examples of such additional epoxy resins include bisphenol-A epoxy resins, phenol novolak epoxy resins, cresol novolak epoxy resins and other glycidyl etherified epoxy resins, glycidyl ester epoxy resins, shrink Glycerylamine epoxy resins, linear aliphatic epoxy resins, cycloaliphatic epoxy resins, heterocyclic epoxy resins, halogenated epoxy resins, and other multifunctional epoxy resins, the amount of this additional epoxy resin is per 100 % (weight) up to 50% (weight) of the total epoxy content (i.e., the total of epoxy resin and additional epoxy resin), when the additional epoxy resin is used in excess, the resulting composition no longer has the composition of the present invention performance characteristics.

The curing agents used in conjunction with the epoxy resin compositions of the present invention are not limited to any particular type. Representative curing agents are acid anhydrides, aromatic polyamines, aliphatic polyamines, imidazoles, and phenolic resins.

Exemplary anhydrides include phthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, methylnaphthalene dicarboxylic acid, 1 , 2,4,5-Pellimetic anhydride, 1,2,4-Pellimetic anhydride, Benzophenone tetracarboxylic anhydride, Dodecylsuccinic anhydride, Chlorendramide, and Chlornorbornene dicarboxylic anhydride.

Exemplary aromatic polyamines include diaminodiphenylmethane, diaminodiphenylsulfone, and amine adducts.

烯二胺，N-氨基乙基哌啶，异佛尔酮二胺，3，9-双（3-氨基丙基）-2，4，8，10-四螺[5.5]十一烷，胺加合物。Exemplary aliphatic polyamines include triethylenetetramine, diethylenetriamine,

Diamine, N-aminoethylpiperidine, isophoronediamine, 3,9-bis(3-aminopropyl)-2,4,8,10-tetraspiro[5.5]undecane, amine adduct.

Exemplary imidazoles include 2-methylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-undecylimidazole, 2-ethyl-4-methylimidazolazine, and 1 -Benzyl-2-methylimidazole.

Exemplary phenolic resins include phenolic novolak resins and alkyl-substituted phenolic novolak resins.

Optional curing agents such as dicyanediamide, m-xylylenediamine can also be used in the present invention.

In the present invention, the above-mentioned curing agents can be used alone or in combination of two or more.

Curing agents can be used together with curing accelerators. Exemplary curing accelerators include imidazoles as described above, for example, 1-benzyl-2-methylimidazole and 2-ethyl-4-methylimidazole, amines such as tertiary amines, such as N,N-benzyl dimethylamine and 2,4,6-tris(dimethylaminomethyl)phenol; and tertiary phosphines such as triphenylphosphine.

Other exemplary curing accelerators are 1,8-diazabicyclo-[5.4.0]-undecene-7-octanoate, a complex of monoethylamine and boron trifluoride, and ® commercially available from Sun Abbot Inc. The trade name Ucat SA102 compound obtained.

In the present invention, the curing accelerators may be used alone or in combination of two or more.

The epoxy resin composition of the present invention can be mixed with a solvent such as acetone, methyl ethyl ketone, toluene, xylene, methyl isobutyl ketone, ethyl acetate, ethylene glycol monomethyl ether, N, N- Dimethylformamide, N,N-dimethylacetamide, methanol, ethanol, etc. They may be used alone or in combination of two or more as a mixed solvent.

The epoxy resin composition of the present invention may or may not contain other additives such as flame retardants and fillers depending on the intended use of the composition.

The epoxy resin composition of the present invention is fully suitable for preparing copper-clad epoxy resin laminates according to conventional methods. In a typical preparation of copper-clad epoxy resin laminates, the epoxy resin composition of the present invention is used. Epoxy resin is dissolved in a solvent to prepare a varnish, which is then impregnated and/or applied to a reinforcing material such as glass cloth and dried at high temperature to remove the solvent to produce a prepreg. In the next step, a copper clad layer is provided on one or both surfaces of the prepreg. The prepreg is used as a single sheet or as a stack of prepreg sheets. The epoxy resin composition is allowed to and solidify under pressure.

The present invention is further described in detail by the following examples and comparative examples. It should be noted that this example is not meant to limit the scope of the invention.

example

In the following examples and comparative examples, viscosity, flexural strength, flexural modulus and deflection temperature under load were evaluated as follows.

viscosity

The viscosity was measured with an E-type viscometer at a temperature of 25°C.

Flexural strength and flexural modulus

A sample with a size of 4 mm x 10 mm x 97 mm was measured in accordance with JIS K6911 using a Tensilon manufactured by TOYO BALDWIN at a sliding beam speed of 1 mm/min with a sensor with a maximum load of 500 kg.

Deflection temperature under load

A sample having a size of 12.5 mm×12.5 mm×125 mm was measured according to JIS K6911 using an apparatus manufactured by Tester Industry K.K.

Synthesis Example 1

Synthesis of novolak resin with bisphenol A as phenol

Into a 1 liter separable flask equipped with a condenser, thermometer, stirrer and dropping vessel were charged 456 grams of bisphenol A and 335 grams of toluene and the contents were heated with stirring. When the temperature in the flask reached 70°C, 2.52 g of oxalic acid dihydrate was added as a catalyst. When the temperature in the flask reached 90°C, 82.7 grams of 37% formaldehyde solution was added dropwise in 2 hours. The contents were stirred at reflux for an additional 1 hour. The temperature of the contents is raised further thereby removing water and toluene from the system. When the temperature reached 150°C, the contents were concentrated at normal temperature for 1 hour, and further concentrated for 1 hour under a reduced pressure of 20 mmHg to obtain a bisphenol A novolak resin (hereinafter referred to as novolak resin (I)). The softening point of this novolak resin (I) was measured to be 93°C with an automatic softening point measuring device manufactured by Metler Inc. The hydroxyl equivalent of this novolak resin was also measured according to JIS K0070, and it was 120 g/equivalent. Its number average molecular weight was 450, and its molecular weight distribution was 1.50.

example 1

Add 400 grams of bisphenol A, 100 grams of o-cresol novolak resin (OCN80 manufactured by Nippon Kayaku K.K; softening point is 80 ℃, Hydroxyl equivalent weight 139 g/eq, number average molecular weight 425, molecular weight distribution 1.30), 1956 g epichlorohydrin, and 39 g water. The temperature of the contents was raised to 65°C. When the reaction mixture became a homogeneous solution, 23.1 g of a 50% aqueous solution of tetramethylammonium chloride was added and the reaction was allowed to proceed for 3 hours with stirring.

In the next step, 331.5 grams of 48% NaOH aqueous solution was added dropwise to the mixture under reduced pressure at 70 °C for 2 hours, and the excess water was removed from the system by azeotroping of epichlorohydrin and water, so that the reaction system remained at 2% ( weight) of water content. The epichlorohydrin distilled off from water is separated from water and recycled to the reaction system. The conditions of azeotropic distillation (including the degree of decompression and heating) should be controlled so that the amount of water removed from the system per unit time should be equal to the sum of the amount of water in the 48% NaOH aqueous solution added to the reaction system and the amount of water generated in the reaction. After the dropwise addition of 48% NaOH aqueous solution was completed, the reaction system was kept at the same temperature and stirred for another 0.5 hours.

After the reaction was completed, epichlorohydrin and water were distilled off from the reaction mixture under reduced pressure. To the remaining mixture were added 750 grams of xylene and 75 grams of water. The reaction mixture was stirred at 80°C for 0.5 hours and allowed to stand to separate into xylene and aqueous phases. Analysis of a sample collected from the xylene phase showed a hydrolyzable chlorine concentration of 1.45% by weight.

Next, 62 g of a 48% aqueous NaOH solution were added to the xylene phase and the reaction mixture was stirred at 95°C for 2 hours. After the reaction was complete, the gel content was removed, and 750 grams of 25% monosodium phosphate aqueous solution was added for neutralization. Water was removed from the resulting neutralized product by using xylene-water azeotropy, and the remaining mixture was filtered with a glass filter to separate inorganic salts in the neutralized product. The filtrate was heated to 150°C under reduced pressure to remove xylene to obtain 680 g of epoxy resin. The epoxy resin thus produced had an epoxy equivalent of 185 g/eq and a hydrolyzable chlorine content of 0.06% by weight.

Example 2

The difference of repeating the procedure of Example 1 is that the amount of bisphenol A used is reduced to 260 grams, and the o-cresol novolak resin used is replaced by the novolak resin (I) synthesized in the reference synthesis example 1. 450 g of epoxy resin having an epoxy equivalent weight of 190 g/equivalent and a hydrolyzable chlorine content of 0.05% by weight were produced.

Example 3

80 g of epoxy resin synthesized in Example 1, 72.6 g of methylhexahydrophthalic anhydride (Liquacid MH-700 produced by Shin-Nippon Rika K.K), and 0.4 g of 1,8-diazabicyclo[5.4 .0]-7-Undecene Octilate (manufactured by Sun-Abbot Inc, Ucat-102) was mixed under stirring at 50°C to make a homogeneous paint solution. This homogeneous solution has a viscosity of 993 centipoise at 25°C.

The homogeneous solution thus produced was poured into molds prepared for preparing test samples for measuring flexural strength and flexural modulus, and additionally poured into molds prepared for test samples for measuring deflection temperature under load, and then placed in Heating at 120°C for 2 hours, heating at 150°C for 2 hours, and finally heating at 170°C for 4 hours for curing. The test specimens thus cured were measured for their flexural strength, flexural modulus and deflection temperature under load, respectively. The results are shown in Table 1.

Example 4

The procedure of Example 3 was repeated, except that the epoxy resin used was replaced by 80 grams of epoxy resin synthesized in Example 2, and the amount of methylhexahydrophthalic anhydride used was reduced to 70.8 grams. The resulting homogeneous solution had a viscosity (at 25°C) of 896 centipoise. This homogeneous solution was also cured into test specimens to determine their flexural strength, flexural modulus, and deflection temperature under load. The results are shown in Table 1.

Comparative example 1

The procedure of Example 1 was repeated except that no bisphenol-A was used and only 584 g of o-cresol novolak resin (OCN80 manufactured by Nippon Kayaku K.K) was used to produce 650 g of novolak epoxy resin. The novolak epoxy resin thus produced had an epoxy equivalent of 203 g/eq and a hydrolyzable chlorine content of 0.05% by weight.

Comparative example 2

Repeat the procedure of Example 1, the difference is that no bisphenol-A is used and the o-cresol novolak resin is replaced with 504 grams of bisphenol Anovolak resin synthesized in reference synthesis example 1 to make 605 grams of novolak epoxy resin, which is made The novolak epoxy resin has an epoxy equivalent weight of 197 g/eq and a hydrolyzable chlorine content of 0.06% by weight.

Comparative example 3

Repeat the procedure of example 3, the difference is the novolak epoxy resin synthesized with 16 grams of comparative example 1, 64 grams of bisphenol A type liquid epoxy resin (epoxy equivalent, 188 grams/equivalent), 71.4 grams of methylhexahydro-phthalate Diformic anhydride, and 0.4 g of 1,8-diazabicyclo[5.4.0]-7-undecene Octilate (Ucat-102, manufactured by Sun-Abbot Inc.) prepare a uniform paint solution. The homogeneous solution had a viscosity of 1946 centipoise at 25°C. The homogeneous solution thus prepared was cured as a test sample to measure flexural strength, flexural modulus and deflection temperature under load. The ratio of the bisphenol A component to the novolak component in the cured product was the same as in Example 3. The results are shown in Table 1.

Comparative example 4

Repeat the procedure of example 3, the difference is to use the novolak epoxy resin synthesized by 37.4 grams of comparative example 2, 42.6 grams of bisphenol A type liquid epoxy resin (epoxy equivalent: 188 grams/equivalent) 69.8 grams of methylhexahydrophthalate Formic anhydride, and 0.4 g of 1,8-diazabicyclo[5.4.0]-7-undecene Octilate (Ucat-102 from Sun-Abbot Inc.) were used to prepare a uniform paint solution. The homogeneous solution had a viscosity of 3379 centipoise at 25°C. The homogeneous solution thus prepared was cured as a test sample to measure flexural strength, flexural modulus, and deflection temperature under load. The ratio of the bisphenol A component to the novolak component in the cured product is the same as in Example 4, and the results are shown in Table 1.

Comparative example 5

Repeat the procedure of Example 3, the difference is to prepare a uniform paint with 80 grams of bisphenol A type liquid epoxy resin (epoxy equivalent 188 grams/equivalent), 71.5 grams of methyl hexahydrophthalic anhydride and 0.4 grams of Ucat-102 solution. The homogeneous solution thus prepared was cured as a test sample to measure its flexural strength, flexural modulus, and deflection temperature under load. The results are shown in Table 1.

Table 1: Properties of Cured Products

Example 3 Example 4 Comparative Example 3 Comparative Example 4 Comparative Example 5

Paint before curing at 25°C 993 896 1946 3379 -

Viscosity, centipoise

Flexural strength, kg/ 12.9 12.9 12.0 12.1 11.8

^mm2

Flexural modulus, kg/ 279 292 280 280 277

^mm2

Deflection temperature under load, 159 164 160 165 140

℃

Synthesis Examples 2 to 5

Synthesis of novolak resin

Into a 1 liter separable flask equipped with a condenser, thermometer, stirrer and dropping vessel was charged 456 grams of bisphenol A and 335 grams of toluene and the contents were stirred and heated. When the temperature in the flask reached 70°C, 2.52 g of oxalic acid dihydrate was added as a catalyst. When the temperature in the flask reached 90°C, 130 g of a 37% aqueous formaldehyde solution was added dropwise over 2 hours, and the reaction was allowed to proceed for another 1 hour under reflux and stirring. Next, the temperature of the system was raised to remove water and toluene from the system. When the temperature reaches 150°C, concentrate the contents at normal temperature for 1 hour, and further concentrate for 1 hour under reduced pressure of 20 mmHg to obtain novolak epoxy resin containing residual bisphenol A, which is hereinafter referred to as novolak resin (2) . The softening point of the obtained novolak resin (2) was measured with an automatic softening point measuring device manufactured by Metler Inc. The residual bisphenol A monomer content as well as the number average molecular weight and molecular weight distribution (Mw/Mn) of the resin were also determined by gel permeation chromatography (GPC). In the measurement of the bisphenol A monomer residual content, 2 columns Shim-Pack-HSG-10 (manufactured by Shimadzu Seisakusho Ltd) and each 1 column Shim-Pack-HSG15 and 20 were connected in series to constitute a separation column. In the determination of molecular weight, HSG-20, 40, 50 and 60 were connected in series. Tetrahydrofuran was used as the eluting solution. The molecular weight distribution was measured as described below. The results are shown in Table 2.

Repeat the above-mentioned procedure of Reference Synthesis Example 2, except that the amounts of bisphenol A, oxalic acid dihydrate, and 37% formaldehyde solution are as shown in Table 2 to prepare novolak resins (3) to (5). The novolak resins (3)-(5) thus obtained were also measured for their softening point, residual bisphenol A monomer content, number average molecular weight, and molecular weight distribution. Note that in the case of Synthesis Example 5, 324 g of o-cresol was used instead of bisphenol A.

Table 2:

novolak resin

(2) (3) (4) (5)

Added raw material weight, grams

Bisphenol-A 456 456 456 -

o-Cresol - - - 324

Oxalic acid dihydrate 2.52 2.52 2.52 3.8

37% formaldehyde solution 130 82.7 33.1 174

The nature of the resulting product

Softening point, ℃ 110 93 72 80

Residual bisphenol-A monomer 22 39 57 23 ^*

Content,%(weight)

Number average molecular weight 556 450 374 425

Molecular weight distribution (Mw/Mn) 1.68 1.50 1.12 1.30

Note: * is the content of dinuclear o-cresol

Synthesis Examples 6 to 15

Synthesis of Glycidyl Etherified Epoxy Resins (Coglycidylation)

Into a 2 liter round bottom flask equipped with a thermometer, stirrer, separator, condenser and drop vessel were charged 200 g of novolak resin (2) with a residual bisphenol-A monomer content of 22% by weight and 1206 g epichlorohydrin, and heat the contents to a temperature of 90°C with stirring. 30 g of water and 3 g of tetramethylammonium chloride were added at a temperature of 90°C and the mixture was stirred for 4 hours. The temperature of this mixture is reduced to 70 ℃, and the pressure is reduced to 500mmHg, under this pressure, with 3 hours, add 137 grams of 48% sodium hydroxide aqueous solution to this mixture from the drip container, simultaneously remove from this system with separator water. Water removal was continued for an additional 30 minutes after the dropwise addition of sodium hydroxide was complete. The system pressure was lowered to 20 mmHg, and the mixture was condensed at 120°C for 1 hour. Then the pressure was returned to normal pressure, 350 g of water and 250 g of toluene were added to the mixture, and the resulting mixture was stirred at 90° C. for 30 minutes. The mixture was allowed to stand still to facilitate separation, and the thus separated aqueous layer was removed, and the remaining resin layer was concentrated at 20 mmHg and 150° C. to obtain 264 g of glycidyl etherified epoxy resin, hereinafter referred to as cyclo Oxygen Resin (6).

The epoxy equivalent of the epoxy resin (6) thus obtained was measured by the dioxane hydrochloride method. Also, the softening point of the epoxy resin (6) was measured using an automatic softening point measuring apparatus manufactured by Metler Inc., and its composition was measured by gel permeation chromatography (GPC) as in the case of Synthesis Examples 2 to 5. The results are shown in Table 3.

The procedure of Synthesis Example 6 was repeated, except that the amounts of novolak resin, bisphenol A, epichlorohydrin, and 48% NaOH aqueous solution were as shown in Table 3 to prepare epoxy resins (7) to (15). The obtained epoxy resins (7) to (15) were also measured for epoxy equivalent, softening point and composition, and the results are also shown in Table 3.

Synthesis Example 16-27 Synthesis of Polymer Resin

In a 1-liter separable flask equipped with a stirrer and a thermometer, add 171 grams of bisphenol A epoxy resin (epoxy equivalent, 188 grams/equivalent), 29.4 grams of epoxy resin (6) prepared in Synthesis Example 6, and 94.3 gram tetrabromobisphenol A, and heat the contents with stirring. When the temperature reached 100°C, 0.2 g of tetraethylammonium chloride was added, and the reaction was accelerated at 160°C for 5 hours to obtain a monoaddition polymer resin, hereinafter referred to as addition polymer resin (16).

The epoxy equivalent weight of the polymer-added resin (16) was determined by the method described above. The number average molecular weight of the resin was determined by gel permeation chromatography (GPC) using Shim-pack-HSG20, 40, 50 and 60 columns connected in series, and its molecular weight distribution was determined by the same method as described above.

The procedure of Synthesis Example 16 was repeated except that the amounts of epoxy resin, bisphenol A epoxy resin, and tetrabromobisphenol A were as shown in Table 4 to prepare polymer-added resins (17) to (25). The addition polymer resins (17) to (25) were also measured for epoxy equivalent, number average molecular weight, and molecular weight distribution.

Repeat the procedure of synthetic example 16 again, difference is to replace tetrabromobisphenol A with the tetrabromobisphenol A epoxy resin of quantity shown in table 4, and the consumption of epoxy resin and bisphenol A epoxy resin is as shown in table 4 , made into polymer-added resins (26) and (27). The epoxy equivalent weight, number average molecular weight, and molecular weight distribution were also determined for the addition polymer resins (26) and (27).

Example 5

Add 2.5 grams of dicyandiamide and 0.15 grams of 2-ethyl-4 dissolved in 20 grams of ethylene glycol monomethyl ether to a solution of 100 grams of polymer resin (20) dissolved in 25 grams of methyl ethyl ketone - Methylimidazole solution made into an epoxy resin composition paint. The varnish thus prepared was impregnated with a glass cloth (WEA-18W105F manufactured by Nitto Boseki Co, Ltd), followed by drying in a drying oven at 140°C for 6 minutes to prepare a prepreg. The prepreg had an epoxy resin composition content of 49% by weight. Evaluation of prepreg appearance

The prepreg was crumpled to collect the epoxy resin composition, and the epoxy resin composition thus collected was placed into a suitable mold to produce a test piece of 1 mm thickness. The test piece was placed in a Reolosolid manufactured by Toyobo Co Ltd to measure the glass transition temperature, Tg, of the epoxy resin composition at a heating rate of 2°C/min.

The prepreg can also be made into a laminate by stacking four sheets of the prepreg and molding the stack at 170°C and a pressure of 20 kg/ ^cm² for 1 hour. The laminate was immersed in water at a temperature of 121°C and 2 kg/ ^cm2 for a predetermined period of time, and then immersed in a solder bath at 260°C for 20 seconds. After the pressure boiling test (PCT), the pressure was determined according to the following standard: Resistance to soldering heat of laminated products:

○: no blistering or delamination,

△: A small amount of foaming or slight delamination, and

X: Many blisters or a lot of delamination.

The results are shown in Table 5.

Examples 6 to 12

The procedure of Example 5 was repeated, and the polymer-added resins (21) to (27) shown in Table 5 were used instead of the polymer-added resin (20) to prepare paints and then prepregs. The varnish and prepreg thus made were measured for their glass transition temperature, PCT, and resistance to soldering heat after impregnation according to Example 5. The results are shown in Table 5.

Comparative Examples 6 to 12

The procedure of Example 5 was repeated except that the epoxy resins (6) to (9) as shown in Table 3 and the addition polymer resins (16) to (19) as shown in Table 4 were used in the amounts shown in Table 6 Epoxy resin composition paints were prepared. Then into prepreg. The varnishes and prepregs thus produced were determined for their glass transition temperature, resistance to soldering heat after PCT, and impregnated as in Example 5. The results are shown in Table 6.

Synthesis Examples 28 to 37

Preparation of Glycidyl Etherified Epoxy Resins (Coglycidylation)

Add 30.7 grams of novolak resin (2) synthesized in Synthesis Example 2, 171 grams of bisphenol A, 17.5 grams of tetrabromobis Phenol A, and 1178 grams of epichlorohydrin, the contents were heated to a temperature of 90°C with stirring. 30 g of water and 3 g of tetramethylammonium chloride were added at a temperature of 90°C, and the mixture was stirred for 4 hours. The temperature of the mixture was lowered to 70°C and the pressure was reduced to 500 mmHg, at which pressure 142.5 g of a 48% aqueous sodium hydroxide solution was added to the mixture from a dropping vessel over 3 hours while water was removed from the system by a separator. The water removal was continued for another 30 minutes after the dropwise addition of the aqueous sodium hydroxide solution was completed. The system pressure was then reduced to 20 mmHg and the mixture was condensed at 120°C for 1 hour. Then the pressure was returned to normal pressure, 350 g of water and 250 g of toluene were added to the mixture, and the resulting mixture was stirred at 90°C for 30 minutes. Allow the mixture to stand still to promote the water layer and remove the separated water layer, and the remaining resin layer is concentrated at 150° C. and 20 mmHg for 1 hour to obtain 1 gram of glycidyl etherified epoxy resin, which is hereinafter referred to as epoxy resin ( 28).

The epoxy equivalent weight of the epoxy resin (28) thus prepared was determined by the dioxane hydrochloride method. Also, the softening point of this epoxy resin (28) was measured with an automatic softening point measuring device produced by Metler Inc., and its composition was measured by gel permeation chromatography (GPC) as in the case of Synthesis Examples 2 to 5.

Repeat the procedure of Synthetic Example 28, the difference is to use novolak resin in the amount shown in Table 7, bisphenol A, tetrabromobisphenol A, epichlorohydrin, and 48% NaOH aqueous solution to prepare epoxy resin (29) to ( 37). For the obtained epoxy resins (29)-(37), the epoxy equivalent, softening point and composition were determined. The results are shown in Table 7.

Synthesis Example 38-48

Synthesis of Additive Polymer Resins

Into a 1 liter separable flask equipped with a stirrer and a thermometer were charged 200 g of epoxy resin (28) prepared in Synthesis Example 28 and 78 g of tetrabromobisphenol A, and the contents were heated with stirring. When the temperature reached 100°C, 0.2 g of tetraethylammonium chloride was added, and the reaction was accelerated at 160°C for 5 hours to obtain a polymer-added resin, hereinafter referred to as polymer-added resin (38).

The epoxy equivalent of the thus prepared polymer-added resin (38) was measured in the same manner as in Synthesis Example 16. The molecular weight of the polymer-added resin (38) was also determined by gel permeation chromatography (GPC) using columns of Shim-pack-HSG20, 40, 50 and 60 connected in series, and its molecular weight distribution was determined as in Example 16 . The results are shown in Table 8.

The procedure of Synthesis Example 38 was repeated, except that epoxy resin, bisphenol A epoxy resin and tetrabromobisphenol-A were used in the amounts shown in Table 8 to prepare the addition polymer resins (39) to (47). The epoxy equivalent weight, number average molecular weight, and molecular weight distribution of the polymer-added resins (39) to (47) were also determined. The results are shown in Table 8.

Example 13

Add 2.5 g of dicyandiamide and 0.15 g of 2-ethyl-4-methylimidazole in 20 g of ethylene glycol monomethyl ether to a solution of 100 g of polymer resin (45) in 25 g of methyl ethyl ketone The solution in is made into a paint of epoxy resin composition. A glass cloth (WEA-18W05F manufactured by Nitto Boseki Co., Ltd.) was impregnated with the varnish thus prepared, followed by drying in a drying oven at 140°C for 6 minutes to prepare a prepreg. The prepreg had an epoxy resin composition content of 49% by weight. Evaluate the appearance of the prepreg

Using this prepreg, the glass transition temperature was determined as in Examples 5 to 12. The impregnability of the prepreg and the resistance to soldering heat after the pressure cooking test (PCT) were also measured. The results are shown in Table 9.

Examples 14 and 15

Repeat the procedure of Example 13, the difference is that the amount shown in Table 9 is used to add polymer resin (46) and (47) instead of adding polymer resin (45), to prepare prepreg paint, and then into prepreg Blank. The varnishes and prepregs thus prepared were tested as in Example 13 for glass transition temperature, resistance to soldering heat and impregnation after (PCT). The results are also shown in Table 9.

Table 9

Example 13 Example 14 Example 15

Composition of epoxy resin composition

Plus Polymer Resin(45) 100

(46) 100

(47) 100

Dicyandiamide 2.5 2.5 2.5

2-Ethyl-4-methylimidazole 0.15 0.15 0.15

The nature of the cured product

Glass transition temperature, Tg℃ 171 170 162

Resistance to soldering heat after PCT

120 minutes 0 0 0

150 minutes 0 0 △

Impregnation of paint on glass cloth good good good good

Comparative Examples 13 to 22

The procedure of Example 13 was repeated except that the epoxy resins (28) to (30) shown in Table 7 and the addition polymer resins (38) to ( 44) Preparation of varnishes of epoxy resin compositions and subsequent prepregs. The glass transition temperature of the lacquer and prepreg thus prepared was determined as in Example 13. Table 10 shows the results of solder heat resistance and immersion resistance after PCT.

As listed above, the epoxy resin of the present invention is easy to mold because it exhibits a relatively low viscosity when mixed with a curing agent. Once cured, the epoxy resins of the present invention exhibit excellent heat resistance as well as high mechanical strength. Therefore, it is especially suitable for use in combination with various types of fibers to form plastic composite materials.

The epoxy resin composition of the present invention contains as its main component the addition polymer resin prepared by the addition polymerization reaction of the special co-glycidyl etherified epoxy resin of the present invention, the composition Exhibits excellent impregnation to materials such as glass cloth, and once cured, the cured product exhibits excellent heat resistance, resistance to blistering, and adhesion to copper cladding.

Claims (15)

1, a kind of epoxy resin (A), it is made of bisphenol (I) and novolac resin (II) It is produced by glycidyl etherification reaction with at least one selected from epihalohydrin and methyl epihalohydrin. 2. The epoxy resin (A) according to claim 1, wherein said bisphenol (I) and said novolak (II) are used in a weight ratio of 1-95:99-5. 3. The epoxy resin (A) according to claim 1, wherein said bisphenol (I) and said novolak resin (II) are used in a weight ratio of 50-90:50-10. 4. The epoxy resin (A) according to claims 1 to 3, wherein said novolac resin (II) has a softening point up to 110°C, a number average molecular weight of 1000 to 300 and a molecular weight distribution of up to 2. 5. An epoxy resin composition comprising a polymer-added resin (B) prepared from bisphenol (I) and a novolak resin (II) with at least one selected from the group consisting of Epoxy resin (A) is prepared by glycidyl etherification of one of epihalohydrin and methyl epihalohydrin; then said epoxy resin (A) is reacted with halogenated bisphenol (Ⅲ) to prepare Add polymer resin (B). 6. The epoxy resin composition according to claim 5, wherein the reaction between said epoxy resin (A) and said halogenated bisphenol (III) is at least one selected from the group consisting of epoxy resin (E) and Epoxidation is carried out in the presence of one of the halogenated bisphenols (F). 7. The epoxy resin composition according to claim 6, wherein said epoxidized halogenated bisphenol (F) is used in an amount of 1 to 15% by weight. 8. A varnish containing, as its main components, a solvent and the epoxy resin composition according to any one of claims 5 to 7. 9. A laminate prepared by impregnating a reinforcement with a lacquer according to claim 8. 10. An epoxy resin composition comprising a polymer-added resin (D) in which bisphenol (I), novolak resin (II), and halogenated bisphenol (III) Glycidyl etherification with at least one selected from epihalohydrin and methyl epihalohydrin to produce an epoxy resin (C); then reacting the epoxy resin (C) with halogenated bisphenol (Ⅲ) Prepared by adding polymer resin (D). 11. The epoxy resin composition according to claim 10, wherein the reaction between said epoxy resin (C) and said halogenated bisphenol (III) is carried out in the presence of epoxy resin (E). 12. The epoxy resin composition according to claim 10 or 11, wherein said novolak resin (II) has a softening point of up to 110°C, a number average molecular weight of 1000 to 300, and a molecular weight distribution of up to 2. 13. The epoxy resin composition according to any one of claims 11 or 12, wherein said bisphenol (I), said novolak resin (II) and said halogenated bisphenol (III) are used The weight ratio is 5-80; 94-5: 1-15. 14. A varnish comprising, as its main components, a solvent and the epoxy resin composition according to any one of claims 10 to 13. 15. A laminate prepared by impregnating reinforcements with a lacquer according to claim 14.