KR20180062984A - Substituted allyl ether resins, methallyl ether resins, epoxy resins, epoxy resin compositions, and cured products thereof - Google Patents

Abstract

[식 중, R₁은 각각 독립적으로 알킬기를 나타내고, R₂는 각각 독립적으로 수소 원자 또는 알킬기를 나타내고, a는 각각 1~3을 나타낸다. n은 1~10의 반복수의 평균값을 나타낸다.]An object of the present invention is to provide a substituted allyl ether resin which is suitable for electric and electronic materials and raw materials thereof, and which is low in halogen and which is inexpensively obtained by the following formula (1), and an epoxy resin using the same.

Wherein each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, and a represents 1 to 3, respectively. and n represents an average value of the number of repeats of 1 to 10.]

Description

Substituted allyl ether resins, methallyl ether resins, epoxy resins, epoxy resin compositions, and cured products thereof

The present invention relates to a substituted allyl ether resin, a metallyl ether resin, an epoxy resin, an epoxy resin composition, and a cured product thereof suitable for use in electric and electronic materials requiring heat resistance.

BACKGROUND ART Epoxy resin compositions have been extensively used in fields such as electric and electronic parts, structural materials, adhesives, and paints due to workability and excellent electrical properties, heat resistance, adhesiveness, moisture resistance (water resistance)

Conventionally, allyl ether compounds have been used as additives for reactive diluents, crosslinking agents, flame retardants and the like, as raw materials for photocurable monomers (Patent Document 1). The allyl ether compound can be used as a raw material for an epoxy resin obtained by an oxidation reaction. The obtained epoxy resin has been developed because it can be used for various applications such as paints, structural materials, and electric and electronic materials (Patent Document 2).

On the other hand, in the field of electric and electronic parts in recent years, the movement of converting gold wires used for wire bonding for connecting an IC chip, a lead frame, and a printed board into a copper wire from the viewpoint of cost reduction has been advanced rapidly. Here, when an epoxy resin produced by a method using a chlorine-containing compound (epichlorohydrin) as a sealing material of a semiconductor using a copper wire is used, the total amount of chlorine remaining in the epoxy resin is increased and the copper wire is corroded have. Therefore, the application of the epoxy resin to a semiconductor or the like is limited, and it is necessary to repeat troublesome purification for use in the above applications. In order to prevent such chlorine-induced corrosion, it is effective to use an epoxy resin obtained by a method not using a chlorine-containing compound. As a technique for producing an epoxy resin without using a chlorine-containing compound, for example, Patent Document 3 discloses a method for producing a bifunctional epoxy resin by reacting a compound having a carbon-carbon double bond with hydrogen peroxide. Recently, a process for producing an epoxy resin using an organic carboxylic acid has also been reported (Patent Documents 4 and 5).

Japanese Patent Application Laid-Open No. 2005-170890 Japanese Patent Application Laid-Open No. H06-067253 Japanese Patent Application Laid-Open No. 2011-225711 Japanese Patent Laid-Open Publication No. 2012-52062 Japanese Patent Application Laid-Open No. 2006-151900 International Publication No. 2014/123051

The inventors of the present invention have developed allyl ether resins that are low in halogen and can be obtained at low cost (Patent Document 6), but further improvement is required. Therefore, an object of the present invention is to provide a substituted allyl ether resin and a metallyl ether resin which are suitable for electric and electronic materials and raw materials thereof, and which are low in halogen and inexpensively obtained, and an epoxy resin using them.

In order to accomplish the above object, the present invention is as follows.

[1] A substituted allyl ether resin represented by the following formula (1).

(Wherein each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3, and n represents an average value of the number of repeating units of 1 to 10)

[2] A methallyl ether resin represented by the following formula (2).

(Wherein each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3, and n represents an average value of the number of repeating units of 1 to 10)

[3] An epoxy resin using the substituted allyl ether resin according to [1] or the metalyl ether resin according to the above [2].

[4] An epoxy resin composition comprising the epoxy resin according to [3], a curing agent and / or a curing catalyst.

[5] A cured product obtained by curing the epoxy resin composition according to [4] above.

(Effects of the Invention)

In the present invention, a low halogen substituted allyl ether resin or a methallyl ether resin suitable for an electric and electronic material and its raw materials is obtained. In addition, the substituted allyl ether resin or the metallyl ether resin of the present invention can provide a precursor of a cured product excellent in low dielectric properties, flame retardancy and toughness by its polymerization or by epoxidation or Clizen transition.

First, the substituted allyl ether resin which is one embodiment of the present invention will be described.

The substituted allyl ether resin of the present invention is represented by the following formula (1).

(Wherein each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3, and n represents an average value of the number of repeating units of 1 to 10)

Here, n is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 2 to 4.

Examples of the alkyl group in the formula include a methyl group, an ethyl group, a propyl group, and an isopropyl group. From the viewpoint of high electron density and reactivity of oxidative epoxidation, the methyl group or the ethyl group is preferable, and the methyl group is particularly preferable.

Next, a description will be given of a methallyl ether resin (hereinafter referred to as " MEP ") which is another embodiment of the present invention.

The MEP of the present invention is represented by the following formula (2).

(Wherein each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3, and n represents an average value of the number of repeating units of 1 to 10)

Here, n is preferably 1 to 10, more preferably 2 to 8, and particularly preferably 2 to 4.

Examples of the alkyl group in the formula include a methyl group, an ethyl group, a propyl group, and an isopropyl group, among which a methyl group is preferable.

Compared with resins such as cresol novolak in general, these materials are excellent in flame retardancy and can produce a composition capable of exhibiting flame retardancy without adding halogen as a flame retardant. It is also useful for environmental load, and it is possible to prevent the movement of ionic components such as chlorine, which is somewhat contained in high hydrophobicity. Not only do they have high electrical reliability, but also low halogen and combinations of these structures are useful as electrical and electronic materials.

The total chlorine remaining in the MEP is preferably 500 ppm or less, more preferably 300 ppm or less, particularly preferably 100 ppm or less.

The product containing MEP obtained by a production method described later is measured by high performance liquid chromatography (hereinafter also referred to as " HPLC "), and its chromatogram contains a peak of MEP of n = 1 in the formula (2) = 2, peaks of impurities may be identified between the peaks of the MEP.

From the viewpoint of reactivity when the MEP is epoxidized, the peak of the impurity is more preferably less than 1.5% by area, particularly preferably less than 1.0% by area, based on the total area of the product containing MEP. If the area ratio exceeds 2.0% by area, there is a fear that the progress of the epoxidation reaction will be greatly affected.

The metallyl ether resin of the present invention preferably has a softening point of 120 캜 or lower. If the softening point of the MEP exceeds 120 캜, it is very difficult to dissolve into the solvent, so that it is difficult to remove the salt contained in the MEP by washing or the like, which is not preferable from the viewpoint of corrosion in particular in fields requiring electrical reliability.

(Method for producing a methallyl ether resin)

The metallyl ether resin of the present invention is obtained by reacting the corresponding phenol resin and the metallyl halide in the presence of a base in a solvent.

(Phenolic resin)

Examples of the phenol resin used in the production of MEP include a reaction product of phenol and 4,4'-bis (chloromethyl) -1,1'-biphenyl, a reaction product of phenol and 4,4'-bis (methoxymethyl) 1,1 ' -biphenyl. ≪ / RTI >

(Methallyl halide)

As the metallyl halide used in the production of MEP, β-methallyl chloride is preferable from the viewpoint of reactivity with the phenol resin.

Here, the? -Methalyl chloride tends to be a polymer (polymethalyl chloride) by polymerizing the metallyl chlorides, but the metallyl chloride used in the production of the compound having the metallyl ether moiety is preferably a poly It is preferable to use a material having a small ratio.

If the content of the poly (methyl chloride) in the metallyl chloride to be used is large, it is not only a cause of increasing the total chlorine amount of the obtained epoxy resin of the present invention obtained using the MEP obtained by using the MEP, but also contributing to the increase of the molecular weight of the obtained epoxy resin There is a risk of leaving a very small amount of gel. In addition, in order to lower the chlorine amount, it is necessary to add a considerable amount of a basic substance, which is not industrially undesirable, and there is a fear that a metallyl alcohol having high toxicity in the system is produced.

The content of the polymethalyl chloride can be easily confirmed by gas chromatography or the like. The content of the specific polymethalyl chloride is preferably 1% or less by area based on the area ratio of the metallyl chloride monomer as measured by gas chromatography More preferably 0.5% by area or less, particularly preferably 0.2% by area or less.

In the production of MEP, the amount of the metallyl halide such as metallyl chloride is usually 1.0 to 2.0 moles, preferably 1.0 to 1.60 moles, more preferably 1.0 to 1.50 moles, per 1 mole of the hydroxyl group of the phenol resin.

In the case of producing the substituted allyl ether resin of the present invention, the substituted allyl ether resin of the present invention can be obtained by using the substituted allyl halide instead of the above-mentioned methallyl halide and employing the production method described below.

[base]

As a base to be used in the production of MEP, an alkali metal hydroxide is preferable, and specific examples thereof include sodium hydroxide, potassium hydroxide and the like. Such an alkali metal hydroxide may be used in a solid state or in the form of an aqueous solution thereof, but is preferably used in the form of a solid formed in a flake form from the viewpoints of solubility in a solvent and handling.

In the production of MEP, the amount of the base such as an alkali metal hydroxide is generally 1.0 to 2.0 moles, preferably 1.0 to 1.60 moles, more preferably 1.0 to 1.50 moles, per 1 mole of the hydroxyl group of the phenol resin.

[menstruum]

The solvent used in the production of the MEP preferably contains an aprotic polar solvent, and more preferably includes water and an aprotic polar solvent. The solubility of the phenolic resin in the solvent can be improved by containing the aprotic polar solvent as the solvent used in the production of the MEP. Examples of such aprotic polar solvents include dimethylsulfoxide, N-methylpyrrolidone, dimethylacetamide, dioxane, dimethoxyethane, diglyme, dimethylformamide and the like, with dimethylsulfoxide being particularly preferred.

In the production of MEP, the amount of the aprotic polar solvent such as dimethylsulfoxide is preferably 20 to 300% by mass, more preferably 25 to 250% by mass, based on the total mass of the phenol resin, 25 to 200% by mass. An aprotic polar solvent such as dimethylsulfoxide is not useful for purification such as washing with water and is difficult to remove because of its high boiling point, so that it is not preferable that the amount of the polar solvent used exceeds 300 mass% with respect to the total mass of the phenol resin .

The solvent used in the production of the MEP may contain an alcohol having 1 to 5 carbon atoms in addition to the above-mentioned water and aprotic polar solvent.

The solvent used in the production of the MEP may include the above-mentioned aprotic polar solvent such as methyl ethyl ketone, methyl isobutyl ketone, toluene and the like and an organic solvent (other organic solvent) other than the alcohol having 1 to 5 carbon atoms. The amount of the other organic solvent is preferably 100 mass% or less, more preferably 0.5 to 50 mass%, based on the amount of the aprotic polar solvent used. When methyl ethyl ketone, methyl isobutyl ketone, toluene or the like is excessively used, the Cl 1 transition occurs during the reaction and the residual phenolic hydroxyl group is increased, so that the amount of the metal chloride in the system is insufficient, Or a problem that the phenolic hydroxyl group is not entirely converted into the metallyl etherification may occur, which is not preferable.

[Reaction conditions, etc.]

In the production of MEP, the reaction temperature of the metallyl etherification reaction of the phenol resin is usually from 30 to 90 캜, preferably from 35 to 80 캜. In order to obtain MEP with higher purity, it is preferable to increase the reaction temperature by dividing into two or more stages. For example, it is particularly preferable to set the temperature to 35 to 50 ° C in the first stage and 45 ° C to 70 ° C in the second stage .

The reaction time of the methallyl etherification reaction of the phenol resin is usually 0.5 to 10 hours, preferably 1 to 8 hours, particularly preferably 1 to 5 hours. The reaction time is not less than 0.5 hour, the reaction proceeds sufficiently, and it is possible to suppress the production amount of the by-product to be low because it is 10 hours or less.

After completion of the reaction, the solvent is distilled off under reduced pressure to obtain a product. The recovered product is dissolved in a ketone compound having 4 to 7 carbon atoms (such as methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, cyclohexanone and the like) at 40 ° C to 90 ° C, Is washed with water until the water layer becomes pH 5 to 8 in a state where it is warmed to 50 to 80 ° C. It is possible to prevent the progress of the reaction from being suppressed by breaking the balance of the catalyst system at the time of the subsequent exocoxidation reaction by washing with water until the pH of the water layer becomes 8 or less.

Further, the methallyl etherification reaction of the phenol resin is usually carried out while blowing an inert gas such as nitrogen into the system (in the liquid or in the liquid). It is possible to prevent the resulting product from being colored by blowing the inert gas into the system while performing the reaction.

The blowing amount per unit time of the inert gas differs depending on the volume of the kiln used in the reaction. For example, the blowing amount per unit time of the inert gas is adjusted so that the volume of the kiln can be substituted for 0.5 to 20 hours desirable.

Next, the epoxy resin of the present invention will be described.

The epoxy resin which is one embodiment of the present invention is represented by the following formula (3).

(Wherein each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3, and n represents an average value of the number of repeating units of 1 to 10)

The epoxy resin, which is another embodiment of the present invention, is represented by the following formula (4).

(Wherein each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3, and n represents an average value of the number of repeating units of 1 to 10)

The epoxy resin of the present invention preferably has an epoxy equivalent of 260 to 285 g / eq., More preferably 260 to 280 g / eq. When the epoxy equivalent is more than 285 g / eq., It means that the amount of epoxy group per unit structure is decreased and the number of epoxy groups is decreased. Therefore, it is not preferable from the viewpoint of heat resistance.

Examples of the alkyl group in the formula include a methyl group, an ethyl group, a propyl group, and an isopropyl group. A methyl group or an ethyl group is preferable, and a methyl group is particularly preferable.

The methyl group-containing epoxy resin tends to have a high elastic modulus with respect to ordinary epoxy resins, and tends to exhibit properties suitable for fiber-reinforced plastics (FRP) and carbon fiber-reinforced plastics (CFRP).

The softening point of the epoxy resin of the present invention is preferably 30 to 130 占 폚, more preferably 40 to 120 占 폚. If the softening point is too low, blocking at the time of storage becomes a problem, and there are many problems such as handling at low temperatures. On the other hand, when the softening point is excessively high, there is a case that the handling is deteriorated at the time of kneading with another resin.

The total chlorine remaining in the epoxy resin obtained by the reaction is preferably 1000 ppm or less, more preferably 600 ppm or less, particularly preferably 300 ppm or less. Further, the amount of sulfuric acid ions extracted by hot water extraction is preferably 1000 ppm or less, more preferably 600 ppm or less.

The pressure of the pressure cooker test (PCT) extracted from the cured product of the present invention is preferably 5 ppm or less, more preferably 2.5 ppm or less, particularly preferably 1.5 ppm or less.

The melt viscosity range of the epoxy resin of the present invention is preferably 0.01 Pa · s to 0.10 Pa · s. When the melt viscosity is low, the molecular weight tends to be small and the content of the skeleton such as the formula (3) or (4) tends to decrease. Particularly preferably 0.02 Pa · s to 0.09 Pa · s.

The methallyl ether resin of the present invention can be made into an epoxy resin of the present invention by oxidation. Examples of the oxidation method include a method of oxidizing with peroxide such as acetic acid peroxide, a method of oxidizing with hydrogen peroxide, a method of oxidizing with air (oxygen), a method of oxidizing with carboxylic acid peroxide, and the like.

Specific examples of the method of exocoxidation by peroxide include the method described in Japanese Patent Application Laid-Open No. 2006-52187.

Although various methods can be adopted in the method of the epoxidation by the hydrogen peroxide water, specifically, the method described in JP-A-59-108793, JP-A-62-234550, JP- 5-213919, JP-A-11-349579, JP-A-1-33471, JP-A-2001-17864, JP-A-3-57102, JP- Japanese Patent Laid-Open Publication No. 2011-225654, Japanese Patent Application Laid-Open No. 2011-079794, Japanese Patent Application Laid-Open No. 2011-084558, Japanese Patent Application Laid-Open No. 2010-083836, Japanese Patent Application Laid-Open No. 2010-095521 You can adapt the way you can.

A particularly preferable method for obtaining an epoxy resin (hereinafter simply referred to as " the epoxy resin of the present invention ") which is one embodiment of the present invention represented by the above formula (4) is also illustrated below. The epoxy resin of the present invention is obtained by reacting hydrogen peroxide with a metallyl ether resin represented by the formula (2) in the presence of a tungstic acid compound, an organic carboxylic acid and a phosphoric acid compound.

(Tungstate compound)

The process for producing the epoxy resin of the present invention is carried out in the presence of a tungstic acid compound. In the present invention, the tungstate compound is not particularly limited as long as it is a compound capable of generating tungstate ion (WO ₄ ^2- ) in water. Examples of the tungstate compound include tungstic acid, tungsten trioxide, ammonium tungstate, ammonium tungstate, potassium tungstate Dihydrate, sodium tungstate dihydrate, calcium tungstate, barium tungstate, and the like. Among them, tungstic acid, tungsten trioxide, tungstic acid, sodium tungstate dihydrate and potassium tungstate dihydrate are preferable from the viewpoint of improvement of the production rate of epoxy group. These tungstic acid compounds may be used alone or in combination of two or more. The amount of the tungstic acid compound to be used is preferably 1 × 10 ^-6 to 0.2 mol, more preferably 0.0001 to 0.2 mol, per 1 mol of the compound represented by the formula (2) from the viewpoint of improvement of the production rate of the epoxy group.

(Organic carboxylic acid)

The process for producing the epoxy resin of the present invention is carried out in the presence of an organic carboxylic acid. In the present invention, the organic carboxylic acid is not particularly limited as long as it acts as a peroxide.

The carboxylic acid constituting the organic carboxylic acid is not particularly limited and includes formic acid, acetic acid, propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hydroxyanic acid, pivalic acid, capronic acid, oxalic acid, malonic acid, Tartaric acid, citric acid, maleic acid, malic acid, benzoic acid, salicylic acid, toluic acid, chlorobenzoic acid, nitrobenzoic acid, phthalic acid and anisic acid.

Among them, the molecular weight is preferably 46 to 150, more preferably 46 to 120 in order to improve the balance between hydrophobicity and hydrophilicity. It is preferable that the carbon chain bonded to the carbon atom of the carboxylic acid is linear. Examples of the organic carboxylic acid having a linear carbon chain bonded to the carbon atom include acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, malonic acid and succinic acid.

Organic and carboxylic acids can easily be generated by reacting organic carboxylic acids or organic carboxylic anhydrides with hydrogen peroxide. Examples of the organic carboxylic acid and its anhydride include formic acid, acetic acid, acetic anhydride, propionic acid, propionic anhydride, butyric acid, isobutyric acid, valeric acid, isovaleric acid, hydroxyanic acid, pivalic acid, benzoic acid and salicylic acid. Formic acid, acetic anhydride, acetic anhydride and propionic acid are particularly preferable from the viewpoints of improving the production rate of the epoxy group or removing after the reaction. The method of generating an organic carboxylic acid in a reaction system can be easily adjusted simply by mixing a widely used reagent. Since the reaction proceeds while consuming the generated carboxylic acid, It is also excellent in that it is not necessary to store a carboxylic acid.

The amount of the organic carboxylic acid to be used is preferably 0.01 to 5.0 moles, more preferably 0.05 to 4.0 moles, per 1 mole of the methallyl ether resin represented by the formula (2) from the viewpoint of improvement of the production rate of the epoxy group.

(Organic solvent)

The process for producing an epoxy resin of the present invention is carried out in the presence of a specific organic solvent. The production rate of the epoxy group can be greatly improved by carrying out the reaction in the presence of a specific organic solvent. This is related to compatibility with a tungstic acid compound, a phosphoric acid compound, an organic carboxylic acid, and the like, and it is presumed that the reaction proceeds smoothly by preventing precipitation of a poorly soluble component when the MEP is dissolved.

In the present invention, from the viewpoint of the solubility of the starting material, alcohols, nitriles and the like can not be used as specific organic solvents. Further, when ketones or sulfoxides are used, acetone, dimethylsulfoxide and the like can not be used because the side reaction proceeds. Examples of suitable organic solvents include diethyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diglyme, triglyme, ethylene glycol diacetate, methyl acetate, ethyl acetate, N, N-dimethylformaldehyde ), N, N-dimethylacetamide (hereinafter "DMA"), N-methylmorpholine, N-methylpyrrolidone, epsilon -caprolactam, toluene, xylene and mesitylene.

A step of reacting a compound having a bifunctional or higher metal-hydride ether moiety with hydrogen peroxide is performed in a two-phase system of an organic phase and a water phase.

The amount of the specific organic solvent to be used is preferably 10 to 1000 parts by mass, more preferably 10 to 500 parts by mass, per 100 parts by mass of the methallyl ether resin represented by the formula (2) from the viewpoint of improving the production rate of the epoxy group.

(Phosphoric acid compound)

The method for producing the epoxy resin of the present invention is carried out in the presence of a phosphoric acid compound. The phosphoric acid compound is not particularly limited as long as it is a compound capable of generating phosphoric acid ion (PO ₄ ^3- ) in water, and examples thereof include phosphoric acid, dihydrogen phosphate alkali metal salt, dihydrogen phosphate alkali metal salt, Alkaline earth metal salts, alkali metal phosphate salts, alkaline earth metal phosphate salts, polyphosphoric acid, alkali metal polyphosphate, alkaline earth metal polyphosphate, tripolyphosphoric acid, tripolyphosphoric acid alkali metal salt and tripolyphosphoric acid alkaline earth metal salt. Among them, those containing salts such as phosphoric acid, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, and potassium phosphate are preferred because they are easily available.

The amount of the phosphoric acid compound to be used is preferably 0.01 to 1.0 mol, more preferably 0.05 to 0.5 mol, per 1 mol of the compound represented by the formula (2) from the viewpoint of improvement of the production rate of the epoxy group.

(Hydrogen peroxide)

In the method for producing an epoxy resin of the present invention, the hydrogen peroxide to be reacted with the metallyl ether resin represented by the above formula (2) is not particularly limited, but is usually dissolved in water and added as hydrogen peroxide solution. The concentration of hydrogen peroxide in the hydrogen peroxide solution is not particularly limited, but from the viewpoint of production of an epoxy group, the concentration of hydrogen peroxide is preferably 10 to 90 mass%. The amount of hydrogen peroxide solution to be used is not particularly limited, but the amount of hydrogen peroxide is preferably 0.3 to 10 moles, more preferably 1 to 6 moles, per 1 mole of the allyl group of the metallyl ether resin. The amount of the hydrogen peroxide solution is 0.3 mole or more per mole of the metallyl group of the metallyl ether resin, so that the epoxidation can proceed efficiently, and the hydrolysis of the resulting epoxy group can be suppressed when the amount is less than 10 moles.

The method for producing the epoxy resin of the present invention is not particularly limited, but an organic solvent such as toluene, xylene, mesitylene, dimethoxyethane, ethyl acetate or tetrahydrofuran in which a methallyl ether resin is soluble is added to the above- It is preferable to add a compound, a phosphoric acid compound, and then add hydrogen peroxide water to initiate the epoxidation reaction. However, the production method of the epoxy resin of the present invention is not limited to this addition order, and the presence of the tungstic acid compound and the phosphoric acid compound can be efficiently carried out by converting the high-surface methallyl ether resin into the epoxy group of the carbon- .

In the method for producing an epoxy resin of the present invention, the reaction temperature at the time of the epoxidation is not particularly limited, but is preferably 10 to 120 ° C, more preferably 25 to 100 ° C. The reaction rate can be made to be more than 10 DEG C, and the hydrolysis reaction of the epoxy group formed can be suppressed when the temperature is 120 DEG C or less.

In the production process of the epoxy resin of the present invention, the reaction time depends on the reaction temperature and the amount of the catalyst, etc. However, in order to ensure a sufficient time for the epoxidation to proceed sufficiently and to produce industrially efficiently, a predetermined amount of hydrogen peroxide It is preferably 1 to 48 hours after the addition, more preferably 3 to 36 hours, particularly preferably 4 to 24 hours.

After completion of the reaction, the excess hydrogen peroxide is removed. As a method of removing hydrogen peroxide, there is a method of separating and washing with water. Methylisobutyl ketone having a weight twice as much as the weight of the resin is added, and liquid separation operation is performed with ion-exchanged water having a weight of 1 time, and the aqueous layer is discarded. This procedure is repeated until the hydrogen peroxide is completely removed. Whether or not the hydrogen peroxide is removed is confirmed by confirming that the potassium iodide starch test is negative.

Then, after the removal of the hydrogen peroxide, the organic phase is concentrated under reduced pressure. In this case, if the heating is excessive, there is a possibility that the resin may cause polymerization. Therefore, the concentration is preferably carried out at 90 to 180 ° C, more preferably 110 to 150 ° C.

≪ Epoxy resin composition &

The epoxy resin composition of the present invention contains a curing catalyst (curing accelerator) and / or a curing agent in addition to the epoxy resin of the present invention. In addition, other epoxy resins may be contained as optional components.

In the epoxy resin composition of the present invention, the epoxy resin of the present invention may be used in combination with another epoxy resin. Examples of other epoxy resins which can be used in combination with the epoxy resin of the present invention include novolak type epoxy resins, bisphenol type epoxy resins, biphenyl type epoxy resins, triphenylmethane type epoxy resins and phenol aralkyl type epoxy resins. Specific examples thereof include bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpenediphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'- (1,1'-biphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis Hydroxyphenyl) ethane, phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol or dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, Benzoyl peroxide, benzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'- (Methoxymethyl) -1,1'-biphenyl, 1,4-bis (chloromethyl) benzene or 1,4-bis (methoxymethyl) benzene and their modifications, tetrabromobisphenol A Halogenated bisphenol Glycidyl ether epoxy resins, glycidyl ester epoxy resins, silsesquioxane epoxy resins (chain, cyclic, ladder, or alicyclic epoxy resins) derived from alcohols or alcohols, alicyclic epoxy resins, glycidylamine- And an epoxy resin having a glycidyl group and / or an epoxy cyclohexane structure in a siloxane structure having at least two or more mixed structures thereof). However, the present invention is not limited thereto.

Specific examples of the curing catalyst that can be used in the present invention include amine compounds such as triethylamine, tripropylamine, and tributylamine; amines such as pyridine, dimethylaminopyridine, 1,8-diazabicyclo [5.4.0] undeca- 2-phenylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenyl-4-methylimidazole, Benzyl-2-methylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine, 2,4-diamino- (2'-ethyl, 4-methylimidazole (1 ')) ethyl-s-triazine, Triazine, 2,4-diamino-6 (2'-methylimidazole (1 ')) ethyl-s-triazine isocyanuric acid adduct, 2-methylimidazole isocyanuric acid 2 : 3 adduct, 2-phenylimidazole Phenyl-3,5-dihydroxymethylimidazole, 2-phenyl-4-hydroxymethyl-5-methylimidazole, 1-cyanoethyl- , 5-dicyanoethoxymethylimidazole, and heterocyclic compounds thereof and heterocyclic compounds such as phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, naphthalenedicarboxylic acid, maleic acid, oxalic acid Diazabicyclo (5.4.0) -7-undecene and the like, and diamine compounds such as 1,8-diazabicyclo (5.4.0) -7-undecene, and tetramethylborate , Their diazole compounds and phenol novolacs, salts of the aforementioned polycarboxylic acids or phosphinic acids, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, Trimethylethylammonium hydroxide, trimethylpropylammonium hydride But are not limited to, hydroxides such as hydroxides, hydroxides, hydroxides, hydroxides, hydroxides, hydroxides, hydroxides, hydroxides, hydroxides, hydroxides, Phosphonium compounds such as triphenylphosphine, tri (toluyl) phosphine, tetraphenylphosphonium bromide, tetraphenylphosphonium tetraphenylborate and the like, 2,4,6-trisaminomethylphenol and the like (Such as zinc salts, tin salts and zirconium salts such as 2-ethylhexanoic acid, stearic acid, behenic acid and myristic acid), phosphoric acid ester metal (such as octylphosphoric acid, stearylphosphoric acid and the like) ), Alkoxy metal salts (tributyl aluminum, tetrapropyl zirconium and the like), acetylacetone salts (acetylacetone zirconium chelate There may be mentioned metal compounds such as acetylacetone titanium chelate, etc.). In the present invention, phosphonium salts, ammonium salts, and metal compounds are particularly preferable in terms of coloration upon curing and changes thereof. In addition, when a quaternary salt is used, a salt with a halogen may leave a halogen in the cured product.

The curing catalyst is used in an amount of 0.01 to 5.0 parts by weight based on 100 parts by weight of the epoxy resin.

As the curing agent for use in the epoxy resin composition of the present invention, known curing agents such as amine compounds, acid anhydride compounds, amide compounds, phenol compounds and carboxylic acid compounds can be used. Those described in JP-A-2006/090662.

Specific examples of the curing agent that can be used include polyamides synthesized by dimer of diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, linolenic acid and ethylene diamine Nitrogen-containing compounds (amines, amide compounds) such as resins; Examples thereof include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic anhydride, anhydrous nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, Carboxylic acid anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic acid anhydride, cyclohexane Acid anhydrides such as 1,3,4-tricarboxylic acid-3,4-anhydride; Various alcohols, carboxylic acid resins obtained by addition reaction of carbinol-modified silicone with the above-mentioned acid anhydride; Bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpendiphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5'-tetramethyl- [1,1 (4-hydroxyphenyl) -4,4'-diol, hydroquinone, resorcin, naphthalene diol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis Ethane or phenols (phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, dihydroxynaphthalene and the like) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, Bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) biphenyl, dihydroxyacetophenone, dicyclopentadiene, furfural, Polycondensates such as 1,1'-biphenyl, 1,4'-bis (chloromethyl) benzene or 1,4'-bis (methoxymethyl) benzene and their modified products, tetrabromobisphenol A Halogenated bisphenols, terpenes and Phenol resins such as a condensate of nolryu; Imidazole, trifluoroborane-amine complex, and compounds of guanidine derivatives, but are not limited thereto. These may be used alone or in combination of two or more.

In the epoxy resin composition of the present invention, the amount of the curing agent to be used is preferably 0.5 to 1.5 equivalents, more preferably 0.6 to 1.2 equivalents based on 1 equivalent of the epoxy group of the epoxy resin. When the amount of the curing agent used is within the above range, good curing properties can be obtained.

In addition, the use of a cyanate ester compound as the other component is preferable. The cyanate ester compound can be made into a heat-resistant cured product having a higher crosslink density by reaction with the epoxy resin in addition to the curing reaction alone. Examples of the cyanate ester compound include 2,2-bis (4-cyanate phenyl) propane, bis (3,5-dimethyl- ) Ethane, derivatives thereof, and aromatic cyanate ester compounds. Further, it can be synthesized by, for example, reacting various phenol resins as described in the above-mentioned curing agent with cyanide or its salts. In the present invention, those having a structure such as 2,2-bis (4-cyanate phenyl) propane or its derivatives (partial polymerizers and the like) which do not have a benzene-like methylene structure in the molecule are preferred, Or two or more of them may be used in combination.

The epoxy resin composition of the present invention may contain a phosphorus-containing compound as a flame retardancy-imparting component. The phosphorus-containing compound may be of reaction type or of addition type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tricresyl phosphate, cresyldiphenyl phosphate, cresyl-2,6-dicyclyl phosphate, 1,3-phenylene bis (dicyclyl phosphate Phosphoric acid esters such as 1,4-phenylenebis (dicyclyl phosphate) and 4,4'-biphenyl (dicyclyl phosphate); 10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H- ; Containing epoxy compounds obtained by reacting an epoxy resin with active hydrogens of the above-mentioned phosphates, and red phosphorus. Phosphoric acid esters, phosphates or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylene bis Phosphate), 1,4-phenylenebis (dicyclyl phosphate), 4,4'-biphenyl (dicyclyl phosphate) or a phosphorus-containing epoxy compound are particularly preferable. The content of the phosphorus-containing compound is preferably 0.1 to 0.6 (weight ratio) of phosphorus-containing compound / total epoxy resin. If it is less than 0.1, flame retardancy is insufficient, and if it exceeds 0.6, hygroscopicity and dielectric properties of the cured product may be adversely affected.

The epoxy resin composition of the present invention may optionally contain a binder resin. As the binder resin, a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamide resin, a polyimide resin, . The blending amount of the binder resin is preferably within a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05 to 20 parts by weight based on 100 parts by weight of the total amount of the epoxy resin and the curing agent. do.

An inorganic filler may be added to the epoxy resin composition of the present invention if necessary. Examples of the inorganic filler include powders of crystalline silica, fused silica, alumina, zircon, calcium silicate, calcium carbonate, silicon carbide, silicon nitride, boron nitride, zirconium, forsterite, stearate, spinel, titania, talc, But the present invention is not limited thereto. These fillers may be used alone or in combination of two or more. The content of these inorganic fillers in the epoxy resin composition of the present invention is generally in the range of 0 to 95% by weight, and is preferably 50 to 95% by weight, It is preferable to use them in a range of 65 to 95% by weight depending on the shape of the package. The epoxy resin composition of the present invention may further contain various additives such as antioxidants, light stabilizers, silane coupling agents, release agents such as stearic acid, palmitic acid, zinc stearate and calcium stearate, pigments and the like, various thermosetting resins can do. Particularly, for the coupling agent, it is preferable to add a coupling agent having an epoxy group or a coupling agent having a thiol.

The epoxy resin composition of the present invention is obtained by uniformly mixing each component. The epoxy resin composition of the present invention can be easily made into a cured product by a method similar to a conventionally known method. For example, an epoxy resin component, a curing agent component and, if necessary, a curing accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a compounding agent are uniformly dispersed by an extruder, a kneader, a roll or a planetary mixer To obtain an epoxy resin composition. When the obtained epoxy resin composition is in the form of a liquid, the composition is impregnated into the substrate by potting or casting, or is poured into a mold, followed by casting or curing by heating. When the obtained epoxy resin composition is solid, it is molded after molding by using a mold or a transfer molding machine, and is cured by heating. The curing temperature and time are 2 to 10 hours at 80 to 200 ° C. As the curing method, it is possible to cure at a high temperature in a short time, but it is preferable to raise the temperature by the stepwise to advance the curing reaction. Concretely, initial curing is performed at 80 to 150 ° C, and post curing is performed at 100 to 200 ° C. As the curing step, the temperature is preferably divided into 2 to 8 steps, and more preferably 2 to 4 steps.

The epoxy resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethyl formamide, dimethylacetamide or N-methylpyrrolidone to prepare an epoxy resin composition varnish , A glass fiber, a carbon fiber, a polyester fiber, a polyamide fiber, an alumina fiber, a paper and the like, followed by heating and drying, is hot-pressed to obtain a cured product of the epoxy resin composition of the present invention. In this case, the solvent is generally used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, in the mixture of the epoxy resin composition of the present invention and the solvent.

Further, the epoxy resin composition of the present invention may be used as a film-like sealing composition. In the case of obtaining such a film-like resin composition, the epoxy resin composition varnish is applied on a release film, the solvent is removed under heating, and B staging is carried out to obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multi-layer substrate or the like, and as a batch film sealing of optical semiconductors.

Specific examples of applications of these compositions include adhesives, paints, coating agents, molding materials (including sheets, films, FRP and the like), insulating materials (sealing materials including printed boards and wire coatings, sealing materials, and cyanate resin compositions for substrates) Or an additive to another resin such as an acrylate ester resin as a curing agent for a resist. In the present invention, it is particularly preferable to use an insulating material for an electronic material (a sealing material including a printed board, a wire covering, etc., a sealing material, a cyanate resin composition for a substrate).

Examples of the adhesive include adhesives for civil engineering, construction, automobile, general office and medical use, as well as adhesives for electronic materials. Among these, adhesives for electronic materials include adhesives for semiconductors such as die-bonding agents and underfills, underfill for BGA reinforcement, anisotropic conductive films (ACF), and anisotropic conductive pastes (ACP) Adhesive for mounting, and the like.

As the sealing material and substrate, there are potting, dipping, transfer mold sealing for capacitors, transistors, diodes, light emitting diodes, ICs and LSIs, potting seals for ICs, LSIs, COB, , Sealing (including underfill for reinforcement) and package substrates for packaging of IC packages such as QFP, BGA, and CSP. It is also suitable for use as a substrate requiring functionality such as a network substrate or a module substrate.

The epoxy resin composition of the present invention is particularly preferably used in a semiconductor device.

The semiconductor device is the above-mentioned IC package group. The semiconductor device is obtained by sealing a silicon chip provided on a support substrate such as a package substrate or a die with the epoxy resin composition of the present invention. The molding temperature and molding method are as described above.

Example

Hereinafter, the present invention will be described concretely with reference to Examples and Comparative Examples, but the present invention is not limited to these Examples. Various analytical methods used in the examples are described below.

Epoxy equivalent: according to JIS K 7236 (ISO 3001)

ICI melt viscosity: according to JIS K 7117-2 (ISO 3219)

Softening point: according to JIS K 7234

Total chlorine:

Automatic sample burning - Ion Chromatograph device AQF-2100H Model Manufactured by Mitsubishi Chemical Corporation

The ion content was measured after combustion decomposition at an argon gas flow rate of 200 ml / min and an oxygen gas flow rate of 400 ml / min.

HPLC:

Column (Inertsil ODS-2)

The eluent was eluted with tetrahydrofuran and 1 mM sodium dihydrogenphosphate solution

The flow rate was 1.0 ml / min.

The column temperature was 40 캜

NMR:

Made by JNM-ECS400 JEOL Ltd.

The medium-

Glass Transition Point (Tg):

TMA thermomechanical measuring device TA-instruments, Q400EM

Measuring temperature range: 40 ℃ ~ 280 ℃

Heating rate: 2 캜 / min

Example 1

In a flask equipped with a stirrer, a reflux condenser and a stirrer, 25 parts by mass of water, 500 parts by mass of dimethylsulfoxide, 500 parts by mass of a phenol resin (phenol-biphenylene type hydroxyl equivalent of 200 g / And the temperature was raised to 45 캜 and dissolved. Subsequently, the mixture was cooled to 38 to 40 DEG C, and 130.0 parts by mass of a flaky caustic soda (purity: 99%, manufactured by Tosoh Corporation) (1.3 mol equivalent based on 1 molar equivalent of the hydroxyl group of the phenol resin) was added over 60 minutes. Thereafter, 294.3 parts by mass (1.3 molar equivalents based on 1 molar equivalent of the hydroxyl group of the phenol resin) of methallyl chloride (purity: 99%, manufactured by Tokyo Chemical Industry Co., Ltd.) was further added dropwise over 60 minutes, The reaction was carried out at 60 to 65 ° C for 1 hour for 5 hours.

After completion of the reaction, water and dimethylsulfoxide were distilled off under heating and decompression at 125 DEG C or lower using a rotary evaporator. Then, 740 parts by mass of methyl isobutyl ketone was added, and the water washing was repeated to confirm that the aqueous layer became neutral. Thereafter, the solvents were distilled off from the oil layer using a rotary evaporator while nitrogen bubbling under reduced pressure to obtain 600 parts by mass of MEP of formula (2) with n = 2.0.

Example 2

A flask equipped with a stirrer, a reflux condenser and a stirrer was charged with 1000 parts by mass of an ethyl acetate solution containing MEP obtained in Example 1 (concentration of MEP: 50% by mass) while nitrogen purge was carried out. 0.04 mole portion of potassium tungstate as a tungstate compound, 0.06 mole portion of potassium phosphate as a phosphoric acid compound, and 60.0 mass parts of acetic acid as an organic carboxylic acid per 100 parts by mass of MEP, and the temperature of the mixture was raised to 50 占 폚. After the temperature was elevated, a 35% aqueous hydrogen peroxide solution was added over 20 minutes while stirring so that the amount of hydrogen peroxide became 2 molar equivalents based on 1 molar equivalent of the metallyl group in the MEP. After completion of the addition, the mixture was directly stirred at 50 占 폚 for 24 hours.

Subsequently, liquid separation treatment was carried out, and the water phase was separated to obtain a solution containing the epoxy resin (EP1) of the present invention. The obtained epoxy resin (EP1) had an epoxy equivalent weight of 288 g / eq., An ICI melt viscosity of 0.07 Pa · s at a softening point of 59 ° C and a temperature of 150 ° C, and a total chlorine content of 15 ppm or less.

Example 3, Comparative Example 1

(EP2; phenol-biphenylene aralkyl type epoxy resin Nippon Kayaku Co., Ltd., NC-3000) was used in place of the epoxy resin (EP1) of the present invention obtained in Example 2, (Phenol resin (H-1 manufactured by Meiwa Plastic Industries, Ltd.) or phenol-biphenylene aralkyl phenol resin (GPH-65 manufactured by Nippon Kayaku Co., Ltd.)), and a curing catalyst (TPP, manufactured by Tokyo Chemical Industry Co., Ltd.) and filler (KIKUROSU MSR2212 manufactured by Tatsumori KK, the ratio of fillers in the table to the total amount of the epoxy resin composition) as a mold release agent, (KBN-303, manufactured by Shin-Etsu Chemical Co., Ltd.), and the mixture was uniformly mixed and kneaded using a mixing roll to prepare a mixture of the present invention Of an epoxy resin composition. This epoxy resin composition was pulverized with a mixer, and tabletted on a tablet machine. The tableted inventive and comparative epoxy resin compositions were transferred (175 DEG C for 60 seconds), and after the demolding, test pieces for curing and evaluation were obtained under the conditions of 160 DEG C x 2 hours + 180 DEG C x 6 hours.

The physical properties of the cured product were measured in the following manner. The curing agent species to be used in the evaluation items of the physical properties of the cured product are shown in Tables 1 and 2 below. The amount of the curing accelerator used is 1% with respect to the weight of the epoxy resin in the samples used for evaluation of heat resistance and shrinkage, In the samples used for evaluation of the flame retardancy, the weight of the epoxy resin was set to 2%.

<Bending Test>

Test was conducted at room temperature and 120 ° C in accordance with JIS K 6911.

<Permittivity test, dielectric tangent test>

Tests were conducted with a cavity resonator method using a 1 GHz cavity resonator manufactured by Kanto Electronic Application and Development Inc. Here, the sample size was 1.7 mm wide × 100 mm long, and the thickness was 1.7 mm.

&Lt; Flame retardancy test &

Determination of flame retardancy: It was conducted in accordance with UL94. Here, the sample size was 12.5 mm wide × 120 mm long, and the thickness was 0.8 mm.

· Combustion time: the sum of the time of the decontamination after 10 batches of 5 samples

&Lt; PCT Extracted Chlorine Measurement >

The epoxy resin cured product was pulverized with a cyclomill, and 1.5 g of the powder remaining at 200 mesh after passing through 100 mesh of the sieve was subjected to PCT extraction (121 캜 x 24 h) with ultrapure water (20 캜). The extract was filtered through 0.45 탆 filter, Converted into a resin unit amount.

It can be seen from Tables 1 and 2 that the cured product using the metallale ether resin of the present invention and the epoxy resin of the present invention is a cured product having excellent low dielectric properties, flame retardancy and toughness as compared with a cured product using a comparative epoxy resin.

Although the present invention has been described in detail with reference to specific embodiments, it is apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the present invention.

The present application is based on Japanese Patent Application (2015-190654) filed on September 29, 2015, the entirety of which is hereby incorporated by reference. Also, all references cited herein are incorporated by reference in their entirety.

(Industrial availability)

The substituted allyl ether resin, the metallyl ether resin, the epoxy resin, the epoxy resin composition and the cured product thereof of the present invention can be used in the fields of electric and electronic parts, structural materials, adhesives, paints and the like.

Claims (5)

A substituted allyl ether resin represented by the following formula (1).

(Wherein each R ₁ independently represents an alkyl group, each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3, and n represents an average value of the number of repeating units of 1 to 10) A methallyl ether resin represented by the following formula (2).

(Wherein each R ₂ independently represents a hydrogen atom or an alkyl group, a represents 1 to 3, and n represents an average value of the number of repeating units of 1 to 10) An epoxy resin using the substituted allyl ether resin according to claim 1 or the methallyl ether resin according to claim 2. An epoxy resin composition comprising the epoxy resin according to claim 3, a curing agent and / or a curing catalyst. A cured product obtained by curing the epoxy resin composition according to claim 4.