JP6041663B2 - Phenol resin, epoxy resin, epoxy resin composition, and cured product thereof - Google Patents

Description

  The present invention relates to a naphthol-containing epoxy resin excellent in flame retardancy.

  Epoxy resins are generally cured with various curing agents, resulting in cured products with excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, etc., adhesives, paints, laminates, moldings It is used in a wide range of fields such as materials and casting materials.

  In particular, naphthol-containing resins are expected to be highly heat-resistant and low-water-absorbing materials due to their rigid and hydrophobic skeletons, and their application in the electrical and electronic fields such as IC sealing materials, laminated materials, and electrical insulating materials are being studied. I came.

  On the other hand, in the electric / electronic field, flame retardancy is required, and in order to achieve the flame retardancy, epoxy resin compositions used for electric / electronic parts include halogen-containing epoxy resins and antimony series. Although flame retardants have been used extensively, the use of halogen-containing epoxy resins and antimony flame retardants has been restricted due to the tightening of regulations in European countries, and no halogen-free flame retardant resins and antimony flame retardants are added. Development of a resin composition excellent in flame retardancy is required.

Patent No. 3575776 Japanese Patent No.3992181 Patent No. 4311597

  In recent years, with the miniaturization and high performance of equipment in the electrical and electronic fields, not only improved mechanical properties and heat resistance, but also moisture resistance, flame resistance, electrical insulation, and low dielectric properties for the resins used. Improvements in properties and the like have been increasingly demanded, and the demand for epoxy resins has increased.

  In such a background, as a potential flame retardant resin candidate, Patent Documents 1 to 3 disclose naphthol-containing epoxy resins containing a naphthol skeleton and a biphenyl skeleton, but the flame retardancy is not sufficient, In addition, the flame retardancy is reduced due to thermal decomposition of the naphthol skeleton, and its application to electrical and electronic parts is limited.

  Since the naphthol-containing resin of the present invention includes a naphthol skeleton having high heat resistance and low water absorption, and exhibits excellent flame retardancy, the resin composition containing the phenol resin and epoxy resin of the present invention is an IC sealing material, a laminate material. It is extremely useful for a wide range of electrical and electronic applications such as electrical insulation materials.

  As a result of intensive studies, the present inventor has introduced a naphthol skeleton and a biphenyl skeleton at a specific ratio into the main skeleton, so that the naphthol-containing epoxy resin exhibits excellent flame retardancy while having heat resistance and low water absorption. It has been found that a cured product can be obtained, and has led to the present invention.

That is, the present invention
(1) Among the phenol resins represented by the formula (2) obtained by condensing phenols, naphthols and the compound represented by the formula (1), the naphthols are α-naphthol, the phenols, A phenolic resin having a naphthol introduction rate of 5 to 40 mol% among naphthols.
(In the above formula, X represents chlorine, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms.)
(In the formula, n is a repeating number and represents an integer of 1 to 50. R is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, Alternatively, it represents an alkenyl group having 2 to 10 carbon atoms, and each R may be the same as or different from each other.
(2) Of the phenol resins represented by the formula (2) obtained by condensing the phenols, naphthols, and the compound represented by the formula (1), the naphthols are β-naphthol, the phenols, A phenolic resin having a naphthol introduction rate of 5 to 35 mol% among naphthols.

(In the formula, X represents chlorine, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms.)
(In the formula, n is a repeating number and represents an integer of 1 to 50. R is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, Alternatively, it represents an alkenyl group having 2 to 10 carbon atoms, and each R may be the same as or different from each other.
(3) Of the phenol resins represented by the formula (2) described in (1), the naphthols are a mixture of α-naphthol and β-naphthol, and the naphthol introduction rate is 5 to 40 of the phenols and naphthols. Phenol resin that is mol%.
(4) Among the phenol resins represented by the formula (2) described in (1), an introduction rate of α-naphthol is 5 to 25 mol%, or a phenol resin into which β-naphthol is introduced.
(5) An epoxy resin represented by formula (3) obtained by reacting the resin according to any one of (1) to (3) with an epihalohydrin.
(In the formula, n is a repeating number and represents an integer of 1 to 50. R is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, Alternatively, it represents an alkenyl group having 2 to 10 carbon atoms, and each R may be the same as or different from each other.
(6) An epoxy resin composition comprising (a) an epoxy resin and (b) a phenol resin represented by the formula (2) according to any one of (1) to (3).
(7) An epoxy resin composition comprising an epoxy resin represented by formula (3) according to (a) and (5) and (b) a curing agent.
(8) An epoxy resin composition containing the epoxy resin represented by formula (3) according to (a) (5) and the phenol resin according to any one of (b) (1) to (3) .
(9) A cured product obtained by curing the epoxy resin composition according to any one of (6) to (8).
A mixture of phenols and naphthols,
About.

The phenolic resin of the present invention has the following formula (2)
(In the formula, n represents the number of repetitions. R represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 2 to 10 carbon atoms. Represents an alkenyl group, and each R may be the same as or different from each other.
It has the structure represented by these.
In the phenol resin represented by the above formula (2) of the present invention, n is usually 1 to 50, preferably 1 to 20, and particularly preferably 1 to 10.
Moreover, as R, a hydrogen atom or a C1-C10 alkyl group is preferable, and a hydrogen atom is especially preferable.

The hydroxyl equivalent of the phenol resin of the present invention is preferably 150 to 500 g / eq, more preferably 180 to 300 g / eq, and particularly preferably 200 to 280 g / eq.
Moreover, as a weight average molecular weight, 500-3000 are preferable.

The specific example of the manufacturing method of the phenol resin of this invention is demonstrated below.
The phenol resin of the present invention can be obtained by condensing phenols, naphthols, and a compound represented by the formula (1).

As the phenols and naphthols that can be used in the production of the phenol resin of the present invention, those represented by the following formulas (4) and (5) can be used.
(In the above formula, R represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. R may be the same or different.
(In the above formula, R represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms. R may be the same or different.
Here, as R, the thing of a C1-C10 alkyl group thru | or a hydrogen atom can be used conveniently.

  Specific examples of such phenols or naphthols include phenol, cresol, ethylphenol, n-propylphenol, isobutylphenol, t-butylphenol, octylphenol, nonylphenol, xylenol, methylbutylphenol, di-t-butylphenol and the like. Various o-, m-, p-isomers, cycloalkylphenols such as cyclopentylphenol, cyclohexylphenol and cyclohexylresole, substituted phenols such as phenylphenol, or phenols such as halogenated phenols such as monobromophenol and dibromophenol Or α-naphthol, β-naphthol, methyl naphthol, ethyl naphthol, monobromonaphthol, dibromonaphthol, allyl And naphthols such as naphthol. These phenols or naphthols may be used alone or in combination of two or more. When two or more types are used in combination, it is preferable to select one or more types from phenols and naphthols in order to obtain excellent cured properties. More preferably, it is preferable to use a mixture of phenol and α-naphthol or / and β-naphthol.

For the production of the phenolic resin of the present invention, the following formula (1)
(In the above formula, X represents a chlorine atom, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms.)
The biphenyl compound represented by these is used.
Specific examples of such biphenyl compounds include bismethoxymethyl biphenyl, bischloromethyl biphenyl, bismethylol biphenyl, and the like.

  The total charge of phenols and naphthols is usually 0.3 to 20 mol, preferably 0.4 to 15 mol, per 1 mol of the compound represented by formula (1). If the total amount of phenols and naphthols charged is too large, the amount of phenols and naphthols that do not participate in the reaction increases, and there is a possibility of excessive use of energy from the viewpoint of waste. If the total amount of phenols and naphthols added is too small, the molecular weight increases and gelation may occur.

  The use ratio of phenols and naphthols can be arbitrarily selected between 5 to 95% by weight of naphthols out of the total charge of phenols and naphthols. If the proportion of naphthols is too low, the naphthol introduction rate in the skeleton will be low, and heat resistance and low water absorption may be reduced. On the other hand, if the proportion of naphthols is too high, the naphthol introduction rate in the skeleton increases, and the flame retardancy may be reduced. Moreover, a preferable use rate changes with kinds of naphthol to be used. For example, when the naphthol is α-naphthol, among phenols and naphthols, 5 to 15% by weight of naphthols and when naphthol is β-naphthol, naphthols are 5 out of phenols and naphthols. A range of ˜20% by weight is preferred. More preferably, when the naphthol is α-naphthol, 10 to 15 wt% of the naphthols among phenols and naphthols, and when the naphthol is β-naphthol, naphthol among the phenols and naphthols The range of 10-20% by weight is preferred. Naphthol can be mixed with α-naphthol and β-naphthol at an arbitrary ratio within a range not impairing flame retardancy.

  In the above condensation reaction, an acid catalyst is used if necessary. Depending on the type of the compound of formula (1), an acid may be produced as a by-product during the reaction, and in this case, the addition of a catalyst is not always necessary. Various acid catalysts can be used, and examples include inorganic or organic acids such as hydrochloric acid, sulfuric acid, p-toluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Moreover, since the orientation of a phenol resin changes with kinds of acid, it should select suitably as needed. For example, if the ortho orientation is increased, the solubility in a solvent may be improved. Further, when the para-orientation is increased, heat resistance tends to be improved in a curing system with an epoxy resin. According to the knowledge of the present inventors, those with higher acidity (for example, acid catalysts such as hydrogen bromide and hydrogen fluoride whose acidity is higher than hydrochloric acid) tend to be more para-oriented. . The amount of the acid catalyst used varies depending on the type of the catalyst, but an appropriate amount may be added within the range of 0.0005% to 200% by weight of the compound represented by the formula (1). Preferably, it selects in the range of 0.1-30 weight%.

  The reaction may be performed without a solvent or a solvent may be used. When the solvent is used, the amount of the solvent used is preferably 50 to 300% by weight, particularly preferably 100 to 250% by weight, based on the total weight of the charged raw materials. Specific examples of the solvent that can be used include methanol, ethanol, isopropyl alcohol, toluene, xylene, acetone, methyl ethyl ketone, and methyl isobutyl ketone, which are inert to the reaction, but are not limited thereto. These solvents can be used alone or in combination. Further, it is preferable to distill off water or alcohols generated during the reaction out of the system using a fractionating tube or the like in order to carry out the reaction quickly.

  In order to increase the naphthol introduction rate, an additive may be used in the reaction system. When the additive is used, the amount of the additive used is preferably 50% by weight or less, particularly preferably 20% by weight or less, based on the total weight of the charged raw materials. When there is too much quantity of an additive, it will become difficult to remove by water washing. Examples of the additive include alcoholic compounds and basic compounds. Specific examples include methanol, ethanol, propanol, sodium carbonate, calcium carbonate, sodium hydroxide, potassium hydroxide and the like.

  The reaction temperature is usually 40 to 200 ° C, preferably 50 to 150 ° C. The reaction time is 0.5 to 20 hours, preferably 1 to 15 hours. The reaction may be carried out while charging all the raw materials at once, or may be carried out by adding them in portions.

  After completion of the reaction, washing with water is carried out until the pH value of the washing liquid becomes 3 to 7, preferably 5 to 7. When washing with water, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkaline earth metal hydroxides such as calcium hydroxide and magnesium hydroxide, ammonia, sodium dihydrogen phosphate and diethylenetriamine are necessary. Various basic substances such as organic amines such as triethylenetetramine, aniline, and phenylenediamine may be used as the neutralizing agent. In some cases, a solvent may be added. The solvent that can be used is not particularly limited as long as it dissolves a high molecular weight substance and is well separated from the aqueous layer, and examples thereof include methyl ethyl ketone and methyl isobutyl ketone. Washing with water may be performed according to a conventional method. For example, warm water in which the neutralizing agent is dissolved is added to the reaction mixture, and the liquid separation extraction operation is repeated.

  The obtained organic layer was heated and reduced with a rotary evaporator to remove the solvent and unreacted phenols, thereby obtaining the phenol resin of the present invention.

When the naphthols are α-naphthol, the introduction rate of naphthol in the phenol resin of the present invention thus obtained is preferably 5 to 40 mol%, more preferably 5 to 25 mol% of the phenols and naphthols. ˜20 mol% is particularly preferred. When the naphthol is β-naphthol, 5-35 mol% is preferable among phenols and naphthols, and 20-35 mol% is more preferable. When the naphthols are a mixture of α-naphthol and β-naphthol, 5 to 40 mol% is preferable among phenols and naphthols, and 20 to 40 mol% is more preferable.
And when (beta) -naphthol is introduce | transduced or (alpha) -naphthol is introduce | transduced, it is preferable from a viewpoint of a flame retardance improvement that an introduction rate is 5-20 mol%.
The naphthol introduction rate is calculated by dividing the molar amount of naphthol introduced into the skeleton by the total molar amount of phenol and naphthol introduced into the skeleton. The molar amount of phenol and naphthol introduced into the skeleton is calculated by calculating the amount of unreacted monomer from each monomer ratio in the HPLC chart and subtracting it from the molar amount of phenol and naphthol charged.

  The phenol resin of the present invention can be reacted with epihalohydrin in the presence of an alkali metal hydroxide to form an epoxy resin, or it can be used as it is as a curing agent for an epoxy resin.

  The specific example of the manufacturing method of the epoxy resin of this invention is demonstrated below.

The epoxy resin of the present invention is obtained by epoxidizing the phenol resin represented by the above formula (2) by a known epoxidation method. For example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to a dissolved mixture of the phenol resin obtained above and an epihalohydrin such as excess epichlorohydrin, epibromohydrin, a-methylepichlorohydrin, g-methylepichlorohydrin, etc. Or can be obtained by reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours with addition. In the epoxy resin of the present invention, when naphthol is α-naphthol, the introduction rate of naphthol is 5 to 40 mol% of phenol and naphthol, and when naphthol is β-naphthol, phenol and naphthol When the naphthols are a mixture of α-naphthol and β-naphthol, it is 5 to 40 mol% of phenols and naphthols.
The naphthol introduction rate is calculated by dividing the molar amount of naphthol introduced into the skeleton by the total molar amount of phenol and naphthol introduced into the skeleton. The molar amount of phenol and naphthol introduced into the skeleton is calculated by calculating the amount of unreacted monomer from each monomer ratio in the HPLC chart and subtracting it from the molar amount of phenol and naphthol charged.

  In the reaction for obtaining the epoxy resin of the present invention, an aqueous solution of the alkali metal hydroxide may be used. In that case, the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system and under reduced pressure. Alternatively, water and epihalohydrin may be continuously distilled off under normal pressure, followed by liquid separation, removal of water, and epihalohydrin being continuously returned to the reaction system.

  Further, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide, trimethylbenzylammonium chloride or the like is added as a catalyst to the dissolved mixture of the phenol resin and epihalohydrin of the present invention and reacted at 50 to 150 ° C. for 1 to 5 hours. A method of adding a solid or aqueous solution of an alkali metal hydroxide to the obtained halohydrin etherified product and reacting at a temperature of 20 to 120 ° C. for 1 to 10 hours to dehydrohalogenate (ring closure) may be used. The amount of the quaternary ammonium salt used in this case is usually 1 to 10 g, preferably 2 to 8 g, per one hydroxyl group of the phenol resin of the present invention.

  The amount of epihalohydrin usually used in these reactions is usually 1 to 20 mol, preferably 2 to 10 mol, per 1 equivalent of the hydroxyl group of the phenol resin of the present invention. The usage-amount of an alkali metal hydroxide is 0.8-1.5 mol with respect to 1 equivalent of hydroxyl groups of the phenol resin of this invention, Preferably it is 0.9-1.1 mol. Furthermore, in order to make the reaction proceed smoothly, it is preferable to carry out the reaction by adding an aprotic polar solvent such as dimethyl sulfone or dimethyl sulfoxide in addition to alcohols such as methanol and ethanol.

  When alcohols are used, the amount used is 2 to 20% by weight, more preferably 4 to 15% by weight, based on the amount of epihalohydrin. Moreover, when using an aprotic polar solvent, it is 5 to 100 weight% with respect to the quantity of epihalohydrin, More preferably, it is 10 to 90 weight%.

  After the reaction product of these epoxidation reactions is washed with water or without washing with water, epihalohydrin, a solvent and the like are removed at 110 to 250 ° C. under a pressure of 10 mmHg or less under reduced pressure. Further, in order to make an epoxy resin with less hydrolyzable halogen, the obtained epoxy resin is dissolved in a solvent such as toluene or methyl isobutyl ketone, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is prepared. In addition, further reactions can be performed to ensure ring closure. In this case, the alkali metal hydroxide is preferably used in an amount of 0.01 to 0.3 mol, particularly preferably 0.05 to 0.000, based on 1 equivalent of the hydroxyl group of the naphthol-containing phenol resin of the present invention used for epoxidation. 2 moles. The reaction temperature is 50 to 120 ° C., and the reaction time is usually 0.5 to 2 hours.

  After completion of the reaction, the produced salt is removed by filtration, washing with water, etc., and further, the epoxy resin of the present invention with little hydrolyzable chlorine is obtained by distilling off a solvent such as toluene and methyl isobutyl ketone under heating and reduced pressure.

The epoxy resin of the present invention thus obtained has the following formula (3)
(In the formula, n represents the number of repetitions. R represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or 2 to 10 carbon atoms. Represents an alkenyl group, etc., and each R may be the same or different.)
It has the structure represented by these.
Here, R is preferably a hydrogen atom or an alkyl group having 1 to 10 carbon atoms.
n is 1-50 normally, 1-20 are preferable and 1-10 are especially preferable.

The epoxy resin of the present invention thus obtained has a naphthol introduction rate of 5-40 mol% of phenols and naphthols when the naphthols are α-naphthol, and phenols when the naphthol is β-naphthol. When naphthols are 5 to 35 mol%, and naphthols are a mixture of α-naphthol and β-naphthol, it is 5 to 40 mol% of phenols and naphthols, exhibiting flame retardancy, Excellent low water absorption.
Moreover, as a softening point, 60-80 degreeC is preferable.
The epoxy equivalent is preferably 200 to 600 g / eq, more preferably 230 to 380 g / eq, and particularly preferably 250 to 340 g / eq.
The naphthol introduction rate is calculated by dividing the molar amount of naphthol introduced into the skeleton by the total molar amount of phenol and naphthol introduced into the skeleton. The molar amount of phenol and naphthol introduced into the skeleton is calculated by calculating the amount of unreacted monomer from each monomer ratio in the HPLC chart and subtracting it from the molar amount of phenol and naphthol charged.

  The epoxy resin composition of the present invention is described below.

  The epoxy resin composition of the present invention is characterized by containing the phenol resin of the formula (2) or / and the epoxy resin of the formula (3), and is excellent in flame retardancy, heat resistance and low water absorption. Give a cured product.

  The epoxy resin composition of the present invention can be used in combination with other epoxy resins used for electric / electronic parts as long as the flame retardancy is not impaired. When used in combination, the proportion of the epoxy resin of the present invention is preferably 30% by weight or more, particularly preferably 40% by weight or more.

Other epoxy resins that can be used in combination with the epoxy resin of the present invention include novolac type epoxy resins, bisphenol A type epoxy resins, and bisphenol F.
Type epoxy resin, triphenylmethane type epoxy resin, phenol aralkyl type epoxy resin, dicyclopentadiene phenol addition reaction type epoxy resin and the like.
Specifically, bisphenol A, bisphenol S, thiodiphenol, fluorene bisphenol, terpene diphenol, 4,4′-biphenol, 2,2′-biphenol, 3,3 ′, 5,5′-tetramethyl- [ 1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenol (Phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, -Hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis (chloromethyl) -1,1'-biphenyl, 4,4'-bis (methoxymethyl) -1,1'-biphenyl, 1,4-bis Polycondensates with (chloromethyl) benzene, 1,4-bis (methoxymethyl) benzene, etc. and their modified products, halogenated bisphenols such as tetrabromobisphenol A, glycidyl ethers derived from alcohols, fats Cyclic epoxy resin, glycidylamine epoxy resin, glycidyl ester epoxy resin, silsesquioxane epoxy resin (chain, cyclic, ladder, or mixed siloxane structure of at least two kinds of glycidyl groups) And / or an epoxy resin having an epoxycyclohexane structure ) And other solid or liquid epoxy resins, but are not limited thereto.

  Furthermore, since it is used for electrical and electronic parts, those having a low hydrolyzable chlorine concentration are preferred. That is, it is preferable that hydrolyzable chlorine is 0.2% by weight or less as defined by the elimination chlorine when the epoxy resin is dissolved in dioxane and treated with 1N KOH for 30 minutes under reflux, 0.15% by weight The following are more preferable.

The epoxy resin composition of the present invention contains a curing agent. Specific examples of the curing agent include a phenol resin, a phenol compound, an amine compound, an acid anhydride compound, an amide compound, and a carboxylic acid compound. Specific examples of curing agents that can be used include phenolic resins, phenolic compounds; bisphenol A, bisphenol F, bisphenol S, fluorene bisphenol, terpene diphenol, 4,4'-biphenol, 2,2'-biphenol, 3,3 ', 5,5′-tetramethyl- [1,1′-biphenyl] -4,4′-diol, hydroquinone, resorcin, naphthalenediol, tris- (4-hydroxyphenyl) methane, 1,1,2,2-tetrakis (4-hydroxyphenyl) ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydride Roxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4′-bis (chloromethyl) -1,1′-biphenyl, 4,4′-bis (methoxymethyl) -1, Polycondensates with 1′-biphenyl, 1,4′-bis (chloromethyl) benzene, 1,4′-bis (methoxymethyl) benzene, and their modified products, and halogenated bisphenols such as tetrabromobisphenol A And polyphenols such as terpene and phenol condensates, but are not limited thereto. These may be used alone or in combination of two or more.
Preferred phenol resins include phenol aralkyl resins (resins having an aromatic alkylene structure) in terms of dielectric constant, and particularly preferred is a structure having at least one selected from phenol, naphthol, and cresol, and serves as the linker. A resin characterized in that the alkylene part is at least one selected from a benzene structure, a biphenyl structure, and a naphthalene structure (specifically, zylock, naphthol zylock, phenol biphenylene novolak resin, cresol-biphenylene novolak resin, phenol-naphthalene) And novolak resin.).
Amine-based compounds, amide-based compounds; diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, dicyandiamide, nitrogen-containing compound anhydride compounds such as polyamide resins synthesized from linolenic acid and ethylenediamine , Carboxylic acid compounds; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl nadic anhydride, nadic anhydride, hexahydrophthalic anhydride, methyl Hexahydrophthalic anhydride, butanetetracarboxylic anhydride, bicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride, methylbicyclo [2,2,1] heptane-2,3-dicarboxylic anhydride , Cyclohexane-1,3,4-tricarboxylic acid-3,4-anhydride, acid anhydrides and the like; various alcohols, carbinol-modified silicone, a carboxylic acid resin obtained by the addition reaction of the aforementioned acid anhydride;
Others: Examples thereof include, but are not limited to, imidazole, trifluoroborane-amine complexes, guanidine derivative compounds, and the like. These may be used alone or in combination of two or more.

The epoxy resin curing agent is used in an amount such that the phenolic hydroxyl group is usually 0.55 to 1.0 equivalent, preferably 0.6 to 0.95 equivalent, relative to the epoxy group of the epoxy resin. When the curing agent is less than 0.55 equivalent, the number of unreacted epoxy groups increases, and workability particularly during transfer molding is reduced. When it exceeds 1.0 equivalent, the amount of unreacted curing agent increases, and the thermal and mechanical properties deteriorate, which is not preferable.

  If necessary, a curing accelerator may be added to the epoxy resin composition of the present invention. Specific examples of the curing accelerator include phosphines such as triphenylphosphine and bis (methoxyphenyl) phenylphosphine, imidazoles such as 2-methylimidazole, 2-ethylimidazole, 2-ethylimidazole and 4-methylimidazole, Tertiary amines such as 2- (dimethylaminomethyl) phenol, trisdimethylaminomethylphenol, diazabicycloundecene, tetrabutylammonium salt, triisopropylmethylammonium salt, trimethyldecanylammonium salt, cetyltrimethylammonium salt, etc. Quaternary phosphonium salts such as quaternary ammonium salts, triphenylbenzyl phosphonium salts, triphenylethyl phosphonium salts, tetrabutyl phosphonium salts (the counter ions of quaternary salts are halogens) Organic acid ions, hydroxide ions, such as, but not particularly specified, in particular an organic acid ion, a hydroxide ion.), Metal compounds such as tin octylate and the like.

  The usage-amount of a hardening accelerator is 0.2-5.0 weight part normally per 100 weight part of epoxy resins, Preferably, it is 0.2-4.0 weight part.

  The curable resin composition of the present invention may contain a phosphorus-containing compound as a flame retardant component. The phosphorus-containing compound may be a reactive type or an additive type. Specific examples of phosphorus-containing compounds include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, trixylylenyl phosphate, cresyl diphenyl phosphate, cresyl-2,6-dixylylenyl phosphate, 1,3-phenylenebis ( Phosphoric acid esters such as dixylylenyl phosphate), 1,4-phenylenebis (dixylylenyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate); 9,10-dihydro-9-oxa Phosphanes such as -10-phosphaphenanthrene-10-oxide, 10 (2,5-dihydroxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide; epoxy resin and active hydrogen of the phosphanes A phosphorus-containing product obtained by reacting with Poxy compounds, red phosphorus and the like can be mentioned, and phosphoric esters, phosphanes or phosphorus-containing epoxy compounds are preferable, and 1,3-phenylenebis (dixylylenyl phosphate), 1,4-phenylenebis (dixylylene). Nyl phosphate), 4,4′-biphenyl (dixylylenyl phosphate) or phosphorus-containing epoxy compounds are particularly preferred. The phosphorus-containing compound content is preferably phosphorus-containing compound / total epoxy resin = 0.1 to 0.6 (weight ratio). If it is 0.1 or less, the flame retardancy is insufficient, and if it is 0.6 or more, there is a concern that it may adversely affect the hygroscopicity and dielectric properties of the cured product.

  Furthermore, you may add antioxidant to the curable resin composition of this invention as needed. Antioxidants that can be used include phenol-based, sulfur-based, and phosphorus-based antioxidants. Antioxidants can be used alone or in combination of two or more. The usage-amount of antioxidant is 0.008-1 weight part normally with respect to 100 weight part with respect to the resin component in the curable resin composition of this invention, Preferably it is 0.01-0.5 weight part. It is.

  Examples of the antioxidant include a phenol-based antioxidant, a sulfur-based antioxidant, and a phosphorus-based antioxidant. Specific examples of phenolic antioxidants include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, stearyl-β- (3 , 5-di-t-butyl-4-hydroxyphenyl) propionate, isooctyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio)- Monophenols such as 6- (4-hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, 2,4-bis [(octylthio) methyl] -o-cresol; 2′-methylenebis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), 4,4′-thiobis (3- Til-6-tert-butylphenol), 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) ) Propionate], 1,6-hexanediol-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t) -Butyl-4-hydroxy-hydrocinnamamide), 2,2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 3,5-di-t -Butyl-4-hydroxybenzylphosphonate-diethyl ester, 3,9-bis [1,1-dimethyl-2- {β- (3-t-butyl-4-hydroxy-5- Bisphenols such as (tilphenyl) propionyloxy} ethyl] 2,4,8,10-tetraoxaspiro [5,5] undecane, bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate) ethyl 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-t- Butyl-4-hydroxybenzyl) benzene, tetrakis- [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, bis [3,3′-bis- (4 '-Hydroxy-3'-tert-butylphenyl) butyric acid] glycol ester, tris- (3,5-di-tert-butyl-4-hydroxybenzyl) -iso Anureate, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -S-triazine-2,4,6- (1H, 3H, 5H) trione, tocophenol And the like.

  Specific examples of the sulfur-based antioxidant include dilauryl-3,3′-thiodipropionate, dimyristyl-3,3′-thiodipropionate, distearyl-3,3′-thiodipropionate, and the like. .

  Specific examples of phosphorus antioxidants include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, tris (nonylphenyl) phosphite, diisodecylpentaerythritol phosphite, tris (2,4-di-t- Butylphenyl) phosphite, cyclic neopentanetetrayl bis (octadecyl) phosphite, cyclic neopentanetetraylbi (2,4-di-t-butylphenyl) phosphite, cyclic neopentanetetraylbi (2,4 -Di-t-butyl-4-methylphenyl) phosphite, bis [2-t-butyl-6-methyl-4- {2- (octadecyloxycarbonyl) ethyl} phenyl] hydrogen phosphite, etc. 9,10-dihydro 9-oxa-10-phosphaphenanthrene-10-oxide, 10- (3,5-di-tert-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10 -Oxaphosphaphenanthrene oxides such as 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide are exemplified.

  These antioxidants can be used alone, but two or more of them may be used in combination. In the present invention, a phosphorus-based antioxidant is particularly preferable.

Furthermore, you may add a light stabilizer to the curable resin composition of this invention as needed.
As the light stabilizer, hindered amine-based light stabilizers, particularly HALS and the like are suitable. HALS is not particularly limited, but representative examples include dibutylamine, 1,3,5-triazine, N, N′-bis (2,2,6,6-tetramethyl-4- Polycondensate of piperidyl-1,6-hexamethylenediamine and N- (2,2,6,6-tetramethyl-4-piperidyl) butylamine, dimethyl-1- (2-hydroxyethyl) -4-hydroxy succinate -2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1,3,3-tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4-piperidyl) imino}], bis (1,2,2, 6,6-pentamethyl-4-pi Peridyl) [[3,5-bis (1,1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate, bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis (1-octyloxy-2,2,6,6-tetramethyl-4-piperidyl) sebacate, 2- (3,5-di -T-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1,2,2,6,6-pentamethyl-4-piperidyl), etc. Only one HALS is used. Two or more types may be used in combination.

  Furthermore, binder resin can also be mix | blended with the curable resin composition of this invention as needed. Examples of the binder resin include butyral resins, acetal resins, acrylic resins, epoxy-nylon resins, NBR-phenol resins, epoxy-NBR resins, polyamide resins, polyimide resins, and silicone resins. However, it is not limited to these. The blending amount of the binder resin is preferably in 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 per 100 parts by weight of the resin component. Part by weight is used as needed.

  Furthermore, the epoxy resin composition of this invention can add an inorganic filler, a pigment, a mold release agent, a silane coupling agent, a softening agent, etc. as needed. In particular, the addition of non-flammable inorganic fillers has the effect of further improving the flame retardancy of the composition, and in terms of flame retardancy, it should be added in a large amount as long as there is no problem with workability and physical properties after curing. Is desirable. Non-combustible inorganic fillers include hydroxides such as aluminum hydroxide, magnesium hydroxide and iron hydroxide. Examples include zinc stannate, silica, alumina, calcium carbonate, aluminum nitride, and silicon nitride.

The epoxy resin composition of the present invention can be obtained by uniformly mixing each component at a predetermined ratio. 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. In the epoxy resin composition of the present invention, for example, an epoxy resin and a curing agent are previously added at 100 to 200 ° C.
After melting at least one of the epoxy resin or the curing agent and dissolving the other in this melt, an inorganic filler, a pigment, a release agent, if necessary with an extruder, roll, kneader, It can be obtained by adding and mixing a flame retardant, a silane coupling agent and the like and a curing accelerator. Moreover, you may mix said each component with an extruder, a roll, a kneader, etc. without passing through a melting process depending on the case. The obtained epoxy resin composition is usually molded and cured using a transfer molding machine or the like, and further performance is improved by post-curing at 80 to 200 ° C. for 2 to 10 hours. Moreover, when setting it as a liquid sealing material, a liquid epoxy resin is used and it can mix and manufacture the epoxy resin composition of this invention at room temperature.

  It can also be used in a form dissolved in a solvent. The curable resin composition of the present invention is dissolved in a solvent such as toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethylacetamide, N-methylpyrrolidone as necessary to obtain a curable resin composition varnish, A prepreg obtained by impregnating a base material such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, paper, etc. and drying by heating is subjected to hot press molding, whereby the curable resin composition A of the present invention. It can be set as a cured product. The solvent used here is usually 10 to 70% by weight, preferably 15 to 70% by weight in the mixture of the curable resin composition of the present invention and the solvent. Moreover, if it is a liquid composition, the epoxy resin hardened | cured material which contains a carbon fiber by the RTM system as it is can also be obtained as it is.

  Moreover, the curable resin composition of this invention can be used also as a modifier of a film type composition. Specifically, it can be used to improve the flexibility of the B-stage. Such a film-type resin composition is formed by applying the curable resin composition of the present invention on the release film as the curable resin composition varnish, removing the solvent under heating, and then performing B-stage. To obtain a sheet-like adhesive. This sheet-like adhesive can be used as an interlayer insulating layer in a multilayer substrate or the like.

  The hardened | cured material of this invention can be used for various uses, such as a molding material, an adhesive agent, a composite material, and a coating material. In particular, since the cured epoxy resin of the present invention exhibits excellent flame retardancy, it is useful in the electrical and electronic fields such as IC sealing materials, laminated materials, and electrical insulating materials.

EXAMPLES Next, although an Example demonstrates this invention further more concretely, this invention is not limited to these Examples. Below, a part is a weight part unless there is particular notice. The hydroxyl equivalent, epoxy equivalent, softening point, and ICI viscosity were measured under the following conditions. The naphthol introduction rate is calculated by dividing the molar amount of naphthol introduced into the skeleton by the total molar amount of phenol and naphthol introduced into the skeleton. The molar amount of phenol and naphthol introduced into the skeleton is calculated by calculating the amount of unreacted monomer from each monomer ratio in the HPLC chart and subtracting it from the molar amount of phenol and naphthol charged.
-Hydroxyl equivalent: Measured by the method described in JIS K-7236, the unit is g / eq. It is.
-Epoxy equivalent Measured by the method described in JIS K-7236, the unit is g / eq. It is.
-Softening point Measured by a method based on JIS K-7234.
-ICI viscosity Measured by a method based on JIS K-7117-2-HPLC
Column; Inertsil ODS-2 (4.6 mm × 150 mm)
(Manufactured by GL Sciences)
Column temperature: 40 ° C
Eluent: Water / acetonitrile gradient: 30% (acetonitrile) → 100% (28 minutes / gradient)
Flow rate: 1 ml / min.
Detection: UV (274 nm)

Example 1
While applying a nitrogen gas purge to a flask equipped with a thermometer, dropping funnel, condenser and stirrer, phenol 207
Part, 28.8 parts of α-naphthol and 0.3 part of paratoluenesulfonic acid (PTS) were added and heated to 80 ° C. with stirring to dissolve. 201 parts of bischloromethylbiphenyl (BCMB) was added over 2 hours and further stirred for 6 hours. While stirring, crystals started to precipitate, but stirring was continued as it was. After completion of the reaction, the reaction was quenched by adding 0.2 parts of disodium hydrogen phosphate. 200 parts of methyl ethyl ketone and 100 parts of warm water were added and washed with water until the wastewater became neutral. The obtained organic layer was heated under reduced pressure using a rotary evaporator to remove the solvent and unreacted phenols to obtain a phenol resin. In the obtained phenol resin, the naphthol introduction rate was 16 mol%, the softening point was 86 ° C., the ICI viscosity was 0.43 Pa · s, and the hydroxyl group equivalent was 223 g / eq. Met.

Examples 2 to 5, Comparative Examples 1 and 2
As described in the following table, a phenol resin was prepared by the same flow as in Example 1 except that the raw material charge was changed.

The resin physical properties of the prepared phenol resin were as shown in the following table.

Example 6
A flask equipped with a stirrer, a reflux condenser, and a stirrer was purged with nitrogen, and 100 parts of phenol resin prepared in Example 1 while being purged with nitrogen, 249 parts of epichlorohydrin (ECH), 58 parts of dimethyl sulfoxide (DMSO), water 2 .5 parts was added and the temperature was raised to 55 ° C. Next, 19 parts of flaky sodium hydroxide was added in portions over 90 minutes, and the reaction was further carried out at 55 ° C. for 90 minutes and at 70 ° C. for 30 minutes. After completion of the reaction, washing with water was performed, and excess solvent such as epichlorohydrin was distilled off from the organic layer under reduced pressure at 130 ° C. using a rotary evaporator. To the residue, 230 parts of methyl isobutyl ketone was added and dissolved, and the temperature was raised to 75 ° C. Under stirring, 6 parts of a 30% aqueous sodium hydroxide solution was added and the reaction was carried out for 1 hour. Then, the organic layer was washed with water until the washing water became neutral, and the resulting organic layer was washed at 180 ° C. using a rotary evaporator. 98 parts of the epoxy resin of the present invention was obtained by distilling off a solvent such as methyl isobutyl ketone under reduced pressure. The resulting epoxy resin had a softening point of 70 ° C., an ICI viscosity of 0.33 Pa · s, and an epoxy equivalent of 296 g / eq. Met.

Examples 7 to 10, Comparative Examples 3 and 4
Epoxy resins were prepared by the same flow as in Example 1 except that the phenol resins prepared in Examples 2 to 5 and Comparative Examples 1 and 2 were used.

The resin physical properties of the prepared epoxy resin were as shown in the following table.

Examples 11 to 15 and Comparative Examples 5 and 6
The compound shown in the column of the composition of the compound of Table 1 was uniformly mixed with the mixing roll, and the epoxy resin composition was obtained. This composition was pulverized and a tablet was obtained using a tablet machine. The obtained tablet was shape | molded with the transfer molding machine, and the test piece of 10x4x90mm was shape | molded. This test piece was post-cured at 180 ° C. for 6 hours. This test piece is held perpendicularly to the clamp, the flame of the burner is adjusted to a blue flame of 19 mm, and 9.5 mm of the flame is contacted to the center of the lower end of the test piece for 10 seconds. Release the burner after flame contact and measure the combustion duration. Immediately after flame extinction, contact the flame for 10 seconds, release the burner, and measure the combustion duration. Table 4 shows the total combustion time for 10 samples.

The epoxy resin, curing agent, and curing accelerator used are shown below.
1. Epoxy resin examples 11 to 15: corresponding to the examples 6 to 10 of the present invention, respectively Comparative examples 5 and 6: corresponding to the epoxy resins of the comparative examples 3 and 4, respectively. Hardener biphenylphenol aralkyl resin (GPH-65, hydroxyl group equivalent 199 g / eq. Manufactured by Nippon Kayaku Co., Ltd.)
3. Curing accelerator TPP: Triphenylphosphine (manufactured by Junsei Co., Ltd.)
4). Filler high purity spherical silica (MSR-2102, manufactured by Tatsumori Co., Ltd.)

Claims (8)

Of the phenol resins represented by formula (2) obtained by condensing phenols, naphthols, and compounds represented by formula (1), naphthols are α-naphthol, and phenols and naphthols Among them, a phenol resin having a naphthol introduction rate of 5 to 35 mol%.
(In the formula, X represents chlorine, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms.)
(In the formula, n is a repeating number and represents an integer of 1 to 50. R is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, Alternatively , it represents an alkenyl group having 2 to 10 carbon atoms, and each R may be the same as or different from each other. Of the phenol resins represented by Formula (2) obtained by condensing phenols, naphthols, and a compound represented by Formula (1), naphthols are β-naphthol, and phenols and naphthols Among them, a phenol resin having a naphthol introduction rate of 5 to 35 mol%.
(In the formula, X represents chlorine, a hydroxyl group, or an alkoxy group having 1 to 4 carbon atoms.)
(In the formula, n is a repeating number and represents an integer of 1 to 50. R is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, Alternatively , it represents an alkenyl group having 2 to 10 carbon atoms, and each R may be the same as or different from each other. Of the phenolic resins represented by the following formula (2), naphthols is a mixture of α- naphthol and β- naphthol, phenol, phenolic resins naphthol introduction rate of the naphthols is 5-35 mol%.
(In the formula, n is a repeating number and represents an integer of 1 to 50. R is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, Alternatively, it represents an alkenyl group having 2 to 10 carbon atoms, and each R may be the same as or different from each other. The epoxy resin represented by Formula (3) obtained by making an epihalohydrin react with the phenol resin as described in any one of Claims 1-3.
(In the formula, n represents an integer of 1 to 50 as the number of repetitions. R represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 14 carbon atoms, or an alkenyl group having 2 to 10 carbon atoms, each R may be the being the same or different.) An epoxy resin composition comprising (a) an epoxy resin and (b) the phenol resin according to any one of claims 1 to 3. (A) An epoxy resin composition comprising the epoxy resin according to claim 4 and (b) a curing agent. An epoxy resin composition containing (a) the epoxy resin according to claim 4 and (b) the phenol resin according to any one of claims 1 to 3. Hardened | cured material formed by hardening | curing the epoxy resin composition of any one of Claims 5-7 .