TW201527345A - Phenolic resin, epoxy resin, epoxy resin composition, prepreg and cured product of said epoxy resin composition or prepreg - Google Patents

Abstract

Provided are: a phenolic resin which is a constituent of an epoxy resin composition that provides a cured product having high heat resistance and high flame retardancy; an epoxy resin which is derived from the phenolic resin; an epoxy resin composition which contains the phenolic resin or the epoxy resin; a prepreg; and a cured product of the epoxy resin composition or the prepreg. The phenolic resin is obtained by: firstly obtaining a phenolic compound (a) by a reaction between a phenolic compound represented by formula (1) and a compound represented by formula (2); and then reacting the thus-obtained phenolic compound (a) with a phosphorus-containing compound represented by formula (3). (In the formulae, each of R1-R3 independently represents a hydrogen atom or the like; and each of m and k represents an integer of 0-4.)

Description

Phenolic resin, epoxy resin, epoxy resin composition, prepreg and hardened materials thereof

This invention relates to a novel phenolic resin, epoxy resin and epoxy resin composition. Further, the present invention relates to a cured product of a prepreg or the like formed by the epoxy resin composition.

The epoxy resin composition is widely used in electrical, electronic parts, structural materials, adhesives, paints, etc., depending on the workability and the excellent electrical properties of the cured product, such as heat resistance, adhesion, and moisture resistance (water resistance). .

However, in recent years, in the field of electric and electronic, along with its development, it is required to improve the moisture resistance, adhesion, and dielectric properties of the resin composition, and to make the filler highly filled (inorganic or organic filler). Further improvements in various properties such as low viscosity and improved reactivity in the molding cycle are further improved. Also, as a structural material, in aerospace materials, entertainment. A material that is lightweight and has excellent mechanical properties, such as the use of sports equipment. Especially in the field of semiconductor sealing, the substrate (the substrate itself or its peripheral materials), which is complicated by thinning, stacking, systemization, and three-dimensionality as the semiconductor changes, requires extremely high degree of heat resistance or high fluidity. Etc. Furthermore, with the expansion of the use of plastic packaging for vehicles, the demand for improved heat resistance has become more severe. Specifically, heat resistance of 150 ° C or higher is required due to an increase in the driving temperature of the semiconductor. In general, an epoxy resin has a tendency that an epoxy resin having a high softening point has high heat resistance, but the opposite surface is difficult to be used for a sealing material because of a tendency to increase in viscosity. Also, there is a decrease in thermal decomposition temperature and flame retardancy. Reduce the problem.

Therefore, since the prior art, epoxy resins having high heat resistance and flame retardancy have been required. Therefore, various epoxy resins have been developed as epoxy resins having good heat resistance (Patent Documents 1 to 5). However, in general, if the epoxy resin is high in Tg, the flame retardancy is lowered. The reason is that it is affected by the increase in crosslink density. According to such characteristics, in the pursuit of high Tg of semiconductor peripheral materials requiring flame retardancy, it is urgent to develop a resin having the opposite characteristics.

Patent Document 1: Japanese Laid-Open Patent Publication No. Hei 11-323162

Patent Document 2: Japanese Patent Laid-Open Publication No. 2004-2573

Patent Document 3: Japanese Laid-Open Patent Publication No. 2006-63315

Patent Document 4: Japanese Patent Laid-Open Publication No. 2003-137971

Patent Document 5: International Publication No. 2011/093474

The present invention has been completed in order to solve such a problem, and provides a phenol resin having a constituent component of an epoxy resin composition having high heat resistance and high flame retardancy in a cured product thereof, and a phenol resin derived from the phenol resin. An epoxy resin, an epoxy resin composition containing the phenol resin or the epoxy resin, a prepreg, and a cured product thereof.

The inventors of the present invention have diligently studied in order to solve the above problems, and as a result, have completed the present invention.

That is, the present invention relates to the following (1) to (7).

(1) A phenol resin (b) obtained by reacting a phenol compound represented by the following formula (1) with a compound represented by the following formula (2) to obtain a phenol compound (a), and further It is obtained by reacting a phosphorus-containing compound represented by the following formula (3).

(In the formula (1), R ₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, Any of a substituted or unsubstituted alkoxy group having a nitro group or a carbon number of 1 to 10. m represents the number of R ₁ and is an integer of 0 to 4).

(In the formula (2), R ₂ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, Any of a substituted or unsubstituted alkoxy group having a nitro group, a decyl group, an allyl group or a carbon number of 1 to 10. k represents the number of R ₂ and is an integer of 0 to 4).

(In the formula (3), R ₃ each independently represents a hydrogen atom, an alkyl group or an aromatic group).

(2) A phenol resin represented by the following formula (4).

(In the formula (4), R ₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, Any one of a substituted or unsubstituted alkoxy group having a nitro group or a carbon number of 1 to 10; R _{2 is} independently present, and represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms; Any of substituted or unsubstituted aryl, hydroxy, nitro, methylidene, allyl or substituted or unsubstituted alkoxy having 1 to 10 carbon atoms; ;k represents the number of R ₂ , an integer from 0 to 4; m represents the number of R ₁ , an integer from 0 to 4; Z represents a hydrogen atom or a structure of the following formula (5), which exists in a plurality of Z At least one represents a structure of the following formula (5).

(In the formula (5), R ₃ each independently represents a hydrogen atom, an alkyl group or an aromatic group).

(3) An epoxy resin obtained by reacting a phenol resin described in the above (1) or (2) with an epihalohydrin.

(4) An epoxy resin composition comprising the phenol resin and the epoxy resin described in the above item (1) or (2).

(5) The epoxy resin composition according to the above item (4), which is used for semiconductor sealing purposes.

(6) A prepreg comprising the epoxy resin composition and the flaky fiber described in the above item (4) The composition of the substrate.

(7) A cured product obtained by curing the epoxy resin composition described in the above item (4) or (5) or the prepreg described in the above item (6).

Since the phenol resin of the present invention contains an epoxy resin containing a liquid crystal nucleus in a high purity, the cured product of the epoxy resin composition containing the phenol resin as a constituent component exhibits excellent heat resistance, flame retardancy, and is suitable for use as Various types of composite materials, adhesives, coatings, etc., including semiconductor sealing materials and prepregs.

The phenol resin (b) of the present invention can be obtained by reacting a phenol compound represented by the following formula (1) with a compound represented by the following formula (2) to obtain a phenol compound (a). It is obtained by reacting a phosphorus-containing compound represented by the formula (3).

(In the formula (1), R ₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, Any of a substituted or unsubstituted alkoxy group having a nitro group or a carbon number of 1 to 10. m represents the number of R ₁ and is an integer of 0 to 4).

(In the formula (2), R ₂ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, Any of a substituted or unsubstituted alkoxy group having a nitro group, a decyl group, an allyl group or a carbon number of 1 to 10. k represents the number of R ₂ and is an integer of 0 to 4).

(In the formula (3), R ₃ each independently represents a hydrogen atom, an alkyl group or an aromatic group).

First, the phenol compound (a) will be described.

The phenol compound (a) is obtained by a reaction of a compound represented by the above formula (1) with a compound represented by the above formula (2).

In the formula (1), R _{1 is} preferably independently present, and is a hydrogen atom, an unsubstituted alkyl group having 1 to 10 carbon atoms, an unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, a nitro group, or An unsubstituted alkoxy group having 1 to 10 carbon atoms.

In order to obtain the phenol compound (a), specific examples of the compound represented by the formula (1) used for the reaction with the compound represented by the formula (2) include 2-hydroxyacetophenone and 3-hydroxyacetophenone. 4-hydroxyacetophenone, 2',4'-dihydroxyacetophenone, 2',5'-dihydroxyacetophenone, 3',4',-dihydroxyacetophenone, 3',5'- Dihydroxyacetophenone, 2',3',4'-trihydroxyacetophenone, 2',4',6'-trihydroxy Acetophenone-hydrate, 4'-hydroxy-3'-methylacetophenone, 4'-hydroxy-2'-methylacetophenone, 2'-hydroxy-5'-methylacetophenone, 4'-hydroxy-3'-methoxyacetophenone, 2'-hydroxy-4'-methoxyacetophenone, 4'-hydroxy-3'-nitroacetophenone, 4'-hydroxy-3 ',5'-Dimethoxyacetophenone, 4',6'-dimethoxy-2'-hydroxyacetophenone, 2'-hydroxy-3',4'-dimethoxyacetophenone , 2'-hydroxy-4',5'-dimethoxyacetophenone, methyl 5-ethionylsalicylate, 2',3'-dihydroxy-4'-methoxyacetophenone hydrate Things.

In order to obtain the phenol compound (a), specific examples of the compound represented by the formula (2) for reacting with the compound represented by the formula (1) include, for example, 2-hydroxybenzaldehyde, 3-hydroxybenzaldehyde, and 4 -hydroxybenzaldehyde, 2,3-dihydroxybenzaldehyde, 2,4-dihydroxybenzaldehyde, 2,5-dihydroxybenzaldehyde, 3,4-dihydroxybenzaldehyde, syringaldehyde, 3,5-di- Third butyl-4-hydroxybenzaldehyde, isovanillin, 4-hydroxy-3-nitrobenzaldehyde, 5-hydroxy-2-nitrobenzaldehyde, 3,4-dihydroxy-5-nitrobenzaldehyde , vanillin, o-vanillin, 2-hydroxy-1-naphthaldehyde, 2-hydroxy-5-nitro-meta-anisaldehyde, 2-hydroxy-5-methylisophthalaldehyde, 2-hydroxy-4- Methoxybenzaldehyde, 1-hydroxy-2-naphthaldehyde, 2-hydroxy-5-methoxybenzaldehyde, 5-nitrovanalin, 5-allyl-3-methoxysalonaldehyde, 3, 5-di-t-butyl sulphonaldehyde, 3-ethoxy sulphonaldehyde, 4-hydroxyisophthalaldehyde, 4-hydroxy-3,5-dimethylbenzaldehyde, 2,4,6-trihydroxybenzene Formaldehyde, 2,4,5-trihydroxybenzaldehyde, 2,3,4-trihydroxybenzaldehyde, 3,4,5-trihydroxybenzaldehyde, 3-ethoxy-4-hydroxybenzaldehyde, and the like. These may be used alone or in combination of two or more.

The phenol compound (a) can be obtained by an aldol condensation reaction of one or more compounds represented by the formula (1) with a compound represented by the formula (2) under acidic conditions or under basic conditions.

The compound represented by the formula (2) is used in an amount of 1.0 to 1.05 mol per mol of the compound 1 shown in the formula (1).

When the aldol condensation reaction is carried out under acidic conditions, examples of the usable acidic catalyst include hydrochloric acid, sulfuric acid, nitric acid, inorganic acid, toluenesulfonic acid, and xylenesulfonate. Organic acids such as acid and oxalic acid. These may be used alone or in combination. The amount of the acidic catalyst used is 0.01 to 1.0 mol, preferably 0.2 to 0.5 mol, based on the compound 1 of the formula (2).

On the other hand, when the aldol reaction is carried out under alkaline conditions, examples of the basic catalyst that can be used include metal hydroxides such as sodium hydroxide and potassium hydroxide, potassium carbonate, sodium carbonate, and the like. An amine derivative such as an alkali metal carbonate, diethylamine, triethylamine, tributylamine, diisobutylamine, pyridine or piperidine, and dimethylaminoethanol and diethylaminoethanol. Amino alcohol derivative.

That is, in the case of an alkaline condition, the alkaline catalysts listed above may be used alone, or a plurality of them may be used in combination. The amount of the basic catalyst used is 0.1 to 2.5 moles, preferably 0.2 to 2.0 moles, relative to the compound 1 mole represented by the formula (2).

In the reaction for obtaining the phenol compound (a), a solvent may also be used as needed. The solvent to be used is not particularly limited as long as it has reactivity with the compound represented by the formula (2), for example, a ketone, and the compound represented by the formula (2) of the raw material is easily dissolved. In terms of alcohol, it is preferred to use an alcohol as a solvent.

The reaction temperature is usually from 10 to 90 ° C, preferably from 35 to 70 ° C. The reaction time is usually 0.5 to 10 hours, but the reactivity varies depending on the kind of the raw material compound, and thus is not limited thereto. After the completion of the reaction, when it is extracted as a resin, unreacted materials, solvents, and the like are removed from the reaction liquid after washing with the reaction product or without washing with water under heating and reduced pressure. In the case of extraction in the form of crystals, crystallization is precipitated by adding the reaction droplets to a large amount of water. The phenol compound produced when the reaction is carried out under alkaline conditions may be dissolved in water, and thus hydrochloric acid or the like is added to form a neutral to acidic condition to precipitate in a crystalline form.

The phenol resin (b) of the present invention can be obtained by subjecting the phenol compound (a) to a phosphorus-containing compound represented by the above formula (3).

The compound represented by the above formula (3) can be used, for example, as HCA (manufactured by Sanko Co., Ltd.) And get.

Further, when the method for producing the phenol resin (b) of the present invention is specifically described, it is preferred to add the phenol compound (a) dropwise or in portions to the phosphorus-containing compound while observing heat. At this time, an organic solvent can also be used as a reaction solvent.

The temperature at which the phenol compound (a) is added dropwise to the phosphorus-containing compound is preferably from 20 ° C to 200 ° C, and is particularly preferably from 50 ° C to 160 ° C in terms of control of reactivity and ease of removal of heat of reaction.

The ratio of the phenol compound (a) to the above-mentioned phosphorus-containing compound is not particularly limited, and for example, the olefin group 1 of the phenol compound (a) is excellent in terms of the water-decomposability of the obtained product. The equivalent amount is preferably from 1 equivalent to 1 equivalent in excess (for example, 1 to 5 equivalents) of the phosphorus-containing compound. Further, when the obtained compound is used as a curing agent for an epoxy resin, the phosphorus compound which is excessively present may be used as it is, or may be used as it is, or may be used after being removed, but the heat resistance and resistance of the finally obtained cured product may be In the aspect of being excellent in wetness, it is preferred that at least 50 parts by weight or more of the phosphorus atom-containing phenol compound of the present invention is contained in 100 parts by weight of the total of the phosphorus atom-containing phenol compound and the phosphorus-containing compound of the present invention. It is preferably contained in an amount of 80 parts by weight or more.

In the above reaction, when an organic solvent is used as the reaction solvent, it is not particularly limited. For example, it is preferably one which is inert to the phosphorus-containing compound or the phenol compound (a), and for example, an aliphatic alcohol, an aromatic hydrocarbon or These mixed solvents. As the aliphatic alcohol, in consideration of the reaction raw material to be used, the solubility of the obtained product, the reaction conditions, the economics of the reaction, and the like, methanol, ethanol, isopropanol, n-propanol, tert-butanol, and iso are included. Butanol, n-butanol, ethylene glycol lower alkyl ether, or propylene glycol lower alkyl ether. Further, examples of the aromatic hydrocarbon solvent include toluene, xylene, and cumene. The solvent is usually used in an amount of from 20 to 500 parts by weight based on 100 parts by weight of the total of the phosphorus-containing compound to be used, but is not limited thereto.

The phenol resin (b) of the present invention obtained as described above has the following formula (4) The structure.

(In the formula (4), R ₁ , R ₂ , k, and m are the same as the formulae (1) to (2), and Z represents a hydrogen atom or a structure of the following formula (5), and at least one of a plurality of Z exists. The structure of the following formula (5) is shown.

(In the formula (5), R _{3 is the} same as the formula (3)).

The hydroxyl equivalent of the phenol resin (b) of the present invention is preferably from 200 to 800 g/eq., more preferably from 220 to 750 g/eq. On the other hand, the softening point is preferably from 100 to 150 °C.

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

The epoxy resin of the present invention is obtained by reacting and epoxidizing an epihalohydrin with an phenol resin (b) of the present invention obtained by the above method in an alcohol solvent. In addition, in the case of epoxidation, only one type of the phenol resin (b) of the present invention may be used, or two or more types may be used in combination. Further, a phenol compound other than the phenol resin (b) may be used in combination with the phenol resin (b) of the present invention.

The phenol compound other than the phenol resin (b) which can be used in combination is not particularly limited as long as it is a phenol compound which is usually used as a raw material of the epoxy resin.

As the epoxy resin of the present invention, in particular, it exhibits excellent solvent solubility and has In terms of a highly flame-retardant cured product, the phenol compound (a) and the formula (3) obtained by reacting a compound represented by the formula (2) with a compound represented by the formula (1) are preferred. An epoxide of the phenol resin (b) of the present invention obtained by reacting the phosphorus-containing compound shown.

In the reaction for obtaining the epoxy resin of the present invention, epichlorohydrin, α-methylepichlorohydrin, β-methylepichlorohydrin, epibromohydrin or the like can be used as the epihalohydrin, but it is preferably industrially easy. Obtained epichlorohydrin. The amount of epihalohydrin used is usually 2 to 20 moles, preferably 2 to 15 moles, and more preferably 2 to 4.5 moles, based on the hydroxyl group of the phenol resin (b). The epoxy resin is obtained by adding a phenol resin (b) to an epihalohydrin in the presence of an alkali metal oxide, and then subjecting the produced 1,2-halool ether group to ring opening and epoxidation. At this time, the epihalohydrin is remarkably less than the usual amount as described above, whereby the molecular weight of the epoxy resin can be prolonged and the molecular weight distribution can be expanded. As a result, the obtained epoxy resin was extracted from the reaction system in the form of a resin having a relatively low softening point, and exhibited excellent solvent solubility.

Further, in the case of performing epoxidation, it is preferred to add an alcohol such as methanol, ethanol or isopropanol, dimethyl hydrazine, dimethyl hydrazine, tetrahydrofuran or the like in terms of the progress of the reaction. The reaction is carried out by an aprotic polar solvent such as an alkane. Among them, an alcohol is preferably used, and the ionic reaction in the epoxidation can be efficiently performed by the polarity of the alcohol solvent, whereby a high-purity epoxy resin can be obtained. Further, in the epoxy resin containing a liquid crystal original of the present invention, the α,β-unsaturated carbonyl moiety exhibits high reactivity and tends to be easily decomposed, but by using an alcohol solvent, since the solvent is mixed, It becomes difficult to accept the decomposition reaction. As the alcohol solvent which can be used, methanol, ethanol, and isopropyl alcohol are preferable. Among them, methanol is particularly preferably used from the viewpoint of compatibility with an epoxy resin.

In the case of using the above alcohols, the amount thereof to be used is usually 2 to 50% by mass, preferably 4 to 35% by mass based on the amount of the epihalohydrin used. Further, in the case of using an aprotic polar solvent, the amount of the epihalohydrin used is usually 5 to 100% by mass, preferably 10 to 80% by mass.

In the above epoxidation reaction, an alkali metal hydroxide can be used.

Examples of the alkali metal hydroxide which can be used in the epoxidation reaction include sodium hydroxide, potassium hydroxide, and the like, and these may be used as they are, or may be used as an aqueous solution. In the case of using an aqueous solution, the method may be as follows: the aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and the water and the table are continuously distilled off by distillation under a reduced pressure or a normal pressure. The mixture of halo alcohols removes water and continuously feeds the epihalohydrin back into the reaction system. The alkali metal hydroxide is used in an amount of usually 0.9 to 3.0 moles, preferably 1.0 to 2.5 moles, more preferably 1.0 to 2.0 moles, per mole of the hydroxyl group of the phenol resin (b) of the present invention. Especially good is 1.0~1.3 m.

Further, the present inventors have found that in the epoxidation reaction, in particular, by using sodium hydroxide in the form of flakes, the amount of halogen contained in the obtained epoxy resin can be remarkably reduced as compared with the use of sodium hydroxide in an aqueous solution. And the flaky sodium hydroxide is preferably added to the reaction system in portions. By the batch addition, the reaction temperature can be prevented from drastically decreasing, whereby the formation of a 1,3-halool or a halomethylene as an impurity can be prevented.

In order to promote the epoxidation reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride is preferably used as a catalyst.

The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol resin of the present invention.

The reaction temperature is usually from 30 to 90 ° C, preferably from 35 to 80 ° C. The reaction time is usually from 0.5 to 10 hours, preferably from 1 to 8 hours. Among them, in the case of using an alcohol solvent, it is preferably 50 ° C to 90 ° C, more preferably 60 to 85 ° C, and particularly preferably 70 to 80 ° C.

After completion of the reaction, the epihalohydrin, the solvent, and the like are removed from the reaction solution after washing the reaction mixture with water or without washing with water under reduced pressure. Further, in order to further reduce the amount of halogen contained in the obtained epoxy resin, the recovered epoxy resin of the present invention may be dissolved in a solvent such as toluene or methyl isobutyl ketone, and sodium hydroxide may be added thereto. An aqueous solution of an alkali metal hydroxide such as potassium hydroxide is reacted to achieve a desired ring closure. In this case, the alkali metal hydroxide is used in an amount of usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on 1 mol of the hydroxyl group of the phenol resin of the present invention. reaction The temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.

After completion of the reaction, the salt produced is removed by filtration, washing with water, etc., and the epoxy resin of the present invention is obtained by distilling off the solvent by heating under reduced pressure. Further, in the case where the epoxy resin of the present invention is precipitated in the form of crystals, the crystal of the epoxy resin of the present invention may be filtered and extracted after dissolving the produced salt in a large amount of water.

The total halogen amount of the epoxy resin of the present invention obtained by using flaky sodium hydroxide as described above is usually 1800 ppm or less, preferably 1600 ppm or less, more preferably 1300 ppm or less. Excessive total halogen will adversely affect the electrical reliability of the cured product.

Hereinafter, the epoxy resin composition of the present invention will be described. The epoxy resin composition of the present invention contains at least one of the epoxy resin of the present invention and the phenol resin of the present invention as an essential component.

In the epoxy resin composition of the present invention, when the epoxy resin of the present invention is contained as an essential component, the epoxy resin of the present invention may be used alone or in combination with other epoxy resins.

Specific examples of the other epoxy resin include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenyldiol, bisphenol AD, and bisphenol I) or phenols (phenol, alkyl). Substituted phenol, aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene, and dihydroxynaphthalene, etc.) with various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkane) Polycondensate of base-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, benzenedialdehyde, crotonaldehyde and cinnamaldehyde; polycondensation of aromatic compounds such as xylene, polycondensation of formaldehyde and phenols Phenols and various diene compounds (dicyclopentadiene, terpenes, ethylene cyclohexane, norbornadiene, vinyl norbornene, tetrahydroindene, two a polymer of vinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, and isoprene; phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, Polycondensate of acetophenone and benzophenone, etc.; condensation of phenols and aromatic dimethanols (benzene dimethanol and biphenyl dimethanol) Polycondensate of phenols and aromatic dichloromethyls (α,α'-dichloroxylene and bischloromethylbiphenyl, etc.); phenols and aromatic bisalkoxymethyls ( Polycondensate of bismethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.; polycondensate of bisphenols and various aldehydes; and glycidol such as alcohols a glycidyl ether epoxy resin after the grouping; an alicyclic epoxy resin; a glycidylamine epoxy resin; and a glycidyl ester epoxy resin, etc., as long as it is a commonly used epoxy resin, It is not limited to these. These may be used alone or in combination of two or more.

When the other epoxy resin is used in combination, the epoxy resin of the present invention preferably accounts for 30% by mass or more, more preferably 40% by mass or more, based on the total epoxy resin component of the epoxy resin composition of the present invention. It is preferably 70% by mass or more, and particularly preferably 100% by mass (in the case where other epoxy resins are not used in combination). In the case where the epoxy resin of the present invention is used as a modifier of the epoxy resin composition, it is added in a ratio of 1 to 30% by mass based on the total epoxy resin.

In the case where the epoxy resin composition of the present invention contains the epoxy resin of the present invention as an essential component, a hardener is preferably used. In this case, as the hardener which can be used, the phenol resin of the present invention described above may be used as the other hardener. Examples of the other curing agent include an amine compound, an acid anhydride compound, a guanamine compound, and a phenol compound. Specific examples of such other curing agents are shown in the following (a) to (e).

(a) Amine-based contents: diaminodiphenylmethane, di-extension ethyltriamine, tri-ethylidenetetramine, diaminodiphenylguanidine, isophoronediamine, and naphthalenetriamine.

(b) An acid anhydride compound: phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, A Methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like.

(c) a guanamine compound: dicyandiamide or a polyamide resin synthesized from a dimer of linoleic acid and ethylenediamine.

(d) Phenolic compounds: polyphenols (bisphenol A, bisphenol F, bisphenol S, hydrazine) Bisphenol, stilbene, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-(1,1'-biphenyl) -4,4,-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane and 1,1,2,2-tetrakis(4-hydroxyphenyl) Ethane, etc.; by phenols (such as phenol, alkyl substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene and dihydroxynaphthalene, etc.) and aldehydes (formaldehyde, acetaldehyde, benzaldehyde, p-hydroxyl Condensation of benzaldehyde, o-hydroxybenzaldehyde and furfural, ketones (p-hydroxyacetophenone and o-hydroxyacetophenone), or diene (dicyclopentadiene and tricyclopentadiene) The obtained phenol resin; by the above phenols and substituted biphenyls (4,4'-bis(chloromethyl)-1,1'-biphenyl and 4,4'-bis(methoxymethyl)- 1,1'-biphenyl, etc.), or substituted phenyls (1,4-bis(chloromethyl)benzene, 1,4-bis(methoxymethyl)benzene, and 1,4-bis(hydroxyl) a phenol resin obtained by polycondensation of phenyl or the like; a modified substance of the above phenol and/or the above phenol resin; and a halogenated phenol such as tetrabromobisphenol A or a brominated phenol resin.

(e) Others: imidazoles, BF ₃ -amine complexes, anthracene derivatives.

Among these other curing agents, amine compounds such as diaminodiphenylmethane, diaminodiphenylanthracene and naphthalene diamine, and catechol and aldehydes, ketones, dienes, and substituents A hardener having a structure in which an active hydrogen group is adjacent to a condensate such as a benzene or a substituted phenol contributes to the arrangement of the epoxy resin, which is preferable.

Other hardeners may be used singly or in combination.

Further, in the case of using the phenol resin of the present invention as a curing agent in the epoxy resin composition of the present invention, in addition to the phenol resin of the present invention, other curing agents may be used in combination. Examples of the curing agent which can be used in combination include an amine compound, an acid anhydride compound, a guanamine compound, and a phenol compound which are the same as described above.

When the other curing agent is used in combination, the ratio of the phenol resin of the present invention to all the hardener components in the epoxy resin composition of the present invention is preferably 5% by mass or more, more preferably 10% by mass or more, and still more preferably 30% by mass or more. In the epoxy resin composition of the present invention, the total amount of the hardener containing the phenol compound of the present invention is preferably used in comparison with the entire epoxy resin ring. The oxy group is equivalent to 0.5 to 2.0 equivalents, and more preferably 0.6 to 1.5 equivalents.

A hardening accelerator may also be added to the epoxy resin composition of the present invention as needed. Specific examples of the curing accelerator include phosphines such as triphenylphosphine and bis(methoxyphenyl)phenylphosphine, 2-methylimidazole, 2-ethylimidazole, and 2-ethyl-4- Imidazoles such as methylimidazole, tertiary amines such as 2-(dimethylaminomethyl)phenol, tris(dimethyl)aminomethylphenol, diazabicycloundecene, and tetrabutylammonium salts a tetra-ammonium salt such as triisopropylmethylammonium salt, trimethylsulfonium ammonium salt or cetyltrimethylammonium salt, triphenylbenzyl phosphonium salt, triphenylethyl phosphonium salt, or tetra a quaternary phosphonium salt such as a butyl sulfonium salt (the relative ion of the quaternary salt is a halogen, an organic acid ion, a hydroxide ion, etc., and is not particularly specified, and particularly preferably an organic acid ion or a hydroxide ion), and a stannous octoate Such as metal compounds and the like.

The curing accelerator is used in an amount of usually 0.2 to 5.0 parts by weight, preferably 0.2 to 4.0 parts by weight per 100 parts by weight of the epoxy resin.

An inorganic filler may be added to the epoxy resin composition of the present invention (hereinafter also referred to as a curable resin composition) as needed. Examples of the inorganic filler include crystalline cerium oxide, molten cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, tantalum nitride, boron nitride, zirconium oxide, forsterite, and the like. A powder such as talc, spinel, titanium dioxide or talc, or beads which have been spheroidized, etc., but is not limited thereto. These may be used alone or in combination of two or more. The content of the inorganic fillers can be from 0 to 95% by weight in the curable resin composition of the present invention. Further, various additives such as a decane coupling agent, a release agent such as stearic acid, palmitic acid, zinc stearate or calcium stearate, a surfactant, a dye, a pigment, and an ultraviolet absorber may be added to the curable resin composition of the present invention. Agent, various thermosetting resins.

Various preparation agents such as a decane coupling agent, a release agent, and a pigment, various thermosetting resins, various thermoplastic resins, and the like may be added to the epoxy resin composition of the present invention as needed. Specific examples of the thermosetting resin and the thermoplastic resin include a vinyl ester resin, an unsaturated polyester resin, a maleimide resin, a cyanate resin, an isocyanate compound, and a benzo compound. a compound, a vinyl benzyl ether compound, a polybutadiene and a modified product thereof, a modified product of an acrylonitrile copolymer, an anthracene resin, a fluororesin, a polyoxyxylene resin, a polyether quinone, a polyether oxime, a polyphenylene ether, Polyacetal, polystyrene, polyethylene, dicyclopentadiene resin, and the like. The thermosetting resin or the thermoplastic resin may be used in an amount of 60% by mass or less based on the epoxy resin composition of the present invention.

The epoxy resin composition of the present invention can be obtained by uniformly mixing the above components, and as a preferred use thereof, a semiconductor sealing material, a printed wiring board, or the like can be given.

The epoxy resin composition of the present invention can be easily made into a cured product by the same method as known in the prior art. For example, an epoxy resin, a hardener, an inorganic filler, and a hardening accelerator, a compounding agent, various thermosetting resins, various thermoplastic resins, and the like which are essential components of the epoxy resin composition of the present invention can be used. , if necessary, using an extruder, a kneader or a roller or the like to sufficiently mix until uniform, to obtain the epoxy resin composition of the present invention, and then by melt injection molding or transfer molding or injection molding, compression molding The epoxy resin composition of the present invention is molded and further heated at a melting point or higher for 2 to 10 hours, whereby a cured product of the epoxy resin composition of the present invention is obtained. By sealing the semiconductor element mounted on a lead frame or the like by the above method, the epoxy resin composition of the present invention can be used for semiconductor sealing applications.

Further, the epoxy resin composition of the present invention can also be used as a varnish containing a solvent. The varnish can be obtained, for example, by containing an epoxy resin of the present invention or a phenol resin of the present invention in at least one of an epoxy resin and a hardener, and optionally containing a mixture of other components such as an inorganic filler. With toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, N, N'-dimethylformamide, N, N'-dimethyl B Indamine, dimethyl hydrazine, N-methylpyrrolidone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, three Glycol ethers such as ethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether Esters such as acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate, cyclic esters such as γ-butyrolactone, petroleum ether, petroleum brain, hydrogenated petroleum An organic solvent such as a petroleum solvent such as a brain or a solvent naphtha is mixed. The amount of solvent relative to the clear The total amount of the paint is usually 10 to 95% by mass, preferably 15 to 85% by mass.

By immersing the varnish obtained as described above in a fiber substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, heating to remove the solvent, and by using the epoxy of the present invention The resin composition is made into a semi-hardened state, and the prepreg of the present invention can be obtained. The term "semi-hardened state" as used herein means a state in which a part of the epoxy group which is a reactive functional group remains unreacted. The prepreg can be thermoformed to obtain a cured product.

Example

Hereinafter, the present invention will be described in detail by way of examples, but the invention is not limited to the examples. In the synthesis examples, examples, and comparative examples, the parts mean parts by mass.

Further, the hydroxyl equivalent and the softening point were measured under the following conditions.

‧hydroxy equivalent

It was measured by the method described in JIS K-7236, and the unit was g/eq.

‧Softening Point

Measured in accordance with the method according to JIS K-7234, the unit is °C.

(Synthesis Example 1)

150 parts of 4'-hydroxyacetophenone, 167 parts of vanillin, and 221 parts of ethanol were placed in a flask equipped with a stirrer, a reflux cooling tube, and a stirring device to dissolve. 22 parts of 97 mass% sulfuric acid was added to the flask, and the temperature was raised to 60 ° C. After reacting at this temperature for 10 hours, the reaction liquid was poured into 1324 parts of water to cause crystallization. After filtration and crystallization, it was washed twice with water of 662 parts of water, and then vacuum-dried to obtain 282 parts of a yellow crystalline phenol compound (a). The endothermic peak temperature measured by DSC of the obtained crystal was 233 °C.

(Example 1)

While performing nitrogen purge, 178 parts of HCA (manufactured by Sanko Co., Ltd.) and 360 parts of xylene were placed in a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, and heated to 100 °C. 200 parts of the phenol compound (a) was added thereto in batches over 1 hour, and then the temperature was raised to At 130 ° C, and heated to reflux for 10 hours. After adding 180 parts of ethanol to the reactant, the solvent was distilled off under reduced pressure using an evaporator to obtain 320 g of the phenol resin (b) (P1) of the present invention. The obtained phenol resin (b) had a hydroxyl equivalent of 243 g/eq. and a softening point of 135.8 °C.

(Example 2)

While performing nitrogen purge, 163 parts of the phenol resin (P1 hydroxyl equivalent: 243 g/eq.) of the present invention, 433 parts of epichlorohydrin (7 moles of phenol resin), and 130 parts of methanol were added to a mixer and a reflux cooling tube. The flask of the stirring apparatus was dissolved under stirring and heated to 70 to 75 °C. Then, 30 parts of flaky sodium hydroxide was added in portions over 90 minutes, and further reacted at 75 ° C for 75 minutes. After completion of the reaction, water was washed with 90 parts of water, and excess solvent such as epichlorohydrin was removed from the oil layer by distillation using a rotary evaporator under reduced pressure. 380 parts of methyl isobutyl ketone was added to the residue to dissolve, and the temperature was raised to 75 °C. 11 parts of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and the reaction was carried out for 1 hour, and then washed with water until the washing water of the oil layer became neutral. The obtained solution was distilled off under reduced pressure using a rotary evaporator to remove methyl isobutyl ketone or the like, whereby 183 parts of the epoxy resin (EP1) of the present invention was obtained. The epoxy equivalent of the obtained epoxy resin was 304 g/eq.

(Examples 3 to 6 and Comparative Example 1)

The epoxy resin (EP1 and EP2), the filler (inorganic filler), the wax, the coupling agent, and the hardening accelerator were blended according to the ratio (equivalent) of Table 1, and uniformly mixed using a kneader. The phenol obtained in Example 1 was kneaded. The resin (P1) or the comparative phenol resin (P3) was used to obtain a curable resin composition. The curable resin composition was pulverized by a stirrer and further tableted by a tableting machine. The tableted curable resin composition (175 ° C × 60 sec) was transferred and molded, and further cured at 160 ° C × 2 hours + 180 ° C × 6 hours after demolding to obtain a test piece for evaluation. . Using the test piece for evaluation, heat resistance and flame retardancy were measured and evaluated based on the following points. The test results are shown in Table 1.

<heat resistance test>

Dynamic viscoelasticity measuring instrument: manufactured by TA-instruments, DMA-2980

Measuring temperature range: -30 ° C ~ 280 ° C

Temperature speed: 2 ° C / min

Test piece size: An article cut into 5 mm × 50 mm (thickness: about 800 μm) was used.

Analysis condition Tg: The peak point (tan δ MAX) of Tan δ in the DMA measurement is set to Tg.

<flammability test>

‧ Determination of flame retardancy: According to UL94. Among them, the sample size was set to have a width of 12.5 mm, a length of 150 mm, and a thickness of 0.8 mm.

‧ Residual flame time: The total of the residual flame time after 10 flames of 5 samples of 1 group.

EP1: Nippon Chemical Pharmaceutical Co., Ltd. manufactures NC2000L

EP2: Nippon Chemical Pharmaceutical Co., Ltd. manufactures NC3000

P3: Mitex Chemical Company manufactures Milex XLC-3L

P2: Mix P1 and P3 in a ratio of 33:67 by weight ratio

P4: Mix P1 and P3 in a ratio of 5:95 by weight ratio

P5: Mix P1 and P3 in a ratio of weight ratio of 10:90

Wax: Carnauba 1

Hardening accelerator: triphenylphosphine (TPP manufactured by Beixing Chemical Co., Ltd.)

Coupling agent: Shin-Etsu Chemical Co., Ltd. manufactures KBM-303

Inorganic filler: molten cerium oxide MSM-2122 manufactured by Lucerne Industrial Co., Ltd. is 83% by weight relative to resin

Hardening accelerator usage:

The sample for evaluation of heat resistance was set to 1% by weight based on the weight of the epoxy resin, and the sample used for evaluation of flame retardancy was set to 2% by weight based on the weight of the epoxy resin.

Wax usage: 0.3% by weight relative to the composition

Coupling agent usage: 0.4% by weight relative to the filler

Epoxy resin ‧ hardener ratio: 1 equivalent

The phenol resin of the present invention is excellent in heat resistance and flame retardancy as compared with the phenol resin of the comparative example.

The present invention has been described in detail with reference to the specific embodiments thereof. It is understood that various changes and modifications may be made without departing from the spirit and scope of the invention.

In addition, the present application is based on a Japanese application filed on October 9, 2013 (Japanese Patent Application No. 2013-211750), the entire contents of which are incorporated by reference. Moreover, all references that are incorporated herein by reference are incorporated in their entirety.

[Industrial availability]

The phenol resin of the present invention can be used for an epoxy resin composition, and the cured product of the epoxy resin composition exhibits excellent heat resistance and flame retardancy, and is therefore suitable for use in various composites including semiconductor sealing materials and prepregs. Materials, adhesives, coatings, etc.

Claims (7)

A phenol resin (b) obtained by reacting a phenol compound represented by the following formula (1) with a compound represented by the following formula (2) to obtain a phenol compound (a), and further having the following formula (3) obtained by reacting a phosphorus-containing compound as shown; (In the formula (1), R ₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, Any of a substituted or unsubstituted alkoxy group having a nitro group or a carbon number of 1 to 10; m represents the number of R ₁ and is an integer of 0 to 4); (In the formula (2), R ₂ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, Any of a substituted or unsubstituted alkoxy group having a nitro group, a decyl group, an allyl group or a carbon number of 1 to 10; k represents the number of R ₂ and is an integer of 0 to 4); (In the formula (3), R ₃ each independently represents a hydrogen atom, an alkyl group or an aromatic group). a phenol resin, which is represented by the following formula (4); (In the formula (4), R ₁ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, a substituted or unsubstituted aryl group having 6 to 10 carbon atoms, a hydroxyl group, Any one of a substituted or unsubstituted alkoxy group having a nitro group or a carbon number of 1 to 10, and R ₂ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and carbon. Any of 6 to 10 substituted or unsubstituted aryl, hydroxy, nitro, formazan, allyl or substituted or unsubstituted alkoxy groups having 1 to 10 carbon atoms; k The number of R ₂ is an integer of 0 to 4; m represents the number of R ₁ and is an integer of 0 to 4; Z represents a hydrogen atom or a structure of the following formula (5), and at least one of a plurality of Z exists Representing the structure of the following formula (5)); (In the formula (5), R ₃ each independently represents a hydrogen atom, an alkyl group or an aromatic group). An epoxy resin which is a phenol resin and epihalohydrin of claim 1 or 2 Obtained by (epihalohydrin) reaction. An epoxy resin composition comprising a phenol resin and an epoxy resin according to claim 1 or 2. An epoxy resin composition as claimed in claim 4, which is used for semiconductor sealing purposes. A prepreg comprising the epoxy resin composition of claim 4 and a sheet-like fibrous substrate. A hardened material obtained by hardening an epoxy resin composition of claim 4 or 5 or a prepreg of claim 6 of the patent application.