TW201529645A - Phenol resin, epoxy resin, epoxy resin composition, and cured product of same - Google Patents

Abstract

The objective of the present invention is to provide a resin from which a cured product having both excellent heat resistance and flame retardancy can be obtained. This phenol resin and epoxy resin are resins having a benzopyran structure, and the phenol resin is represented by formula (1) below. (In the formula R1 represents independent C1-6 alkyl groups, R2 represents independent hydrogen atoms or C1-6 alkyl groups, k represents an integer from 1-4, and n represents an integer from 0-10).

Description

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

The present invention relates to an epoxy resin composition suitable for use in electrical and electronic materials requiring heat resistance and a cured product thereof.

The epoxy resin composition is widely used in electrical/electronic parts, structural materials, and adhesives due to workability and excellent electrical properties, heat resistance, adhesion, and moisture resistance (water resistance) of the cured product. Coatings and other fields.

However, in recent years, in the field of electric/electronics, along with its development, it is required to represent high purity of a resin composition, as well as moisture resistance, adhesion, dielectric properties, and to make a filler (inorganic or organic filler). Further improvement in various properties such as low filling of high filling and improvement of reactivity in a molding cycle is further improved. In addition, as a structural material, materials requiring light weight and excellent mechanical properties are required for aerospace materials, entertainment/sports applications, and the like. In particular, in the field of semiconductor sealing, the substrate (the substrate itself or its peripheral materials), thinning, stacking, systemization, and stereoscopic start become complicated with the change of the semiconductor, and a very high level of heat resistance or high flow is required. Characteristics such as sex (Non-Patent Document 1). In addition, in particular, with the expansion of the use of plastic packaging for in-vehicle use, the demand for improvement in heat resistance has become stricter (Non-Patent Document 2). Specifically, heat resistance of 150 ° C or higher is required as the driving temperature of the semiconductor rises. Usually, the epoxy resin is stored An epoxy resin having a high softening point tends to have high heat resistance, but on the other hand, a decrease in thermal decomposition temperature and a decrease in flame retardancy are problems.

Therefore, epoxy resins having high flame retardancy and heat resistance have been required in the past. In addition, as an epoxy resin having good heat resistance, an epoxy resin having a dioxane structure as disclosed in Patent Document 1 and Non-Patent Document 3 has been developed by attempting a reaction between acetone and resorcin. However, the flavane structure is difficult to produce high flame retardancy. In addition, since the structure obtained from the reaction product of the above two compounds is a flavane structure, the results are obtained from Patent Document 1 and Non-Patent Document 3, so that the development of a phenol resin which is resistant to flame retardancy and heat resistance is placed on other skeletons. Phenolic resin. In this case, the demand for a phenol resin which satisfies the characteristics excellent in both flame retardancy and heat resistance needs to be improved.

Patent Document 1: Japanese Laid-Open Patent Publication No. 2010-275221

Non-patent literature

Non-Patent Document 1: "2008 STRJ Report Semiconductor Blueprint Special Committee Heisei 20 Annual Report", Chapter 8, p1-1, [online], March 2009, JEITA (Company) Electronic Information Technology Industry Association Semiconductor Technology Blueprint Committee, [Search on May 30, 2012], Internet <URL: http://strj-jeita.elisasp.net/strj/nenjihoukoku-2008.cfm>

Non-Patent Document 2: Takakura Shinno, etc., Matsushita Electric Technology Co., Ltd. Vehicle-related device technology High-temperature action IC for vehicles, No. 74, Japan, May 31, 2001, 35-40

Non-Patent Document 3: P. Livant et al., J. Org. Chem., 1997, Vol. 62, 737-742.

When the epoxy resin is generally subjected to high Tg, the flame retardancy is lowered. This system is cross-linked The effect of increasing the degree. However, in the context of demanding high Tg for semiconductor peripheral materials requiring flame retardancy, it is expected to urgently develop resins having such opposite characteristics. Therefore, it is imperative to find an epoxy resin that can expect such characteristics.

The inventors of the present invention have completed the present invention as a result of intensive studies in order to solve the above problems.

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

(1) A phenol resin which is represented by the following formula (1),

(wherein R ₁ each independently represents an alkyl group having 1 to 6 carbon atoms; and R ₂ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; k represents an integer of 1 to 4; and n represents 0 to 10; Integer)

(2) The phenol resin according to the above (1), wherein the average value of n in the above formula (1) constituting the molecule of the resin is 0.05 or more and 4.0 or less.

(3) The phenol resin according to the above (1), wherein, in the ¹³ C-NMR spectrum, when the peak area of the CH ₃ carbon derived from the ketone is set to 1, the peak area of the CH ₂ carbon is 0 or more and 0.2 or less.

(4) An epoxy resin obtained by reacting epihalohydrin with the phenol resin according to any one of the above items (1) to (3).

(5) An epoxy resin composition comprising the one of the above items (1) to (3) Phenolic resin and epoxy resin.

(6) An epoxy resin composition comprising the epoxy resin, the curing agent, and any hardening accelerator described in the above (4).

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

The phenol resin and epoxy resin of the present invention are phenol resins or epoxy resins having a benzopyran structure. As described above, the phenol resin or the epoxy resin has a benzopyran structure, and a resin excellent in both heat resistance and flame retardancy can be obtained.

The phenol resin of the present invention can be obtained by reacting a dihydroxybenzene (a) with a ketone (b).

First, the description will be given for the dihydroxybenzenes (a). The dihydroxybenzenes (a) are compounds represented by the following formula (2).

(In the formula (2), R ₂ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; k represents an integer of 1 to 4)

As the dihydroxybenzenes (a), catechol, 3-methylcatechol, 4-tert-butyl catechol, and 3,5-di-t-butyl-o-phenylene can be exemplified. Phenol, resorcinol, 2-methyl resorcinol, 5-methyl resorcinol, 2,5-dimethyl resorcinol, 4-butyl resorcinol, 4-hexyl Hydroquinone, hydroquinone, 2-methylhydroquinone, 2,6-dimethyl hydroquinone, 2,3-dimethyl hydroquinone, 2,3,5-trimethyl The base is hydroquinone, 2-tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, etc., but is not limited thereto. Preferred are catechol, resorcinol, hydroquinone, and particularly resorcinol. Here, in the formula (1), in order to obtain that n is greater than 0 (for example, n is 1 or more), resorcin can be preferably used.

Next, the ketones (b) will be described. The ketone is a compound represented by the following formula (3).

(In the formula (3), R ₁ represents the same meaning as the formula (1))

Examples of the ketone (b) include acetone, methyl ethyl ketone, methyl butyl ketone, 3-methyl-2-butanone, methyl isobutyl ketone, 3-pentanone, and 2-methyl group. -3-pentanone, 2,4-dimethyl-3-pentanone or the like is preferably acetone or methyl ethyl ketone, and particularly preferably acetone.

The phenol resin of the present invention is obtained by a condensation reaction of one or more compounds represented by the formula (2) with a compound represented by the formula (3) under acidic conditions. Further, the reaction can also be carried out under basic conditions, but it is preferably under acidic conditions.

The compound represented by the formula (3) is usually used in an amount of 0.25 with respect to the compound 1 represented by the formula (2). ~5.0 moules, preferably 0.3 to 2.5 moules.

In the case where the condensation reaction is carried out under acidic conditions, the acidic catalyst which can be used is not particularly limited, and examples thereof include organic acid catalysts such as toluenesulfonic acid, xylenesulfonic acid, and oxalic acid, and inorganic acid catalysts such as hydrochloric acid and sulfuric acid. These may be used alone or in combination. The amount of the acidic catalyst used is usually 0.001 to 15 moles, preferably 0.002 to 10 moles, per mole of the compound 1 represented by the formula (3).

In the case where the condensation reaction is carried out under alkaline conditions, the same can be carried out in the same manner, and the basic catalyst to be used is not particularly limited as long as it is known.

In the reaction for obtaining the phenol resin of the present invention, a solvent may also be used as needed. The solvent which can be used is not particularly limited as long as it does not have reactivity with the compound represented by the formula (2) as in the case of a ketone, and it is easy to dissolve the compound represented by the formula (2) in the raw material. In other words, it is preferred to use an alcohol as a solvent.

Specific examples of the solvent that can be used include alcohols such as methanol, ethanol, and isopropanol, and dimethyl hydrazine, dimethyl hydrazine, tetrahydrofuran, and An aprotic polar solvent such as an alkane, methyl ethyl ketone or methyl isobutyl ketone, or an aromatic hydrocarbon such as toluene or xylene.

In the case of using a solvent, the amount used is not particularly limited, and for example, it can be used in an amount of from 100 to 500 parts by weight based on the compound 1 shown in the formula (2).

The reaction temperature is usually 10 to 150 ° C, preferably 50 to 140 ° C, and particularly preferably 85 ° C to 140 ° C for the reaction. The reaction time is usually 0.5 to 20 hours, but the reactivity varies depending on the type of the raw material compound, and is not limited thereto.

In order to obtain the phenol resin of the present invention, after the reaction of the compounds of the above formulas (2) and (3) is completed, the reaction is further carried out at a high temperature as the second stage. The high temperature reaction of the second stage is preferably carried out at 100 ° C or higher. In terms of ending the reaction, it is preferred to remove water by-produced at this time by azeotropy or the like. By performing the second-stage reaction, the peak of CH ₂ carbon in the ¹³ C-NMR spectrum is reduced to form a compound having the structure represented by the general formula (1).

After the reaction is completed, the acid is neutralized with an alkali. The base is not particularly limited, and examples thereof include sodium hydroxide, sodium carbonate, sodium tripolyphosphate, and ammonia. At this time, in order to uniformly disperse the base, it is preferably added dropwise in the form of an aqueous solution.

After the completion of the reaction, when the product is extracted as a resin, the reaction product is washed with water or not, and the unreacted product or solvent is removed from the reaction liquid under heating and reduced pressure. In order to efficiently remove unreacted materials, water washing can also be carried out under alkaline conditions. In the case where the product is extracted in a crystalline form, the crystal is precipitated by dropping a reaction liquid into a large amount of water.

The phenol resin of the present invention obtained in this manner is a phenol resin represented by the following formula (1).

(wherein R ₁ each independently represents an alkyl group having 1 to 6 carbon atoms; and R ₂ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; k represents an integer of 1 to 4; and n represents 0 to 10; Integer)

In the chromatogram obtained by gel permeation chromatography (GPC) analysis of the phenol resin of the present invention, the peak area of the molecule having a structure of n=0 is usually 20 to 95 area% with respect to the total area of all the peaks. It is preferably 30 to 80 area%.

In the case of the ¹³ C-NMR spectrum, when the peak area of the CH ₃ carbon derived from acetone is 1, the peak area of the CH ₂ carbon is usually 0 or more and 0.3 or less, preferably 0.2 or less, and particularly preferably 0.1 or less, preferably 0.05 or less. In particular, it is preferable because it exhibits excellent flame retardancy by being 0.2 or less.

The average value of n in the formula (1) constituting the molecule of the resin is preferably from 0.05 to 4, particularly preferably from 0.1 to 3. The reason for this is that the dielectric constant can be lowered by the number of repetitions. Here, the content ratio of the molecule (phenol compound) in which n is not 0 in the obtained phenol resin is a content ratio calculated by gel permeation chromatography (GPC) (relative to all peaks in the chromatogram) The ratio of the total area is preferably from 5 to 80 area%, more preferably from 20 to 70 area%.

Further, the hydroxyl equivalent is preferably from 125 to 250 g/eq., particularly preferably from 140 to 200 g/eq. The softening point is preferably from 100 to 200 ° C, particularly preferably from 120 to 180 ° C.

The phenol resin of the present invention is useful as a resin material such as a cyanate resin or an epoxy resin.

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

The epoxy resin of the present invention is obtained by subjecting a phenol resin of the present invention obtained by the above method to reaction with an epihalohydrin in a solvent to carry out epoxidation. Here, a phenol compound other than the phenol resin of the present invention may be used in combination with the phenol resin of the present invention.

The phenol compound other than the phenol resin of the present invention 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.

According to the epoxy resin of the present invention, a cured product having high heat resistance and high flame retardancy due to a high melting point is obtained.

In the reaction for obtaining the epoxy resin of the present invention, as the epihalohydrin, epichlorohydrin, α-methylepichlorohydrin, β-methylepichlorohydrin, epibromohydrin or the like can be used, and it is preferably industrially easy. Obtained epichlorohydrin. The amount of the epihalohydrin used is usually 2 to 20 moles, preferably 2 to 15 moles, and more preferably 2 to 8 moles, per mole of the hydroxyl group of the phenol resin of the present invention. The epoxy resin is obtained by adding a phenol compound to an epihalohydrin in the presence of an alkali metal oxide, and then subjecting the formed 1,2-halool ether group to ring opening to carry out an epoxidation reaction. At this time, the epihalohydrin is used in a significantly less than usual amount as described above, whereby the molecular weight of the epoxy resin can be increased, and the molecular weight distribution can be expanded. As a result, the obtained epoxy resin was extracted from the system in the form of a resin having a relatively low softening point, showing excellent solvent solubility.

Further, in the case of 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 reaction progress. The reaction is carried out by an aprotic polar solvent such as an alkane. Among them, an alcohol is preferable, and the ionic reaction in the epoxidation can be efficiently performed by the polarity of the alcohol solvent, and the epoxy resin can be obtained in high purity. 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. Further, when an aprotic polar solvent is used, the amount of the epihalohydrin used is usually 5 to 100% by mass, preferably 10 to 80% by mass.

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 an aqueous solution thereof may be used. In the case of using an aqueous solution, it may be a method in which an aqueous solution of the alkali metal hydroxide is continuously added to the reaction system, and is continuously distilled off by liquid separation under reduced pressure or at normal pressure. The mixture of water and epihalohydrin removes water and only the epihalohydrin is continuously returned to the reaction system. alkali metal The amount of hydroxide used is usually from 0.9 to 3.0 moles, preferably from 1.0 to 2.5 moles, more preferably from 1.0 to 2.0 moles, and more preferably from 1.0 to 1.3, relative to the hydroxyl group of the phenol resin of the present invention. Moor.

Further, 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. Further, the flaky sodium hydroxide is preferably added to the reaction system in portions. By batchwise addition, it is possible to prevent a rapid decrease in the reaction temperature, thereby preventing the formation of a 1,3-halool or a halomethylene as an impurity.

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, based on the hydroxyl group of the phenol compound 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 reactant is washed with water or without washing with water, and the epihalohydrin or solvent is removed from the reaction solution under heating and 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 cause the ring to be surely closed. In this case, the amount of the alkali metal hydroxide used is usually 0.01 to 0.3 mol, preferably 0.05 to 0.2 mol, based on the hydroxyl group of the phenol compound of the present invention. The reaction temperature is usually 50 to 120 ° C, and the reaction time is usually 0.5 to 2 hours.

After completion of the reaction, the resulting salt is removed by filtration, washing with water, etc., and the solvent is distilled off under reduced pressure under heating to obtain an epoxy resin of the present invention. Also, in the ring of the present invention When the oxygen resin is precipitated as a crystal, the crystal of the epoxy resin of the present invention may be removed by filtration after dissolving the produced salt in a large amount of water.

As the epoxy resin obtained in the above manner, the glycidyl compound of the above formula (1) is obtained, and when the phenol resin as the raw material contains the phenol compound represented by the above formula (2), the above formula can also be obtained. (2) A glycidyl compound. Therefore, it is a mixture of at least two epoxy resins. Here, regarding the obtained epoxy resin, the content ratio of the glycidyl compound of the above formula (2) by the measurement of gel permeation chromatography (GPC) in the resin (relative to the chromatogram) The ratio of the total area of all the peaks is preferably from 1 to 25 area%, more preferably from 1 to 20 area%.

As described above, the total halogen amount of the epoxy resin of the present invention obtained by using flaky sodium hydroxide is usually 1800 ppm or less, preferably 1600 ppm or less, and more preferably 1300 ppm or less. In the case where the amount of the halogen is excessive, the hardening property of the cured product is adversely affected, and the ruthenium remains as an uncrosslinked end. Therefore, there is a concern that the molecules are not aligned in the molten state at the time of hardening, and the cured physical properties are lowered. .

The epoxy resin composition of the present invention is described below. 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, the epoxy resin of the present invention can 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, biphenol, bisphenol AD, and bisphenol I) or phenols (phenol, alkyl-substituted phenol). , aromatic substituted phenol, naphthol, alkyl substituted naphthol, dihydroxybenzene, alkyl substituted dihydroxybenzene and dihydroxy naphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl substitution) Benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, benzenedialdehyde, crotonaldehyde and cinnamaldehyde A polycondensate, a polycondensate of an aromatic compound such as xylene, and a polycondensate of formaldehyde and a condensate of a phenol, a phenol and various diene compounds (dicyclopentadiene, decene, vinylcyclohexene, hail a polymer of norbornadiene, vinyl norbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc. Polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanol (benzene dimethanol and Polycondensates of benzenes and other aromatic dichloromethyls (α,α'-dichloroxylene and bischloromethylbiphenyl), phenols and aromatics Polycondensate of bisalkoxymethyl (dimethoxymethylbenzene, bismethoxymethylbiphenyl, bisphenoxymethylbiphenyl, etc.), polycondensate of bisphenols and various aldehydes And a glycidyl ether epoxy resin, an alicyclic epoxy resin, a glycidylamine epoxy resin, or a glycidyl ester epoxy resin obtained by glycidylating an alcohol or the like. , As long as it is generally used as an epoxy resin, it is not limited to such. These may be used alone or in combination of two or more.

When the other epoxy resin is used in combination, the epoxy resin composition of the present invention preferably accounts for 30% by mass or more, more preferably 40% by mass, based on the total epoxy resin component of the epoxy resin composition of the present invention. The above is more preferably 70% by mass or more, and particularly preferably 100% by mass (in the case where other epoxy resins are not used in combination). However, when 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.

Examples of the curing agent which can be used in the epoxy resin composition of the present invention include an amine compound, an acid anhydride compound, a guanamine compound, and a phenol compound. Specific examples of such other hardeners are shown in the following (a) to (e).

(a) an amine compound diaminodiphenylmethane, di-ethyltriamine, tri-ethyltetramine, Diaminodiphenyl hydrazine, isophorone diamine, naphthalene diamine, etc.

(b) An acid anhydride compound phthalic anhydride, trimellitic anhydride, pyromellitic dianhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl Methylnadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc.

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

(d) phenolic compound polyphenols (bisphenol A, bisphenol F, bisphenol S, bisphenol, stilbene, 4,4'-dihydroxybiphenyl, 2,2'-dihydroxybiphenyl, 3,3',5,5'-tetramethyl-(1,1'-biphenyl)-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tri-(4 -hydroxyphenyl)methane and 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, etc.; by phenols (eg phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, Dihydroxybenzene and dihydroxynaphthalene, etc.) with aldehydes (formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, furfural, etc.), ketones (p-hydroxyacetophenone, o-hydroxyacetophenone, etc.) Or a phenol resin obtained by condensation of a diene (dicyclopentadiene, tricyclopentadiene, etc.); by the above phenols and substituted benzenes (4,4'-bis(chloromethyl)) -1,1'-biphenyl and 4,4'-bis(methoxymethyl)-1,1'-biphenyl, etc.), or substituted phenyls (1,4-bis(chloromethyl)benzene) a phenol resin obtained by polycondensation of 1,4-bis(methoxymethyl)benzene, 1,4-bis(hydroxymethyl)benzene or the like; a modification of the above phenols and/or the above phenol resin Halogenated phenols such as tetrabromobisphenol A and brominated phenol resins

(e) Other imidazoles, BF ₃ -amine complexes, anthracene derivatives

Among these other hardeners, amine compounds such as diaminodiphenylmethane, diaminodiphenylphosphonium and naphthalene diamine, and catechol and aldehydes, ketones, dienes, and substituted A hardener having a structure in which an active hydroxyl group is adjacent, such as a condensate of a benzene or a substituted phenyl group, contributes to an epoxy The arrangement of the resins is therefore preferred.

Other hardeners may be used singly or in combination. When the other curing agent is used in combination, the ratio of the phenol compound of the present invention to the total hardener component in the epoxy resin composition of the present invention is preferably 20% by mass or more, more preferably 30% by mass or more. It is preferably 70% by mass or more, and particularly preferably 100% by mass (in the case where other hardeners are not used in combination).

In the epoxy resin composition of the present invention, the amount of all the hardeners containing the phenol resin of the present invention is preferably from 0.5 to 2.0 equivalents, more preferably from 0.6 to 1.5, based on 1 equivalent of the epoxy group of the entire epoxy resin. equivalent.

In the epoxy resin composition of the present invention, a hardening accelerator may be added 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, trimethylaminomethylphenol, diazabicycloundecene, tetrabutylammonium salts, three a quaternary ammonium salt such as isopropylmethylammonium salt, trimethylsulfonium ammonium salt or cetyltrimethylammonium salt, triphenylbenzyl phosphonium salt, triphenylethyl phosphonium salt, tetrabutyl phosphonium Four grades of strontium salts such as salt (the relative ions of the fourth-order salt are halogen, organic acid ion, hydroxide ion, etc., not specifically specified, especially organic acid ions, hydroxide ions), metal compounds such as stannous octoate Wait.

The amount of the hardening accelerator used is 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.

The epoxy resin composition of the present invention may contain an inorganic filler as needed.

The inorganic filler contained in the epoxy resin composition of the present invention is not limited as long as it is well known. Specific examples of the inorganic filler include boron nitride, aluminum nitride, and tantalum nitride. Inorganic powder fillers such as tantalum carbide, titanium nitride, zinc oxide, tungsten carbide, aluminum oxide, and magnesium oxide, fibrous fillers such as synthetic fibers and ceramic fibers, and colorants. The shape of the inorganic filler may be any of powder (block, spherical), single fiber, long fiber, and the like.

The amount of the inorganic filler used in the epoxy resin composition of the present invention is usually 2 to 1000 parts by mass based on 100 parts by mass of the resin component in the epoxy resin composition. These inorganic fillers may be used alone or in combination of two or more.

In the epoxy resin composition of the present invention, various blending agents such as a decane coupling agent, a releasing agent, and a pigment, various thermosetting resins, various thermoplastic resins, and the like may be added 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. Compound, vinyl benzyl ether compound, polybutadiene and modified substance thereof, modified product of acrylonitrile copolymer, oxime resin, fluororesin, polyoxyn epoxide, polyether oximine, polyether oxime, polyphenylene ether , polyacetal, polystyrene, polyethylene, dicyclopentadiene resin, and the like. The thermosetting resin or the thermoplastic resin is usually used in an amount of 60% by mass or less in the epoxy resin composition of the present invention.

The epoxy resin composition of the present invention is 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 previously known. For example, an epoxy resin, a hardener, an optional hardening accelerator, a blending agent, various thermosetting resins, various thermoplastic resins, and the like, which are essential components of the epoxy resin composition of the present invention, are optionally used, and an extruder is used. The kneader or the roller or the like is sufficiently mixed until it becomes uniform, and the epoxy resin composition of the present invention is obtained, and the obtained composition is molded by a melt casting molding method or a transfer molding method, an injection molding method, a compression molding method, or the like. And further at its melting point Heating is carried out for 2 to 10 hours, whereby a cured product of the epoxy resin composition of the present invention can be 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 at least one of an epoxy resin and a hardener containing at least one of the epoxy resin of the present invention or the phenol resin of the present invention, and optionally having a thermal conductivity of 20 W/ A mixture is obtained from other components such as an inorganic filler such as m‧K, and the mixture is mixed with toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, cyclopentanone, N, N. '-Dimethylformamide, N,N'-dimethylacetamide, dimethyl hydrazine, N-methylpyrrolidone, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, dipropylene glycol Glycol ethers such as dimethyl ether, dipropylene glycol diethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, ethyl acetate, butyl acetate, methyl cellosolve acetate, ethyl cellosolve acetate , butyl cellosolve acetate, carbitol acetate, propylene glycol monomethyl ether acetate, dialkyl glutarate, dialkyl succinate, dialkyl adipate and other esters, γ-butyl It is obtained by mixing an organic solvent such as a cyclic ester such as a lactone, a petroleum ether, a petroleum brain, a hydrogenated petroleum brain, or a solvent naphtha. The amount of the solvent is usually 10 to 95% by mass, preferably 15 to 85% by mass based on the total varnish.

After the varnish obtained in the above manner is impregnated into a fiber substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber, and paper, the solvent is removed by heating, and the epoxy resin of the present invention is composed. The article is in a semi-hardened state, whereby the prepreg of the present invention can be obtained. In addition, the "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 may be subjected to hot press forming to obtain a cured product.

[Examples]

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 are parts by mass.

Further, the hydroxyl equivalent, the epoxy equivalent, the softening point, and the ICI melt viscosity were measured under the following conditions.

‧hydroxy equivalent

The measurement was carried out by the method described in JIS K-7236, and the unit was g/eq.

‧Epoxy equivalent

The measurement was carried out by the method described in JIS K-7236, and the unit was g/eq.

‧Softening Point

The measurement was carried out in accordance with the method according to JIS K-7234, and the unit was °C.

‧ICI melt viscosity

The measurement was carried out according to the method according to JIS K 7117-2, and the unit was Pa‧s.

Example 1 (Synthesis of phenol resin 1)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 330 parts of resorcin and 174 parts of acetone were added while being purged with nitrogen, and the mixture was dissolved under stirring, and the temperature was raised to 100 °C. 88 parts of 98% sulfuric acid was added dropwise thereto, and as a result, the reaction liquid was vigorously exothermic and raised to 125 °C. After cooling to 80 ° C at room temperature, the reaction was continued for 10 hours. Then, Dean-Stark was placed in the flask, and while dehydrating by azeotropy, the temperature was raised to 120 ° C, and the reaction was further carried out for 10 hours. After completion of the reaction, the mixture was neutralized with 10% sodium hydroxide, and 1000 parts of methyl isobutyl ketone was added to dissolve the resin. Then, water washing is performed until the washing water becomes neutral, and from the obtained solution, methyl isobutyl ketone or the like is distilled off under reduced pressure using a rotary evaporator, thereby obtaining 318 parts of the phenol resin (P1) of the present invention. . The obtained phenol resin P1 had a hydroxyl equivalent of 170 g/eq., a softening point of 146 ° C, and an ICI melt viscosity of 5.4 Pa·s. In GPC, the n=0 component was 41 area%, and the formula (1) The average value of n was 0.44, and the peak of CH ₂ carbon was not detected.

Comparative Example 1 (synthesis of phenol resin 2)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 330 parts of resorcin and 174 parts of acetone were added while being purged with nitrogen, and the mixture was dissolved under stirring, and the temperature was raised to 100 °C. 88 parts of 98% sulfuric acid was added dropwise thereto, and as a result, the reaction liquid was vigorously exothermic and raised to 125 °C. After cooling to 80 ° C at room temperature, the reaction was continued for 10 hours. After completion of the reaction, the mixture was neutralized with 10% sodium hydroxide, and 1000 parts of methyl isobutyl ketone was added to dissolve the resin. Then, the water was washed until the washing water became neutral, and from the obtained solution, methyl isobutyl ketone or the like was distilled off under reduced pressure using a rotary evaporator, whereby 342 parts of a phenol resin (P2) was obtained. The obtained phenol resin P2 had a hydroxyl equivalent of 215 g/eq., a softening point of 127 ° C, and an ICI melt viscosity of 8.0 Pa·s. In GPC, the n=0 component was 12 area%, in ¹³ C-NMR, When the peak area of CH ₃ carbon derived from acetone was set to 1, the peak area of CH ₂ carbon was 0.27.

Comparative Example 2 (synthesis of phenol resin 3)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 300 parts of resorcin, 78 parts of acetone, and 0.3 parts of p-toluenesulfonic acid were added, and the reaction was carried out at 80 ° C for 2 hours. Then, 78 parts of acetone was added, and the reaction was carried out at 80 ° C for 2 hours. Then, it was washed with pure water until the washing water became neutral, and the distillate portion was removed from the obtained solution by a rotary evaporator under reduced pressure to obtain 228 parts of a white crystalline phenol resin (P3). The obtained phenol resin P3 had a melting point of 200 ° C and a hydroxyl equivalent of 118 g / eq.

Example 2 (Synthesis of Epoxy Resin 1)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 210 parts of the phenol resin (P1) of the present invention, 462 parts of epichlorohydrin (4 moles equivalent to the phenol resin), and methanol 28 were added while performing nitrogen purge. The mixture was dissolved under stirring and heated to 70-75 °C. Then, 51.1 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further carried out at 75 ° C for 75 minutes. After completion of the reaction, the mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer by using a rotary evaporator under reduced pressure. 532 parts of methyl isobutyl ketone was added to the residue to dissolve, and the temperature was raised to 75 °C. 16.8 parts of a 30% by weight aqueous sodium hydroxide solution and 6.3 parts of methanol were 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, and the obtained solution was reduced by using a rotary evaporator. Methyl isobutyl ketone or the like was removed by distillation under reduced pressure, whereby 35 parts of the epoxy resin (E1) of the present invention was obtained. The obtained epoxy resin E1 had an epoxy equivalent of 259 g/eq., a softening point of 72 ° C, and an ICI melt viscosity of 150 ° C of 0.21 Pa·s.

Comparative Example 3 (synthesis of epoxy resin 2)

In a flask equipped with a stirrer, a reflux cooling tube, and a stirring device, 237 parts of a phenol resin (P2), 953 parts of epichlorohydrin (9.2 moles equivalent to a phenol resin), and 62 parts of methanol were added while performing nitrogen purge. Dissolve under stirring and raise the temperature to 70-75 °C. Then, 46.4 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further carried out at 75 ° C for 75 minutes. After completion of the reaction, the mixture was washed with water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer by using a rotary evaporator under reduced pressure. 570 parts of methyl isobutyl ketone was added to the residue to dissolve, and the temperature was raised to 75 °C. After stirring, 14.9 parts of a 30% by weight aqueous sodium hydroxide solution and 6.8 parts of methanol were added, and the reaction was carried out for 1 hour, and then washed with water until the washing water of the oil layer became neutral, and the obtained solution was reduced by using a rotary evaporator. Methyl isobutyl ketone or the like was removed by distillation under pressure, whereby 296 parts of an epoxy resin (E2) was obtained. The obtained epoxy resin E2 has an epoxy equivalent of 276 g/eq., and the softening point is The ICI melt viscosity at 71 ° C and 150 ° C was 0.15 Pa ‧ .

Comparative Example 4 (synthesis of epoxy resin 3)

336 parts of phenol resin (P3), 1082 parts of epichlorohydrin (4 moles equivalent to phenol resin), and 70 parts of methanol were added to a flask equipped with a stirrer, a reflux cooling tube, and a stirring device while performing nitrogen purge. Dissolve under stirring and raise the temperature to 70-75 °C. Then, 121.1 parts of flaky sodium hydroxide was added in portions over 90 minutes, and then the reaction was further carried out at 75 ° C for 75 minutes. After completion of the reaction, the mixture was washed with water, and distilled under reduced pressure using a rotary evaporator to remove excess solvent such as epichlorohydrin from the oil layer. To the residue, 950 parts of methyl isobutyl ketone was added to dissolve, and the temperature was raised to 75 °C. 39.0 parts of a 30% by weight aqueous sodium hydroxide solution and 11.4 parts of methanol were 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, and the obtained solution was reduced by using a rotary evaporator. Methyl isobutyl ketone or the like was removed by distillation under pressure, whereby 466 parts of an epoxy resin (E3) was obtained. The obtained epoxy resin E3 had an epoxy equivalent of 207 g/eq., a softening point of 79 ° C, and an ICI melt viscosity of 150 ° C of 0.57 Pa·s.

Example 3, Comparative Examples 5, 6

The blends shown in the composition column of the blend of Table 1 were uniformly mixed by a mixing roll to obtain an epoxy resin composition. This composition was pulverized, and an ingot was obtained by a tablet press. The obtained ingot was molded by a transfer molding machine to form a test piece of 10 × 4 × 90 mm. The test piece was heated at 160 ° C for 2 hours, and further heated at 180 ° C for 8 hours to carry out post-hardening.

The test piece was held vertically on the splint, and the flame of the burner was adjusted to a blue flame of 19 mm so that the central portion of the lower end of the test piece was in contact with the flame for 9.5 mm for 10 seconds. After contacting the flame, remove the burner and measure the duration of the combustion. Immediately after the flame has extinguished, the flame is exposed for 10 seconds, after which the burner is removed and the duration of the combustion is measured. The total value of the combustion time of each sample 10 times is shown in Table 1.

Further, the heat resistance (DMA) in Table 1 was measured under the following conditions.

‧heat resistance (DMA)

Dynamic viscoelasticity measuring device: TA-instruments, DMA-2980

Measuring temperature range: -30~280°C

Temperature speed: 2 ° C / min

Tg: set the peak point of Tan-δ to Tg

XLC: Phenyl aralkyl type phenol resin (Milex (trade name) XLC-3L manufactured by Mitsui Chemicals, Inc.)

TPP: Triphenylphosphine (manufactured by Pure Chemical Co., Ltd.)

Filler: molten cerium oxide filler (MSR-2212 manufactured by Longsen Co., Ltd.)

Example 4, Comparative Example 7

The components were blended in a ratio (parts) of Table 2, and kneaded and ingot by a mixing roll, and then a resin molded body was prepared by transfer molding, and heated at 160 ° C for 2 hours, and further heated at 180 ° C for 8 hours. A cured product of the epoxy resin composition of the present invention and the comparative resin composition was obtained. The results of measuring the physical properties of the hardened materials under the following conditions are shown in Table 2.

‧TMA (Thermo-Mechanical Analysis)

TMA Thermomechanical Measuring Device: TM-7000 manufactured by Vacuum Technology Co., Ltd.

Heating rate: 2 ° C / min.

‧ peel strength

According to JISK-6911

‧Water absorption and humidity

Weight increase rate (%) of a disk-shaped test piece having a diameter of 5 cm × a thickness of 4 mm after boiling for 24 hours under conditions of 100 ° C - water immersion, 85 ° C - 85%, and 121 ° C - 100%

‧ dielectric properties

Measurement at 1 GHz according to K6991

PN: Phenolic novolac (H-1 manufactured by Minghe Chemical Industry Co., Ltd.)

As is clear from the results of Table 1, the cured product of Example 3 had high flame retardancy and heat resistance with respect to Comparative Examples 5 and 6. Further, according to the results of Table 2, the epoxy resin of the present invention has high heat resistance as compared with the heat resistant resin shown in Comparative Example 7, and is excellent in low water absorbability and low dielectric properties, and thus is particularly preferably used. For electronic materials.

The present invention has been described in detail with reference to the specific embodiments thereof, and 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 patent application filed on Nov. 19, 2013 (Japanese Patent Application No. 2013-238463) and Japanese Patent Application (Japanese Patent Application No. 2014-125009) filed on Jun. All of them are invoked by reference. Again, all references cited are incorporated herein in their entirety.

[Industrial availability]

The epoxy resin composition using the phenol resin of the present invention has excellent heat resistance and flame retardancy, and therefore is suitable for electrical/electronic parts, particularly insulating materials for electric and electronic parts, structural materials, adhesives, paints, and the like. it works.

Claims (7)

a phenol resin which is represented by the following formula (1), (wherein R ₁ each independently represents an alkyl group having 1 to 6 carbon atoms; and R ₂ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms; k represents an integer of 1 to 4; and n represents 0 to 10; The integer). The phenol resin according to the first aspect of the invention, wherein the average value of n in the formula (1) constituting the molecule of the resin is 0.05 or more and 4.0 or less. The phenol resin according to the first aspect of the patent application, wherein, in the ¹³ C-NMR spectrum, when the peak area of the CH ₃ carbon derived from the ketone is set to 1, the peak area of the CH ₂ carbon is 0 or more. 0.2 or less. An epoxy resin obtained by reacting epihalohydrin with a phenol resin according to any one of claims 1 to 3. An epoxy resin composition comprising the phenol resin and epoxy resin according to any one of claims 1 to 3. An epoxy resin composition comprising the epoxy resin, the hardener, and any hardening accelerator of claim 4 of the patent application. A hardened material obtained by hardening an epoxy resin composition of claim 5 or 6.