CN118591574A

CN118591574A - Epoxy resin, polyhydroxyl resin, epoxy resin composition, cured epoxy resin, and process for producing polyhydroxyl resin

Info

Publication number: CN118591574A
Application number: CN202380018252.4A
Authority: CN
Inventors: 大村昌己; 大神浩一郎
Original assignee: Nippon Steel and Sumikin Chemical Co Ltd
Current assignee: Nippon Steel Chemical and Materials Co Ltd
Priority date: 2022-02-25
Filing date: 2023-02-09
Publication date: 2024-09-03
Also published as: WO2023162693A1; TW202340293A

Abstract

The present invention provides an epoxy resin, a polyhydroxy resin, and an epoxy resin composition using the same, which are useful for insulating materials for electric/electronic parts, are excellent in handleability as a solid at ordinary temperature, and are excellent in low viscosity and solvent solubility at the time of molding, and a cured product obtained therefrom and having high thermal conductivity and high heat resistance. An epoxy resin is represented by the following general formula (1). (wherein A represents an aromatic group comprising a benzene ring, a biphenyl ring or a naphthalene ring, G represents a glycidyl group, R independently represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 3 to 10.)

Description

Epoxy resin, polyhydroxyl resin, epoxy resin composition, cured epoxy resin, and process for producing polyhydroxyl resin

Technical Field

The present invention relates to an epoxy resin, a polyhydric hydroxyl resin, an epoxy resin composition, and a cured epoxy resin and a method for producing a polyhydric hydroxyl resin, and more particularly to an epoxy resin, a polyhydric hydroxyl resin, and an epoxy resin composition which are useful as an insulating material for electric/electronic parts such as semiconductor sealing, laminated boards, and heat dissipating substrates, and which are solid at ordinary temperature, have low viscosity at molding, and are excellent in solvent solubility. Further, the present invention relates to an epoxy resin cured product having excellent high thermal conductivity, heat resistance and low thermal expansion properties, which is obtained by curing the epoxy resin cured product using the epoxy resin cured product. Further, the present invention relates to a method for producing the polyhydroxyresin.

Background

Epoxy resins have been used in a wide variety of industrial applications, but in recent years, their required properties have been gradually increasing. In the fields of electric/electronic and power electronics (power electronics) in which electronic circuits have been developed to have higher densities and higher frequencies, heat dissipation of an epoxy resin composition used for an insulating part is a problem because heat generation from the electronic circuits is increased. The heat dissipation property has been dealt with by the thermal conductivity of the filler, but further higher integration is demanded to improve the thermal conductivity of the epoxy resin itself as a matrix.

As an epoxy resin composition having excellent high thermal conductivity, an epoxy resin composition using an epoxy resin having a mesogen structure is known, and for example, patent document 1 discloses an epoxy resin composition containing a bisphenol type epoxy resin and a polyhydric phenol resin curing agent as essential components, and discloses that the epoxy resin composition has excellent stability and strength at high temperature and can be used in a wide range of fields such as adhesion, casting, sealing, molding, lamination and the like. Patent document 2 discloses an epoxy compound having two mesogenic structures connected by a bent chain in a molecule. Further, patent document 3 discloses a resin composition containing an epoxy compound having a mesogen group.

However, the epoxy resin having such a mesogen structure has a high melting point, and when the mixing treatment is performed, the high melting point component is difficult to dissolve, and a dissolution residue is generated, so that there is a problem that the hardenability or heat resistance is lowered. In addition, high temperatures are required to uniformly mix such epoxy resins with hardeners. At high temperatures, the curing reaction of the epoxy resin proceeds rapidly and the gelation time becomes short, so that there is a problem that the mixing process is severely limited and difficult to handle. In order to overcome this disadvantage, a third component having good solubility is added, so that the melting point of the resin is lowered and the resin is easily and uniformly mixed, but the cured product thereof has a problem of lowering the thermal conductivity.

As a high heat conductive resin capable of melt mixing treatment, patent document 4 discloses an epoxy resin obtained by epoxidizing a mixture of hydroquinone and 4,4' -dihydroxybiphenyl, and patent document 5 discloses an epoxy resin obtained by epoxidizing a mixture of 4,4' -dihydroxydiphenylmethane and 4,4' -dihydroxybiphenyl. However, these resins lack solvent solubility and limited application uses. Patent document 6 discloses an epoxy resin composition having a diphenyl ether structure, but the curing agent is limited, and the thermal conductivity and heat resistance of a general curing agent such as phenol novolac are insufficient.

On the other hand, a calixarene compound is known as a cyclic compound as a structure exhibiting strong crystallinity, but low solvent solubility is a problem. Patent document 7 discloses a resin composition obtained by mixing a resorcinol-aldehyde polycondensate with an epoxy resin, but the use of the resin composition as a curing agent is limited, and the heat resistance of the cured product is 210 ℃ or lower. Patent document 8 discloses a resin containing a naphthalene-containing cyclic compound, but the content of the cyclic compound is low and the effect of thermal stabilization is insufficient.

Prior art literature

Patent literature

Patent document 1: japanese patent laid-open No. 7-90052

Patent document 2: japanese patent laid-open No. 9-118673

Patent document 3: japanese patent laid-open No. 11-323162

Patent document 4: WO2009/110424

Patent document 5: japanese patent laid-open publication No. 2010-43245

Patent document 6: japanese patent application laid-open No. 2012-17405

Patent document 7: japanese patent laid-open No. 2001-106868

Patent document 8: japanese patent laid-open publication No. 2012-201798

Disclosure of Invention

Problems to be solved by the invention

Accordingly, an object of the present invention is to solve the above-mentioned problems, and to provide an epoxy resin, a polyhydroxyl resin, and an epoxy resin composition using the same, which are useful for insulating materials for electric/electronic parts such as semiconductor sealing, laminated boards, heat dissipating substrates, etc. having excellent reliability, are excellent in handleability as a solid at ordinary temperature, and have low viscosity and excellent solvent solubility at the time of molding, and to provide a cured product having high thermal conductivity and high heat resistance obtained therefrom, and to provide a method for producing a polyhydroxyl resin as a raw material thereof.

Technical means for solving the problems

The present inventors found through diligent studies that: the present invention has been accomplished in view of the above problems, and has been accomplished by the present invention as a result of the foregoing problems, which have been solved by an epoxy resin composition comprising a specific epoxy resin and/or a polyhydric hydroxyl resin, and which has excellent thermal conductivity and heat resistance of a cured product thereof.

Namely, the present invention relates to an epoxy resin represented by the following general formula (1).

[ Chemical 1]

(Wherein A represents an aromatic group comprising a benzene ring, a biphenyl ring or a naphthalene ring, G represents a glycidyl group, R independently represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 3 to 10.)

The epoxy resin of the present invention is preferably an epoxy resin represented by the following general formula (2).

[ Chemical 2]

(Wherein G represents a glycidyl group, R represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 3 to 10.)

The present invention also relates to a polyhydric hydroxyl resin represented by the following general formula (3).

[ Chemical 3]

(Wherein R independently represents a hydrocarbon group having 1 to 10 carbon atoms and n represents a number of 3 to 10.)

The present invention is also an epoxy resin composition comprising the epoxy resin as an essential component and/or the polyhydric resin as an essential component as a curing agent, and is an epoxy resin cured product obtained by curing the epoxy resin composition.

The present invention also relates to a method for producing a polyhydroxyl resin represented by the general formula (3), which is obtained by reacting hydroquinone represented by the following formula (4) with an aldehyde represented by the following formula (5) and/or formula (6) in the presence of a strong acid.

[ Chemical 4]

[ Chemical 5]

(Wherein R represents a hydrocarbon group having 1 to 10 carbon atoms.)

[ Chemical 6]

(Wherein R represents a hydrocarbon group having 1 to 10 carbon atoms.)

ADVANTAGEOUS EFFECTS OF INVENTION

The epoxy resin and the polyhydric hydroxyl resin as the hardener of the present invention have good melt-kneading property at 100 ℃ or lower and excellent solvent solubility, and therefore are suitable for use in epoxy resin compositions for lamination, molding, casting, adhesion and other applications, and cured products thereof. The cured product is also excellent in heat resistance, thermal decomposition stability, and thermal conductivity, and is therefore suitable for sealing of electric/electronic parts and circuit board materials.

Drawings

FIG. 1 is an FD-MS spectrum of the phenolic compound (polyhydroxyresin) obtained in example 1.

FIG. 2 is a GPC chart of the phenolic compound (polyhydroxy resin) obtained in example 1.

FIG. 3 is the FD-MS spectrum of the epoxy resin obtained in example 2.

FIG. 4 is a GPC chart of the epoxy resin obtained in example 2.

Detailed Description

The present invention will be described in detail below.

The epoxy resin of the present invention is represented by the general formula (1), wherein A represents an aromatic group containing a benzene ring, a biphenyl or a naphthalene ring. A may be mixed in plural. G represents a glycidyl group. R independently represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 3 to 10. As shown by the "independent" mentioned above, the epoxy resin of formula (1) of the present invention can be a mixture having a different structure a. n is a repetition number (number average) and represents a number of 3 to 10. Preferably a mixture of components having different values of n.

The epoxy resin of the present invention may be a mixture with a linear epoxy resin represented by the following general formula (7). The linear component is preferably 60% or less, more preferably 40% or less. When the amount of the linear component is large, the heat resistance tends to be low.

[ Chemical 7]

(Wherein A represents an aromatic group comprising a benzene ring, a biphenyl ring or a naphthalene ring, G represents a glycidyl group, R independently represents a hydrocarbon group having 1 to 10 carbon atoms, and m represents a number of 0 to 15)

In the general formula (1) or the general formula (7), R independently represents a hydrocarbon group having 1 to 10 carbon atoms. R may be a mixture of hydrocarbons of different carbon numbers. R may be chain-shaped only or aromatic, and if it is chain-shaped only, the higher the carbon number, the better the solvent solubility, but the heat resistance tends to be lowered. In particular, for heat resistance, a hydrocarbon group having 7 or less carbon atoms is preferable. Further preferably 1 to 4 carbon atoms. When R contains an aromatic group, the heat resistance is excellent, but the solvent solubility tends to be low.

The epoxy resin of the present invention is preferably a structure represented by the general formula (2). The substitution position of the glycidyl group is preferably para. In the case of the meta resorcinol type, the glycidyl groups of the cyclic compounds are close, and there is a concern that the reaction is difficult to control in terms of the steric structure. On the other hand, in the case of para-hydroquinone type, a stable structure capable of controlling the reaction can be obtained, and a cured product having high heat resistance can be obtained. In addition, the structure of a in the general formula is preferably biphenyl or naphthalene ring in terms of heat resistance, and is preferably benzene ring in terms of solvent solubility.

The softening point of the epoxy resin of the present invention or the mixture thereof with the epoxy resin represented by the general formula (7) which may be optionally contained is preferably 130 ℃ or lower. If the temperature is higher than 130 ℃, the melt-kneading property is lowered, and if the resin composition has crystallinity, the solvent solubility is further lowered.

The method for producing the epoxy resin of the present invention is not particularly limited, and the epoxy resin can be produced by reacting a phenolic compound (polyhydroxy resin) having a cyclic structure represented by the following formula (8) with epichlorohydrin. The reaction may be carried out in the same manner as in the usual epoxidation reaction.

[ Chemical 8]

(Wherein A represents an aromatic group comprising a benzene ring, a biphenyl ring or a naphthalene ring, R each independently represents a hydrocarbon group having 1 to 10 carbon atoms, and n represents a number of 3 to 10)

As described above, the phenolic compound of formula (8) is preferably a hydroquinone type having a para-position hydroxyl group, and in order to obtain the epoxy resin represented by formula (2), a is more preferably a benzene ring as in formula (3).

The reaction of the phenolic compound of formula (8) with epichlorohydrin may be carried out, for example, by the following method: a method comprising dissolving a phenolic compound in an excess of epichlorohydrin, and then reacting the resulting mixture at 50 to 150℃and preferably 60 to 100℃for 1 to 10 hours in the presence of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide. The amount of the alkali metal hydroxide to be used in this case is in the range of 0.8 to 2.0 mol, preferably 0.9 to 1.5 mol, based on 1 mol of the hydroxyl groups in the phenolic compound. The epichlorohydrine is used in an excessive amount relative to the hydroxyl groups in the phenolic compound, and is usually 1.5 to 15 moles relative to 1 mole of the hydroxyl groups in the phenolic compound. After the completion of the reaction, excess epichlorohydrin is distilled off, the residue is dissolved in a solvent such as toluene or methyl isobutyl ketone, and the solvent is distilled off after filtration and washing with water to remove inorganic salts, whereby the target epoxy resin can be obtained.

When a phenolic compound containing a linear polyhydric hydroxyl resin represented by the general formula (9) is used as a raw material, the epoxy resin of the present invention is obtained as a mixture with the epoxy resin represented by the general formula (7).

[ Chemical 9]

(Wherein A, R, m has the same meaning as the above formula (7)

The purity of the epoxy resin of the present invention, particularly the amount of hydrolyzable chlorine, is preferably low in terms of improving the reliability of electronic parts to be used. Although not particularly limited, it is preferably 1000ppm or less, and more preferably 500ppm or less. The hydrolyzable chlorine amount in the present invention is a value measured by the following method. Specifically, the sample was dissolved in 30ml of dioxane, 1N-KOH 10ml was added thereto, the mixture was refluxed by boiling for 30 minutes, cooled to room temperature, and 100ml of 80% acetone water was further added thereto, and the solution was subjected to potential difference titration with 0.002N-AgNO ₃ aqueous solution.

Here, the phenolic compound represented by the formula (8) is not limited, and can be obtained, for example, by the following method: aldehydes such as acetaldehyde, propionaldehyde, n-butyraldehyde, paraldehyde (paraldehyde), benzaldehyde, 4-methylbenzaldehyde, 3-methylbenzaldehyde, 2-methylbenzaldehyde, 4-ethylbenzaldehyde, 2, 4-dimethylbenzaldehyde, 3, 4-dimethylbenzaldehyde, 4-isopropylbenzaldehyde, 4-tert-butylbenzaldehyde are condensed with a phenol compound such as hydroquinone, catechol, resorcinol, 4 '-biphenol, 2' -biphenol, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 4-dihydroxynaphthalene, 2, 5-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 2, 8-dihydroxynaphthalene in the presence of an organic acid or an inorganic acid (for example, refer to the methods described in Olde chemical journal (ALDRICHIMICA ACTA, page 1. 1995,3, et cetera).

As the aldehydes, various mixtures can be used, but in terms of heat resistance and solvent solubility, it is preferable that the acetaldehyde having R as a methyl group or the paraldehyde of trimer be 50% or more of the total aldehydes in terms of the molar ratio of acetaldehyde charged.

The molar ratio of the phenolic compound to the condensing agent for the aldehyde is not particularly limited, but is preferably 0.3 to 1.2 mol, more preferably 0.5 to 1.0 mol, based on 1 mol of the phenolic compound. In the case where the aldehyde is a multimeric aldehyde, the molar amount of the multimer is preferably multiplied by the polymerization degree of the multimer to satisfy the range of the molar amount. For example, since 1 mole of paraldehyde is 3 moles in terms of acetaldehyde, when paraldehyde is used, the use of 0.1 to 0.4 mole relative to 1 mole of phenolic compound is a preferable range.

The catalyst is not particularly limited as long as the reaction proceeds, and known catalyst species such as inorganic acids and organic acids can be used. Specific examples thereof include hydrobromic acid, hydrochloric acid, sulfuric acid, phosphoric acid, oxalic acid, trifluoroacetic acid, p-toluenesulfonic acid, methanesulfonic acid, boron trifluoride and the like. Hydrochloric acid and sulfuric acid are particularly preferred as the strong acid.

The amount of the catalyst is preferably 0.1 to 30.0% by mass, more preferably 1.0 to 10.0% by mass, based on the phenolic compound. If the amount of the catalyst is less than the lower limit of the above range, the reaction rate tends to be low, and if it exceeds the upper limit, the reaction control tends to be difficult.

The reaction solvent is not particularly limited, but is preferably water or a hydrocarbon solvent. Examples of the hydrocarbon solvent include n-hexane, cyclohexane, toluene, and the like. The reaction solvent may be used alone or in combination of two or more.

The reaction temperature of the phenolic compound and the aldehyde is preferably 20 to 150 ℃, more preferably 60 to 110 ℃. If the reaction temperature is less than the lower limit of the above range, the reaction tends to be slow, and if it exceeds the upper limit, the reaction control tends to be difficult.

The reaction product precipitated by the reaction between the phenolic compound and the aldehyde can be recovered by a known solid-liquid separation treatment such as filtration. After the recovery, washing with water, purification, recrystallization, and the like may be performed as needed.

In the phenolic compound represented by the formula (8), in order to produce the polyhydroxyl resin represented by the general formula (3), the aldehyde represented by the general formula (5) and/or the aldehyde represented by the general formula (6) is preferably reacted with the hydroquinone represented by the formula (4). More preferably, acetaldehyde and/or paraldehyde in which R is methyl in the formulae (5) and/or (6) are used, and the conditions are as described above.

In the epoxy resin of the present invention, other epoxy resins having two or more epoxy groups in the molecule may be used as the epoxy resin component in addition to the epoxy resin of the formula (1) or any epoxy resin of the formula (7) used as the essential component. Examples of the compounds include bisphenol A, bisphenol F, 3',5,5' -tetramethyl-4, 4' -dihydroxydiphenylmethane, 4' -dihydroxydiphenylsulfone, 4' -dihydroxydiphenylsulfide, 4' -dihydroxydiphenylketone, fluorenebisphenol, 4' -biphenol, 3', dihydric phenols such as 5,5' -tetramethyl-4, 4' -dihydroxybiphenyl, 2' -biphenol, resorcinol, catechol, t-butylcatechol, t-butylhydroquinone, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 4-dihydroxynaphthalene, 2, 5-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 2, 8-dihydroxynaphthalene, allylated or polyallylated product of the dihydroxynaphthalene, allylated bisphenol A, allylated bisphenol F, and allylated phenol novolac or phenols of three or more types such as phenol novolak, bisphenol A novolak, orthocresol novolak, metacresol novolak, p-cresol novolak, xylenol novolak, poly-p-hydroxystyrene, tris- (4-hydroxyphenyl) methane, 1, 2-tetrakis (4-hydroxyphenyl) ethane, flutriamine (fluoroglycinol), pyrogallol, t-butylpyrogallol, allylated pyrogallol, polyallylated pyrogallol, 1,2, 4-benzene triol, 2,3, 4-trihydroxybenzophenone, phenol aralkyl resin, naphthol aralkyl resin, dicyclopentadiene resin, etc, or glycidyl etherate derived from halogenated bisphenol such as tetrabromobisphenol A. These epoxy resins may be used singly or in combination of two or more.

The epoxy resin composition of the present invention may contain any of the components described below in addition to the epoxy resin and the hardener. In this case, the epoxy resin composition of the present invention preferably uses the epoxy resin represented by the general formula (1) and/or the polyhydroxy resin represented by the general formula (8) as a hardener, and more preferably uses the general formula (3).

In the case of using the epoxy resin composition represented by the general formula (1), the blending ratio of the epoxy resin of the general formula (1) is preferably 30wt% or more, more preferably 50wt% or more of the total epoxy resin. If the amount is less than the above, the effect of improving the physical properties such as heat resistance in the production of a cured product may be reduced.

In the case of an epoxy resin composition using an epoxy resin represented by the general formula (1), as the curing agent, all curing agents generally known as curing agents for epoxy resins can be used, and dicyandiamide, acid anhydrides, polyhydric phenols, aromatic amines, aliphatic amines, and the like are used. Among these, in the field where high electrical insulation is required for a semiconductor sealing material or the like, polyhydric phenols are preferably used as a curing agent. In addition, as the hardening agent having excellent high thermal conductivity, dihydric phenols are preferably used. Specific examples of the curing agent are shown below.

Examples of the polyhydric phenols include dihydric phenols such as bisphenol a, bisphenol F, bisphenol S, fluorene bisphenol, 4 '-biphenol, 2' -biphenol, hydroquinone, resorcinol, and naphthalene diol, and ternary or higher phenols such as tris- (4-hydroxyphenyl) methane, 1, 2-tetrakis (4-hydroxyphenyl) ethane, phenol novolak, o-cresol novolak, naphthol novolak, and polyvinyl phenol. Further, there are polyhydric phenol compounds synthesized by condensing phenols such as phenols, naphthols, bisphenol a, bisphenol F, bisphenol S, fluorene bisphenol, 4 '-biphenol, 2' -biphenol, hydroquinone, resorcinol, naphthalene diol and the like with condensing agents such as formaldehyde, acetaldehyde, benzaldehyde, parahydroxybenzaldehyde, paraxylylene glycol and the like.

Examples of the acid anhydride hardener include phthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylbicycloheptenedicarboxylic anhydride (METHYL HIMIC ANHYDRIDE), dodecenyl (dodecynyl) succinic anhydride, nadic anhydride (NADIC ANHYDRIDE), and trimellitic anhydride.

Examples of the amine-based curing agent include aromatic amines such as 4,4' -diaminodiphenylmethane, 4' -diaminodiphenylpropane, 4' -diaminodiphenylsulfone, m-phenylenediamine, and p-xylylenediamine, aliphatic amines such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine.

In the epoxy resin composition, one or a mixture of two or more of these hardeners may be used.

The blending ratio of the epoxy resin to the hardener is preferably in the range of 0.8 to 1.5 in terms of equivalent ratio of the epoxy group to the functional group in the hardener. If the amount is outside the above range, unreacted epoxy groups or functional groups in the curing agent remain after curing, and the reliability of the sealing function is lowered, which is not preferable.

The epoxy resin composition of the present invention is not limited to the above formula (1) if the polyhydric hydroxyl resin represented by the above formula (8) (preferably the formula (3)) is used as the hardener. The epoxy resin used in this case is not limited to any particular one, but is preferably an epoxy resin having a divalent rigid structure in terms of heat resistance and thermal conductivity, examples thereof include glycidyl ethers derived from 4,4' -dihydroxydiphenyl sulfone, 4' -dihydroxydiphenyl sulfide, 4' -dihydroxydiphenyl ketone, 4' -dihydroxydiphenyl ether, 4' -biphenol, 2' -biphenol, hydroquinone, resorcinol, catechol, 1, 2-dihydroxynaphthalene, 1, 3-dihydroxynaphthalene, 1, 4-dihydroxynaphthalene, 1, 5-dihydroxynaphthalene, 1, 6-dihydroxynaphthalene, 1, 7-dihydroxynaphthalene, 1, 8-dihydroxynaphthalene, 2, 3-dihydroxynaphthalene, 2, 4-dihydroxynaphthalene, 2, 5-dihydroxynaphthalene, 2, 6-dihydroxynaphthalene, 2, 7-dihydroxynaphthalene, 2, 8-dihydroxynaphthalene, more preferred are glycidyl ether compounds derived from 4,4' -dihydroxydiphenyl ketone, 4' -dihydroxydiphenyl ether, 4' -biphenol and hydroquinone. In this case, the blending ratio of the polyhydric hydroxyl resin represented by the general formula (8) (preferably the general formula (3)) as the hardener is preferably 20wt% or more, more preferably 50wt% or more of the total hardener. If the amount is less than the above, the effect of improving the physical properties such as heat resistance in the production of a cured product may be reduced.

The epoxy resin composition of the present invention may be suitably formulated with an oligomer or polymer compound such as polyester, polyamide, polyimide, polyether, polyurethane, petroleum resin, indene/coumarone resin, phenoxy resin, or the like as another modifier. The amount of the additive is usually in the range of 1 to 30 parts by weight based on 100 parts by weight of the total resin components.

The epoxy resin composition of the present invention may contain additives such as inorganic fillers, pigments, flame retardants, shaking property imparting agents, coupling agents, and fluidity improving agents. Examples of the inorganic filler include silica powder such as spherical or crushed fused silica and crystalline silica, alumina powder, glass powder, mica, talc, calcium carbonate, alumina, and alumina hydrate, and the amount of the inorganic filler blended in the case of using the inorganic filler for a semiconductor sealing material is preferably 70 wt% or more, and more preferably 80 wt% or more.

Examples of pigments include organic or inorganic extender pigments and flake pigments. As the shaking property imparting agent, there may be mentioned: silicon-based, castor oil-based, aliphatic amide wax, oxidized polyethylene wax, organobentonite-based, and the like.

The epoxy resin composition of the present invention may optionally contain a hardening accelerator. Examples thereof include amines, imidazoles, organic phosphines, lewis acids, and the like, and specifically: and quaternary substituted phosphonium/tetra-substituted borates such as 1, 8-diazabicyclo (5, 4, 0) undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol, and the like, and tetraphenylboron salts such as 2-methylimidazole, 2-phenylimidazole, 2-ethyl-4-methylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole, and the like, tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphines, tetraphenylphosphonium/tetraphenylborates, tetraphenylphosphonium/ethyltriphenylborates, tetrabutylphosphonium/tetrabutylborate, and the like, and 2-ethyl-4-methylimidazole/tetraphenylborate, and N-methylmorpholine/tetraphenylborate, and the like. The amount of the additive is usually in the range of 0.01 to 5 parts by weight based on 100 parts by weight of the total resin components.

Further, as necessary, a releasing agent such as carnauba wax or OP wax, a coupling agent such as γ -glycidoxypropyl trimethoxysilane, a coloring agent such as carbon black, a flame retardant such as antimony trioxide, a low stress agent such as silicone oil, a lubricant such as calcium stearate, and the like are used in the epoxy resin composition of the present invention.

The epoxy resin composition of the present invention can be prepared into a prepreg by impregnating a fibrous material such as a glass cloth, a aramid nonwoven fabric, or a polyester nonwoven fabric such as a liquid crystal polymer with an organic solvent-dissolved varnish, and then removing the solvent. In addition, a laminate may be formed by coating a sheet-like material such as copper foil, stainless steel foil, polyimide film, or polyester film, as the case may be.

The epoxy resin composition of the present invention can be cured by heating to obtain a cured resin product of the present invention. The cured product can be obtained by molding the epoxy resin composition by casting, compression molding, transfer molding, or the like. The temperature at this time is usually in the range of 120℃to 220 ℃. The heat resistance may exhibit a Tg of 250℃or higher, and may exhibit a Tg of 300℃or higher. The cured product of the present invention has a specific heat resistance as compared with a typical cured epoxy resin having a Tg of about 250 ℃. In addition, although it is difficult to achieve both the electric leakage resistance because the carbon residue is high and the carbonized layer is easily formed in the cured product having high heat resistance, it is difficult to form the carbonized layer because the carbon residue is low, suggesting that the electric leakage resistance or the voltage resistance is excellent. Therefore, the present invention is expected to be applied to the field of electronic materials, particularly, power devices and vehicle-mounted applications requiring heat resistance, electronic materials used under high voltage, and the like.

Examples

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples. The present invention is not limited to these. Unless otherwise specified, "parts" means parts by weight and "%" means% by weight. The measurement methods were each measured by the following methods.

1) Epoxy equivalent weight

A potential difference titration apparatus was used, methyl ethyl ketone was used as a solvent, tetraethylammonium bromide acetic acid solution was added, and the measurement was performed by the potential difference titration apparatus using a 0.1mol/L perchloric acid-acetic acid solution.

2) OH equivalent

1, 4-Dioxane was used as a solvent by using a potential difference titration apparatus, acetyl chloride was obtained by using 1.5mol/L, excess acetyl chloride was decomposed by using water, and titration was performed by using 0.5mol/L potassium hydroxide.

3) Melting point

The peak temperature of differential scanning calorimeter (DIFFERENTIAL SCANNING calometer, DSC) was determined by using a differential scanning calorimeter (manufactured by Seiko electronic nanotechnology (SII Nano Technology) Co., ltd.) at a temperature rise rate of 5℃per minute (EXSTAR) 6000 DSC/6200). That is, the DSC peak temperature is taken as the melting point of the resin.

4) Melt viscosity

The measurement was performed at 150℃using a CAP2000H type rotational viscometer manufactured by Brookfield (BROOKFIELD).

5) Softening point of

The measurement was carried out by the ring and ball method according to Japanese Industrial Standard (Japanese Industrial Standards, JIS) -K-2207.

6) GPC measurement

The body (manufactured by Tosoh Co., ltd., HLC-8220 GPC) was a device comprising a column (manufactured by Tosoh Co., ltd., TSKgel SuperMultiporeHZ-N4) connected in series, and the column temperature was set at 40 ℃. In addition, tetrahydrofuran (THF) was used for the eluent, and a differential refractive index detector was used for the detector at a flow rate of 0.35 mL/min. The measurement sample was obtained by dissolving 0.1g of the sample in 10mL of THF in 50. Mu.L and filtering the solution by a microfilter (microfilter). The data were processed using GPC-8020 model II version 6.00 manufactured by Tosoh Co., ltd.

7) Glass transition point (Tg)

Dynamic viscoelasticity was measured under a nitrogen flow at a temperature rise rate of 3 ℃/min and 10Hz by using a thermo-mechanical measuring device (manufactured by Seiko electronic nanotechnology (SII Nano Technology) Co., ltd., erst (EXSTAR) DMS 6100), and the peak value of tan delta was taken as the glass transition temperature.

8) 5% Weight reduction temperature (Td 5), residual carbon ratio

The 5% weight reduction temperature (Td 5) was measured under a nitrogen atmosphere at a temperature rise rate of 10 ℃/min using a thermogravimetric/differential thermal analysis device (manufactured by smart electronic nanotechnology (SII Nano Technology), EXSTAR DMA 7300). The weight loss at 700℃was measured and calculated as the residual carbon content.

9) Thermal conductivity

The thermal conductivity was measured by a transient hot wire method (TRANSIENT HOT WIRE METHOD) using an LFA447 type thermal conductivity meter manufactured by the relaxation resistance (NETZSCH).

10 Melt-kneading property)

Melt-kneading property at 100℃was confirmed. Let o: can mix, delta: difficult to mix, x: with unmelted components.

11 Solvent solubility)

2G of the resin composition and 2g of methyl ethyl ketone were weighed into a sample bottle, and after the mixture was heated and dissolved, the temperature was gradually lowered in a constant temperature bath, and the temperature in the bath in which the resin was deposited was measured.

The precipitation temperature was set to 25 ℃ or lower as o, 26 ℃ or higher but less than 60 ℃ as delta, and 60 ℃ or higher as x.

12 Field Desorption ionization mass spectrometry (Field Desorption-Mass Spectrometry, FD-MS)

The measurement was performed using a mass spectrometer JMS-T100GCV (manufactured by Japanese electronics Co.). The sample was dissolved in acetone for measurement.

Example 1

A2L four-necked separable flask including a thermometer, a stirrer, a cooling tube and a Dean-Stark tube was charged with 110.0g of hydroquinone, 16.0g of 36% hydrochloric acid and 220.0g of water, and the mixture was stirred under a nitrogen stream while heating to 90℃to obtain 32.4g of n-butyraldehyde and 19.8g of paraldehyde, and the mixture was reacted for 6 hours while being dehydrated under reflux. After cooling to room temperature, filtration, neutralization, washing with water and drying under reduced pressure were repeated, whereby 102g of a pale yellow solid phenolic compound (hardener a) was obtained. The hardener a has an OH equivalent of 70g/eq and a number average molecular weight of 1200. The FD-MS spectrum of the obtained phenolic compound is shown in FIG. 1, and the GPC chart is shown in FIG. 2. In fig. 1, the cyclic compound of n=4 (only r=ch ₃ is 544, r=ch ₃/CH₂CH₂CH₃ =1/3 is 573, r=ch ₃/CH₂CH₂CH₃ =2/2 is 600) and the cyclic compound of n=5 (only r=ch ₃ is 680, r=ch ₃/CH₂CH₂CH₃ =1/4 is 708, and r=ch ₃/CH₂CH₂CH₃ =2/3 is 736) of the general formula (3) were confirmed.

Example 2

The reaction was carried out in the same manner as in example 1 except that n-butyraldehyde was not used and the amount of paraldehyde used was 39.6g, to obtain 98g of a phenolic compound. The phenolic compound obtained had an OH equivalent of 70g/eq and a number average molecular weight of 1200.

Next, 25.0g of the obtained phenolic compound, 500g of epichlorohydrin and 100g of diethylene glycol dimethyl ether were charged into a 1L four-necked separable flask, and 32.4g of a 48% aqueous sodium hydroxide solution was added dropwise thereto at 65℃under reduced pressure (about 130 Torr) over 3 hours. During this time, the water produced was removed from the system by azeotropy with epichlorohydrin, and the distilled epichlorohydrin was returned to the system. After the completion of the dropwise addition, the reaction was continued for 1 hour and dehydration was performed. After the completion of the reaction, 34.0g of an epoxy resin (epoxy resin a) was obtained as a pale yellow solid by filtration and drying under reduced pressure. The softening point of the obtained epoxy resin A was 101 ℃, the epoxy equivalent was 155g/eq, and the number average molecular weight was 1600. The FD-MS spectrum of the obtained epoxy resin is shown in fig. 3, and the GPC diagram is shown in fig. 4. M/z=992, 1240, 1489, which are the main peaks of fig. 3, correspond to the cyclic compounds of the general formula (2) r=ch ₃, n=4, 5, 6, respectively.

Example 3

A reaction was carried out in the same manner as in example 1 except that the amount of n-butyraldehyde used was 13.0g and the amount of paraldehyde used was 31.7g, to obtain 91g of a phenolic compound. The phenolic compound obtained had an OH equivalent of 75g/eq and a number average molecular weight of 1290. 25.0g of the obtained phenolic compound was epoxidized in the same manner as in example 2 to obtain 34.0g of an epoxy resin (epoxy resin B) as a pale yellow solid. The softening point of the obtained epoxy resin B was 69 ℃, the epoxy equivalent was 160g/eq, and the number average molecular weight was 1660.

Comparative example 1

A flask equipped with a dean-Stark tube was charged with 300.0g of hydroquinone, 28.9g of p-formaldehyde and 263.1g of diethylene glycol dimethyl ether, and dissolved by heating to about 100℃under stirring under a nitrogen stream. Then, 0.33g of p-toluenesulfonic acid was added thereto, and the mixture was heated to 160℃and reacted for 6 hours while dehydrating the mixture to give a phenolic compound. Diethylene glycol dimethyl ether was distilled off, methyl isobutyl ketone was added thereto, followed by neutralization, washing with water, filtration, and then methyl isobutyl ketone was distilled off under reduced pressure to obtain 295g of a phenolic compound (hardener b). The hardener b has an OH equivalent of 75g/eq, a number average molecular weight of 1500 and a softening point of 80 ℃.

Comparative example 2

The reaction was carried out in the same manner as in example 1 except that instead of using n-butyraldehyde, the amount of paraldehyde was 39.6g and resorcinol was 110.0g instead of hydroquinone, to obtain 105g of a white solid phenolic compound (hardener c). The hardener c has an OH equivalent of 73g/eq and a melting point of 300 ℃ or higher.

Further, when the obtained phenolic compound was subjected to epoxidation in the same manner as in example 2, the obtained phenolic compound had self-polymerizability, and the reaction was difficult to control and could not be synthesized.

Examples 4 to 6 and comparative examples 3 to 7

Epoxy resin A obtained in example 2, epoxy resin B obtained in example 3, epoxy resin C (o-cresol novolak type epoxy resin, YDCN-700-3, epoxy equivalent 200g/eq., softening point 65 ℃ C., manufactured by Nitro iron chemical & materials) and epoxy resin D (4, 4 '-dihydroxydiphenyl ether type epoxy resin, epoxy equivalent 163g/eq.; YSLV-80DE, manufactured by Nitro iron chemical & materials) were used as epoxy resin components, and hardener a obtained in example 1, hardener B obtained in comparative example 1, hardener C obtained in comparative example 2, and hardener D (4, 4' -dihydroxydiphenyl ether, OH equivalent 101 g/eq.; manufactured by Tokyo chemical industry) were used as hardeners, and triphenylphosphine was used as a hardening accelerator, and the formulation shown in Table 1 was used to obtain an epoxy resin composition. The values in the table represent parts by weight in the formulation. The epoxy resin composition was molded at 175℃and cured at 175℃for 5 hours to obtain a cured product test piece, which was subjected to various physical property measurements. In comparative example 7 alone, the resin composition was dissolved in 30g of cyclohexanone by heating, and cured while applying a pressure of 15 minutes at 130℃and 2MPa for 80 minutes at 250℃under reduced pressure by vacuum pressing, and the resulting material was subjected to physical property evaluation.

TABLE 1

From these results, it is clear that the epoxy resin obtained in examples is excellent in melt-kneading property and solvent solubility, and the cured product thereof is excellent in thermal stability and thermal conductivity, and therefore, is suitable for power devices and vehicle-mounted applications.

Claims

1. An epoxy resin is represented by the following general formula (1);

[ chemical 1]

2. The epoxy resin according to claim 1, which is represented by the following general formula (2);

[ chemical 2]

3. A polyhydroxyl resin represented by the following general formula (3);

[ chemical 3]

4. An epoxy resin composition comprising an epoxy resin and a hardener, characterized in that the epoxy resin according to claim 1 is used as an essential component.

5. An epoxy resin composition comprising an epoxy resin and a hardener, wherein the epoxy resin composition comprises the polyhydroxyl resin according to claim 3 as an essential component as a part or all of the hardener.

6. An epoxy resin cured product obtained by curing the epoxy resin composition according to claim 4 or 5.

7. A method for producing a polyhydroxyresin represented by the general formula (3) above, characterized by comprising the steps of,

The hydroquinone represented by the following formula (4) and the aldehyde represented by the following formula (5) and/or formula (6) are reacted in the presence of a strong acid.

[ Chemical 4]

[ Chemical 5]

(Wherein R represents a hydrocarbon group having 1 to 10 carbon atoms.)

[ Chemical 6]

(Wherein R represents a hydrocarbon group having 1 to 10 carbon atoms).