JP5581180B2 - Epoxy resin composition having fluorene skeleton and cured product thereof - Google Patents

Description

  The present invention relates to a curable composition (epoxy resin composition) containing an epoxy compound having a fluorene skeleton (specifically, 9,9-bis (condensed polycyclic aryl) fluorene skeleton) and a cured product thereof.

  The epoxy resin is cured with various curing agents to form a cured product having excellent mechanical properties, water resistance, chemical resistance, heat resistance, electrical properties, and the like. Therefore, epoxy resins are used in a wide range of fields such as adhesives, paints, laminates, molding materials and casting materials. Conventionally, bisphenol A-type epoxy resins and the like are known as the most commonly used epoxy resins in the industry, but such epoxy resins sometimes have insufficient heat resistance depending on applications.

  On the other hand, compounds having a 9,9-bisphenylfluorene skeleton such as bisphenolfluorene (BPF) and bisphenoxyethanol fluorene (BPEF) are known to have an excellent function in heat resistance. It is also known to be used as a resin raw material.

  For example, JP 2005-162785 A (Patent Document 1) discloses a resin composition composed of a compound having a fluorene skeleton and a thermoplastic resin. , 9-bis (4-glycidyloxyphenyl) fluorene, 9,9-bis (4-glycidyloxy-3-methylphenyl) fluorene, 9,9-bis (4-glycidyloxyethoxyphenyl) fluorene, 9,9- It describes that glycidyl ethers such as bis (4-glycidyloxyethoxy-3-methylphenyl) fluorene can be used.

  Since such an epoxy resin has a 9,9-bisphenylfluorene skeleton, characteristics such as heat resistance can be improved to some extent as compared with a conventional epoxy resin such as a bisphenol A type epoxy resin. However, with rapid technological innovation in recent years, improvements in various high-functional properties such as high heat resistance are being demanded more rapidly.

  Therefore, a compound obtained by further improving such a compound having a fluorene skeleton in terms of heat resistance or the like has been studied. JP 2007-99741 A (Patent Document 2) describes that 9,9-bis (hydroxy) naphthylfluorenes can be used as an epoxy resin raw material. Alternatively, it is described that a reaction product of diols composed entirely of 9,9-bis (hydroxy) naphthylfluorenes and epichlorohydrin can be mentioned. However, this document does not describe the details of the epoxy resin, and does not specifically examine the epoxy resin.

JP 2009-155256 A (Patent Document 3) discloses an epoxy compound having an oxyalkylene group such as 9,9-bis (glycidyloxy C _2-4 alkoxynaphthyl) fluorene, which is 9,9-bis ( It is described that melt viscosity can be remarkably reduced as compared with an epoxy compound such as a reaction product of hydroxy) naphthylfluorenes and epichlorohydrin. In the comparative example of this document, it is described that 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene was an epoxy compound having very high viscosity and poor handling properties. 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene.

However, in the epoxy compound of this document, even if the melt viscosity can be reduced by introducing an oxyalkylene group, there is a possibility that characteristics such as heat resistance and refractive index in the cured product may be lowered.
Japanese Patent Laying-Open No. 2005-162785 (Claim 1, paragraph numbers [0043] and [0044]) JP 2007-99741 A (Claim 1, paragraph numbers [0064] to [0065]) JP 2009-155256 A (claims, paragraph numbers [0016], [0138] to [0141])

  Accordingly, an object of the present invention is to provide a fluorene skeleton-containing epoxy resin composition having excellent properties such as high heat resistance, low linear expansion, and high refractive index, and a cured product obtained by curing the composition.

  Another object of the present invention is to provide a fluorene skeleton-containing epoxy resin composition having a significantly low bending elastic modulus at a high temperature, even though it has a high bending elastic modulus near room temperature, and a cured product obtained by curing the composition. Is to provide.

  In order to achieve the above object, the inventors of the present invention, among epoxy compounds having a 9,9-bisarylfluorene skeleton, particularly have no oxyalkylene group such as 9,9-bis (glycidyloxynaphthyl) fluorene. When a curable composition containing a compound is cured, it is possible to obtain a cured product having characteristics such as high heat resistance and low linear expansion, and exhibiting a unique behavior having a remarkably low flexural modulus at high temperatures. The headline and the present invention were completed.

  That is, the curable composition of the present invention includes a compound represented by the following formula (1) and a curing agent.

(In the formula, ring Z represents a condensed polycyclic aromatic hydrocarbon ring, R ¹ and R ² represent a substituent, R ³ represents a hydrogen atom or a methyl group, k represents an integer of 0 to 4, and m represents 0 or more. Integer, n is an integer of 1 or more.)
The compound represented by the formula (1) may typically be 9,9-bis (glycidyloxynaphthyl) fluorene.

  Further, the curing agent may be non-volatile or have a high boiling point (for example, a boiling point of 150 ° C. or higher). Typically, the curing agent may contain a phenolic curing agent (phenolic resin curing agent, phenols having a fluorene skeleton, etc.). The curable composition of the present invention may further contain a curing accelerator (for example, phosphines).

  The present invention includes a cured product obtained by curing the curable composition. Such a cured product has a characteristic that the flexural modulus at a high temperature is extremely small. For example, the flexural modulus at 200 ° C. of the cured product of the present invention may be 12 MPa or less (for example, 10 MPa or less). The flexural modulus at 23 ° C. may be 3200 MPa or more.

  Typically, the cured product of the present invention may have a glass transition temperature by TMA method of 180 ° C. or higher, a flexural modulus at 23 ° C. of 3400 MPa or higher, and a flexural modulus at 200 ° C. of 8 MPa or lower.

  In the present specification, the “class” such as a compound name includes a case of “having no substituent” and a case of “having a substituent”, and “may have a substituent”. May mean.

  The composition (or cured product thereof) of the present invention has excellent characteristics such as high heat resistance, low linear expansion, and high refractive index. In particular, the composition of the present invention (or a cured product thereof) has a characteristic that it has a significantly low bending elastic modulus at a high temperature even though it has a high bending elastic modulus near normal temperature. Therefore, the composition of the present invention (or a cured product thereof) is a material that can sufficiently withstand high-temperature applications while having the above-described excellent characteristics. For example, in a multilayer printed wiring board material, etc. Can relieve the stress on the substrate acting during reflow.

(Curable composition)
The curable composition (epoxy resin composition) of this invention contains the compound (epoxy compound) represented by the said Formula (1) as an epoxy compound (an epoxy resin, an epoxy resin component).

In the formula (1), the condensed polycyclic aromatic hydrocarbon ring represented by the ring Z is a condensed bicyclic hydrocarbon ring (for example, a C _8-20 condensed bicyclic ring such as an indene ring or a naphthalene ring). Hydrocarbon rings, preferably C _10-16 condensed bicyclic hydrocarbon rings), condensed tricyclic hydrocarbon rings (for example, anthracene ring, phenanthrene ring, etc.), etc. It is done. Preferred examples of the condensed polycyclic aromatic hydrocarbon ring include a naphthalene ring and an anthracene ring, and a naphthalene ring is particularly preferable. The two rings Z substituted at the 9-position of fluorene may be the same or different rings, and may usually be the same ring.

  In addition, the substitution position of the ring Z substituted at the 9th position of fluorene is not particularly limited. For example, the naphthyl group substituted at the 9th position of fluorene may be a 1-naphthyl group, a 2-naphthyl group, or the like. Particularly preferred is a 2-naphthyl group.

In the formula (1), examples of the substituent represented by the group R ¹ include a cyano group, a halogen atom (fluorine atom, chlorine atom, bromine atom, etc.), a hydrocarbon group [eg, alkyl group, aryl Non-reactive substituents such as a group (C _6-10 aryl group such as a phenyl group) and the like, and the like. Examples of the alkyl group include C _1-6 alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and a t-butyl group (for example, a C _1-4 alkyl group, particularly a methyl group). . In addition, when k is plural (two or more), the groups R ¹ may be different from each other or the same. Further, the groups R ¹ substituted on the two benzene rings constituting the fluorene (or fluorene skeleton) may be the same or different. Further, the bonding position (substitution position) of the group R ¹ with respect to the benzene ring constituting the fluorene is not particularly limited. The preferred substitution number k is 0 to 1, in particular 0. In the two benzene rings constituting fluorene, the number of substitutions k may be the same or different from each other.

Examples of the substituent R ² substituted on the ring Z include an alkyl group (for example, a C _1-12 alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, preferably a C _1-8 alkyl group). More preferably a C _1-6 alkyl group), a cycloalkyl group (C _5-8 cycloalkyl group such as a cyclohexyl group, preferably a C _5-6 cycloalkyl group etc.), an aryl group (for example, a phenyl group). , C _6-14 aryl groups such as tolyl group and xylyl group, preferably C _6-10 aryl group, more preferably C _6-8 aryl group, etc., aralkyl groups (C _6-10 such as benzyl group, phenethyl group, etc.) Hydrocarbon groups such as aryl-C _1-4 alkyl groups; alkoxy groups (C _1-8 alkoxy groups such as methoxy groups, preferably C _1-6 A group such as a alkoxy group), a cycloalkoxy group (such as a C _5-10 cycloalkyloxy group), and an aryloxy group (such as a C _6-10 aryloxy group) —OR ⁴ [wherein R ⁴ represents a hydrocarbon group ( The above-exemplified hydrocarbon groups and the like). A group —SR ⁴ such as an alkylthio group (C _1-8 alkylthio group such as a methylthio group, preferably a C _1-6 alkylthio group); wherein R ⁴ is as defined above; an acyl group (acetyl group) C _1-6 acyl group such as); alkoxycarbonyl group (such as C _1-4 alkoxy-carbonyl group such as methoxycarbonyl group); halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom etc.); hydroxyl group Nitro group; cyano group; substituted amino group (for example, dialkylamino group such as dimethylamino group) and the like.

Of these, the group R ² is preferably a hydrocarbon group, an alkoxy group, a cycloalkoxy group, an aryloxy group, an aralkyloxy group, an acyl group, a halogen atom, a nitro group, a cyano group, a substituted amino group, and the like. Particularly preferred group R ² is a hydrocarbon group [eg, alkyl group (eg, C _1-6 alkyl group)], alkoxy group (eg, C _1-4 alkoxy group), halogen atom (fluorine atom, chlorine atom, bromine). Atoms, iodine atoms, etc.).

In the same ring Z, when m is plural (two or more), the groups R ² may be different from each other or the same. In the two rings Z, the groups R ² may be the same or different. The preferred substitution number m may be 0 to 8, preferably 0 to 6 (for example, 1 to 5), more preferably 0 to 4, particularly 0 to 2 (for example, 0 to 1). In the two rings Z, the number of substitutions m may be the same or different from each other.

In the formula (1), the group R ³ is a hydrogen atom or a methyl group, and preferred R ³ is a hydrogen atom.

  In the formula (1), the substitution number n may be 1 or more, and may be, for example, 1 to 4, preferably 1 to 3, more preferably 1 to 2, particularly 1. The number of substitutions n may be the same or different in each ring Z, and is usually the same in many cases. The substitution position of the epoxy group-containing group is not particularly limited as long as it is substituted at an appropriate substitution position of ring Z. In particular, the epoxy group-containing group is at least substituted with a hydrocarbon ring different from the hydrocarbon ring bonded to the 9-position of the fluorene in the condensed polycyclic hydrocarbon ring (for example, the 5-position, 6-position, etc. of the naphthalene ring). There are many cases.

  Specific examples of the compound represented by the formula (1) include 9,9-bis (glycidyloxynaphthyl) fluorene [for example, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene, 9 , 9-bis (5-glycidyloxy-1-naphthyl) fluorene and the like], and the like, and the like.

  The compound represented by the formula (1) is not particularly limited. For example, the compound represented by the following formula (2) [for example, 9,9-bis (hydroxynaphthyl) fluorene] and the following formula ( It can manufacture by making the compound represented by 3) react.

(In the formula, X represents a halogen atom (bromine atom, chlorine atom, etc.), and Z, R ¹ , R ² , k, m, and n are the same as described above.)
In the compound represented by the formula (3), examples of the halogen atom represented by the group X include a chlorine atom, a bromine atom and an iodine atom, and a chlorine atom and a bromine atom (particularly a chlorine atom). Is preferred. Specific compounds represented by the formula (3) include epihalohydrins [or halomethyloxiranes such as epichlorohydrin (chloromethyloxirane), epibromohydrin (bromomethyloxirane), etc.], 1-halomethyl- 2-methyloxirane (1-chloromethyl-2-methyloxirane etc.) etc. are mentioned.

  In the reaction with the compound represented by the formula (2), the ratio of the compound represented by the formula (3) is, for example, 1 mol of the hydroxyl group of the compound represented by the formula (2). It may be about 2 to 30 mol (for example, 2.1 to 25 mol), preferably 2.5 to 20 mol, and more preferably about 3 to 15 mol (for example, 3 to 10 mol).

  In the reaction (reaction between the compound represented by the formula (2) and the compound represented by the formula (3)), a catalyst may be appropriately used. Examples of the catalyst include a base (base catalyst), for example, a metal carbonate (an alkali metal such as sodium carbonate or an alkaline earth metal carbonate, an alkali metal such as sodium hydrogencarbonate or an alkaline earth metal bicarbonate), a carboxylic acid, and the like. Metal salt (such as alkali metal acetate or alkaline earth metal salt such as sodium acetate and calcium acetate), metal hydroxide (alkaline metal hydroxide such as sodium hydroxide and potassium hydroxide, alkaline earth such as calcium hydroxide) Examples thereof include inorganic bases such as metal hydroxides) and ammonia; organic bases such as amines and basic ion exchange resins (for example, strongly basic anion exchange resins having a quaternary ammonium base). The bases may be used alone or in combination of two or more.

  Although the usage-amount of a catalyst (for example, basic catalyst) also depends on the kind of catalyst, for example, it is 0.1-20 mol with respect to 1 mol of compounds represented by the said Formula (2), Preferably it is 0. It may be about 2 to 10 mol, more preferably about 1 to 5 mol.

  The reaction may be performed in the absence of a solvent or in a solvent.

  The reaction temperature and reaction time can be appropriately selected according to the type of raw material used. The reaction temperature may be, for example, 30 to 120 ° C, preferably 35 to 100 ° C, more preferably about 40 to 70 ° C. The reaction time may be, for example, 30 minutes to 48 hours, usually 1 to 36 hours, preferably about 2 to 24 hours.

  The reaction may be performed while refluxing or may be performed while removing by-products. The reaction may be performed with stirring, may be performed in air or in an inert atmosphere (such as nitrogen or a rare gas), and may be performed under normal pressure, increased pressure, or reduced pressure.

  In addition, the produced | generated compound (compound represented by said Formula (1)) combined separation means, such as filtration, concentration, extraction, crystallization, recrystallization, column chromatography, etc., and these by the usual method. Separation and purification may be performed by separation means.

  The compound produced by the reaction may be a compound that does not belong to the category of the compound represented by the formula (1) [for example, represented by the unreacted formula (2), as long as the properties as a product are not impaired. Etc.] may be included. In such a mixture, the ratio of the compound represented by the formula (1) to the whole mixture is, for example, 65% by weight or more (for example, 68 to 99.9% by weight), preferably 70% by weight or more (for example, 75 to 99.7% by weight), more preferably about 80 to 99.5% by weight.

  The epoxy equivalent of the compound represented by the formula (1) (or the compound produced by the reaction, the same shall apply hereinafter) is, for example, 250 to 1500 g / eq, preferably 280 to 1000 g / eq, and more preferably 300 to 700 g / eq. It may be about eq, and usually about 300 to 500 g / eq.

  The melt viscosity at 180 ° C. (rotation speed: 900 rpm) of the compound represented by the formula (1) is, for example, 1000 to 7000 mPa · s, preferably 1500 to 6000 mPa · s (for example, 2000 to 5000 mPa · s), More preferably, it may be about 3000 to 4000 mPa · s.

  Moreover, the 5 weight% reduction | decrease temperature of the compound represented by said Formula (1) is 350 degreeC or more (for example, 350-500 degreeC), for example, Preferably it is 360-450 degreeC, More preferably, it is about 370-400 degreeC. There may be.

  Furthermore, the refractive index at 25 ° C. and 589 nm of the compound represented by the formula (1) is 1.66 or more (for example, 1.67 to 1.75), preferably 1.68 to 1.73, more preferably. May be about 1.69 to 1.72.

  In addition, the composition of this invention may comprise an epoxy compound (epoxy resin component) only with the compound represented by said Formula (1), and if it is a range which does not impair the effect of this invention, it will be another epoxy. It may contain a compound. Other epoxy resins include glycidyl ether type epoxy resins, such as bisphenol type epoxy resins (bisphenol A type epoxy resins, bisphenol F type epoxy resins, etc.), phenol novolac type epoxy resins, cresol novolac type epoxy resins, dicyclopentadiene modified Phenol (or cresol) novolac type epoxy resin, biphenyl type epoxy resin, triphenolalkane type epoxy resin (such as triphenolmethane type epoxy resin), phenol aralkyl type epoxy resin, heterocyclic type epoxy resin (epoxy resin containing xanthene unit) ), Stilbene type epoxy resins, condensed ring aromatic hydrocarbon modified epoxy resins (1,6-bis (glycidyloxy) naphthalene, bis (2,7-bis (glycidyloxy)) ) Naphthalene ring-containing epoxy resins such as naphthalene) alkanes), glycidyl ester type epoxy resins, other epoxy resins having a fluorene skeleton. These other epoxy resins may be used alone or in combination of two or more.

  When using another epoxy resin, the ratio of the compound represented by the formula (1) to the entire epoxy resin component is, for example, 50 to 99.5% by weight, preferably 70 to 97% by weight, and more preferably 90%. It may be about -98% by weight.

The composition of the present invention further contains a curing agent. Examples of the curing agent (curing agent for epoxy resin) include amine-based curing agents [particularly, primary amines such as chain aliphatic amines (for example, chains such as ethylenediamine, hexamethylenediamine, diethylenetriamine, and triethylenetetramine). Cycloaliphatic amines such as mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, 3,9-bis (3-aminopropyl) -2,4 , 8,10-tetraoxaspiro (5.5) undecane and other monocyclic aliphatic polyamines; bridged cyclic polyamines such as norbornanediamine), araliphatic polyamines (eg, xylylenediamine), aromatic amines (For example, metaphenylenediamine, diaminodiphenylmethane, etc.) , Polyaminoamide curing agents, acid anhydride curing agents (eg, aliphatic acid anhydrides such as dodecenyl succinic anhydride, polyadipic anhydride; tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hexahydrophthalic anhydride, Aliphatic acid anhydrides such as methylhexahydrophthalic anhydride, methyl hymic anhydride, methylcyclohexene dicarboxylic acid anhydride; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic anhydride, etc. Aromatic phenols), phenolic curing agents {eg, phenolic resins (eg, novolak resins such as phenolic novolak resins and cresol novolac resins); phenols having a fluorene skeleton [eg, 9,9-bis (hydroxyphenyl) Fluorene (eg, 9, -Bis (4-hydroxyphenyl) fluorene), 9,9-bis (alkyl-hydroxyphenyl) fluorene (eg, 9,9-bis (4-hydroxy-3-methylphenyl) fluorene, 9,9-bis ( 9,9-bis (mono or diC _1-4 alkyl-hydroxyphenyl) fluorene) such as 4-hydroxy-3,5-dimethylphenyl) fluorene, 9,9-bis (aryl-hydroxyphenyl) fluorene (eg, 9,9-bis (hydroxyphenyl) fluorene such as 9,9-bis (mono- or di-C _6-10 aryl-hydroxyphenyl) fluorene) such as 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene Compounds represented by the formula (2) (9,9-bis (hydroxynaphthyl) fluorenes) Etc.] phenol compounds such}, and the like. These curing agents may be used alone or in combination of two or more.

  Since the epoxy resin has a relatively high viscosity, a non-volatile or relatively high boiling point curing agent may be suitably used. When the curing agent has a boiling point, the boiling point of the curing agent is, for example, 120 ° C. or higher (for example, 130 to 400 ° C.), preferably 150 ° C. or higher (for example, 160 to 350 ° C.), and more preferably 180 ° C. or higher (for example, , 190 to 330 ° C.), particularly about 200 ° C. or more (for example, 220 to 300 ° C.).

  Among such curing agents, typical curing agents include phenolic curing agents such as phenolic resin-based curing agents (such as phenolic resins).

  The hydroxyl group equivalent of the phenol resin-based curing agent may be, for example, about 80 to 300, preferably 90 to 270, and more preferably about 100 to 250.

  In the curable composition, the ratio of the curing agent is such that the functional group of the curing agent is 0.1 to 5.0 with respect to 1 mol of the epoxy group of the compound (or epoxy resin component) represented by the formula (1). Mol, preferably 0.3 to 2.0 mol (for example, 0.5 to 1.5 mol), more preferably 0.7 to 1.2 mol (for example, 0.9 to 1.1 mol). As such, the ratio of both components may be adjusted.

  The curable composition may further contain a curing accelerator. The curing accelerator can be selected according to the type of the curing agent, for example, amines [eg, tertiary amines (eg, triethylamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylamino Methyl) phenol, 1,8-diazabicyclo (5.4.0) undecene-1), imidazoles (eg, alkylimidazoles such as 2-methylimidazole; arylimidazoles such as 2-phenylimidazole) and derivatives thereof ( For example, salts such as phenol salts, phenol novolak salts, carbonates, formates, etc.)], alkali metal or alkaline earth metal alkoxides, phosphines (such as triphenylphosphine), amide compounds (such as dimer acid polyamide), Lewis acids Complexation Products (boron trifluoride / ethylamine complex, etc.), sulfur compounds [polysulfide, mercaptan compounds (thiol compound), etc.], boron compounds (phenyldichloroborane, etc.), condensable organometallic compounds (organic titanium compounds, organoaluminum compounds, etc.) Etc. The curing accelerators may be used alone or in combination of two or more.

  The ratio (addition amount) of the curing accelerator is, for example, 0.01 to 30 parts by weight, preferably 0.05 to 100 parts by weight with respect to 100 parts by weight of the compound (or epoxy resin component) represented by the formula (1). It may be about 20 parts by weight, more preferably about 0.1 to 10 parts by weight.

  If necessary, the curable composition may be prepared by adding a diluent (a reactive diluent such as a monofunctional epoxy compound, a solvent, etc.) and a conventional additive such as a colorant, a stabilizer (a heat stabilizer, an oxidation agent). An inhibitor, an ultraviolet absorber, etc.), a filler, an antistatic agent, a flame retardant, a flame retardant aid, and the like. Diluents and additives may be used alone or in combination of two or more.

  The curable composition of the present invention has excellent properties such as high heat resistance and low bending elasticity at high temperatures, and is relatively high viscosity even at high temperatures. It may be a thing. Moreover, since the curable composition of the present invention has a relatively high viscosity, it often requires a high temperature for molding, and may be a composition that does not substantially contain a solvent.

(Cured product)
The present invention also includes a cured product (or molded product) obtained by curing (or crosslinking) the curable composition. Such a cured product can be obtained by reacting (curing) the curable composition. Such a curing treatment may be performed while molding or molding (or preforming) the curable composition according to the shape of the cured product. In addition, as a shape of hardened | cured material, one-dimensional or two-dimensional hardened | cured material, such as a three-dimensional hardened | cured material, a cured film, and a hardened pattern, a point or a dot-like hardened | cured material, etc. are mentioned. Specifically, the molded body is a product having a desired shape formed from a cured product of the curable composition, a cured film formed from a cured product of the curable composition formed on a substrate ( Coating film) or the like. For example, the curable composition is melted by heating, poured into a predetermined mold and heated to be cured, and a molded body having a desired shape can be obtained. Moreover, a cured film can be formed on a base material by apply | coating the liquid said curable composition on a base material, drying, and then heating. The molding method and the curing conditions are not particularly limited. For example, when molding using a predetermined mold, a molding method by heating and pressurization or a low-temperature molding method called cold press is used.

  When the curable composition is heated and melted, the heating temperature is, for example, 80 ° C. or higher (for example, 90 to 400 ° C.), preferably 100 ° C. or higher (for example, 110 to 350 ° C.), and more preferably 120 ° C. or higher. (For example, 130 to 300 ° C.), particularly about 140 to 250 ° C. (for example, 145 to 220 ° C.), or about 100 to 200 ° C. (for example, 120 to 180 ° C.).

  The curing treatment can be performed by heating or the like, and may be performed in combination. Usually, the curing treatment is often performed at least by heating.

  In the curing treatment, the heating temperature may be, for example, about 50 to 250 ° C., preferably 70 to 220 ° C., and more preferably about 80 to 200 ° C. (for example, 100 to 190 ° C.). The heating time may be, for example, about 10 minutes to 24 hours, preferably 30 minutes to 18 hours, and more preferably about 1 to 12 hours (for example, 2 to 8 hours). The curing treatment may be performed stepwise, for example, after heat treatment at a relatively low temperature, heat treatment may be performed at a relatively high temperature (for example, about 150 to 350 ° C., preferably about 160 to 300 ° C.). .

  Moreover, when forming hardened | cured material in a film form (film form, thin film form), you may form by apply | coating the said curable composition to a board | substrate (or base | substrate). The substrate is, for example, an insulating substrate such as resin, glass or ceramic, a semiconductor substrate such as crystalline silicon or amorphous silicon, a conductor substrate such as metal, a conductor layer formed on these substrates, or a composite of these. Things.

  The coating method for forming a coating film (thin film) on the substrate is not particularly limited. For example, spin coating method, roll coating method, bar coating method, slit coating, gravure coating method, spray coating method, dipping method, screen printing. Law.

  The thickness of the coating film may be, for example, 0.01 μm to 10 mm, preferably 0.05 μm to 1 mm, more preferably about 0.1 to 100 μm, depending on the use of the cured product.

  The resin composition applied to the substrate may be subjected to a drying treatment as necessary. A drying process can be performed using a well-known method. The drying treatment may be performed, for example, under normal pressure, under pressure or under reduced pressure, or may be performed by heating with a heating means (hot plate, oven, etc.). Although the temperature at the time of warming changes also with the solvent to be used and the drying method, it is 40-200 degreeC normally, Preferably it is 50-170 degreeC, More preferably, about 60-150 degreeC may be sufficient.

  As described above, the coating film applied to the substrate is usually subjected to a curing treatment after being dried as necessary. In the curing process, the heating temperature and heating time can be selected from the same ranges as described above.

  The cured product thus obtained has characteristics such as high heat resistance and low linear expansion. For example, the glass transition temperature of the cured product of the present invention by the TMA method is 175 ° C. or higher (eg, 177 to 300 ° C.), preferably 180 ° C. or higher (eg 182 to 250 ° C.), more preferably 185 ° C. or higher (eg, 187-230 ° C.), particularly 190 ° C. or higher (eg, 190-210 ° C.).

  In addition, the cured product of the present invention has a characteristic that it has a high flexural modulus near room temperature, but a remarkably small flexural modulus at high temperatures. For example, the flexural modulus at 200 ° C. of the cured product of the present invention is 12 MPa or less (for example, 0.5 to 11 MPa), preferably 10 MPa or less (for example, 1 to 9 MPa), more preferably 8 MPa or less (for example, 2 to 2 MPa). 7 MPa). Moreover, the bending elastic modulus at 23 ° C. of the cured product of the present invention is 3000 MPa or more (for example, 3100 to 6000 MPa), preferably 3200 MPa or more (for example, 3300 to 5000 MPa), more preferably 3400 MPa or more (for example, 3500 to 4000 MPa). It may be a degree.

  Hereinafter, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples.

  Various characteristics were measured and evaluated by the following methods.

(GPC (gel permeation chromatography))
A sample was dissolved in tetrahydrofuran using HLC-8320GPC manufactured by Tosoh Corporation, and measurement was performed at a flow rate of 1.0 mL / min, an injection amount of 100 μL, and a temperature of 40 ° C.

(HPLC)
Using Hitachi L-2000, sample dilution rate of 2000 times (acetonitrile), temperature 30 ° C., wavelength 254 nm, flow rate 0.5 mL / min, water / acetonitrile (weight ratio) = 30/70 for 30 minutes, Then, it measured for 30 minutes by water / acetonitrile (weight ratio) = 0/100.

(Epoxy equivalent)
It measured by JIS K7236 (titration method).

(Total chlorine content)
It was measured by the TOX100 combustion method.

(viscosity)
Using an E-type viscometer (cone plate type), the measurement was performed at 900 rpm.

(5% weight loss temperature)
Using Tg / DTA, measurement was performed under conditions of 30 to 500 ° C. and 10 ° C./min.

(Refractive index)
Using a multi-wavelength Abbe refractometer “DR-M2 / 1550” (manufactured by Atago Co., Ltd.), measurement was performed at a light source wavelength of 589 nm and a measurement temperature of 25 ° C.

(Bending test (strength, elastic modulus, bending strain))
Bending tests at 23 ° C. and 200 ° C. were performed under the following conditions.
Test method: JIS K 7171
Test temperature: 23 ° C, 200 ° C
Test speed: 5 ° C / min
Distance between fulcrums: 64mm (support radius 5mm)
Test apparatus: Instron 5582 type universal material testing machine Test piece: Circular saw-diamond electrodeposited blade + # 400 polishing paper finish 80 × 10 × 4 (mm).

(Tg and linear expansion coefficient)
The glass transition temperature (Tg) by the TMA method and the linear expansion coefficient in a predetermined temperature range were measured under the following conditions.
Test method: JIS K 7197
Temperature increase rate: 5 ° C / min Measurement mode: Compression (load 20mN)
Atmosphere: N ₂ (50 ml / min)
Test equipment: TMA8310 (Rigaku)
Test piece: Draining cutting whetstone + # 400 polishing paper finish 10 × 5 × 3 (mm).

(Tg (dynamic viscoelasticity))
The dynamic viscoelastic modulus was measured under the following conditions to obtain Tg by the DMA method.
Test apparatus: Rheogel-E4000
Measurement mode: Temperature-dependent chuck: Pulling condition: 30 Hz Measurement temperature range 25-280 ° C., step temperature = 1 ° C., heating rate = 3 ° C./min. Test piece: thickness of about 500 μm.

(Synthesis Example 1)
9,9-bis (6-hydroxy-2-naphthyl) fluorene (synthesized according to Example 1 of JP 2007-99741 A) 45.1 in a separable flask equipped with a three-way cock and having an internal volume of 300 ml. Part by weight (0.1 mol) and 92.0 parts by weight (1.0 mol) of epichlorohydrin (manufactured by Kanto Chemical Co., Inc.) were charged, heated to 50 ° C. and dissolved, and the inside of the reactor was purged with nitrogen.

  Then, 10.0 parts by weight (0.25 mol) of flake sodium hydroxide was added to the reactor in 4 portions every 20 minutes while maintaining around 60 ° C. and stirred for about 7 hours. Reacted.

  After confirming the disappearance of the raw materials by HPLC, the epichlorohydrin remaining in the system was concentrated and removed at 60 ° C. and 100 Torr, and then 110 g of methyl isobutyl ketone was added and kept at 60 ° C.

  Thereafter, filtration under reduced pressure was performed to remove salts generated during the reaction. Subsequently, 66.0 parts by weight (0.495 mol) of a 30% aqueous sodium hydroxide solution was added dropwise while maintaining the temperature at 80 ° C. After the entire amount was added, the mixture was stirred for about 1 hour, and 55 parts by weight of pure water was added. Further, the washing was repeated 5 times with 55 parts by weight of pure water, then dried through a filter paper covered with 15 parts by weight of anhydrous magnesium sulfate (manufactured by Kanto Chemical), and then dried at 90 ° C. and 10 torr for 15 hours. Obtained .58 parts by weight of white powder (yield 62.8%). As a result of analyzing the obtained white powder by HPLC and GPC, the target product (compound represented by the following formula, 9,9-bis (6-glycidyloxy-2-naphthyl) fluorene) is contained with a purity of 85% or more. It was confirmed to be a white powder.

  The white powder obtained had an epoxy equivalent of 311 g / eq, a total chlorine content of 2700 ppm, a melt viscosity at 180 ° C. of 3200 mPa · s, a 5 wt% weight reduction temperature of 382 ° C., a refractive index (25 ° C., 589 nm ( D line)) was 1.70.

Example 1
The white powder obtained in Synthesis Example 1 and a phenol novolak resin (manufactured by Gunei Chemical Industry Co., Ltd., PSM-4261, hydroxyl group equivalent 105, softening temperature of about 80 ° C.) as a curing agent, the former / the latter (equivalent ratio) ) = 1/1, and melt-mixed at 160 ° C. for 5 minutes using a two roll (manufactured by Inoue Seisakusho, roll rotation speed: front 23.0 rpm, back 20.7 rpm). To the molten mixture, triphenylphosphine as a curing accelerator was added at a ratio of 1% by weight, and again mixed at 110 ° C. for 3 minutes using a two-roll. Thereafter, the obtained mixture was pulverized in a mortar.

The pulverized mixture was put into a mold and pressed and hardened with a cold pressure (about 100 kgf / cm ² ) to form a tablet. The tablet is put in a mold (150 mm × 150 mm × 0.5 mm) heated to 150 ° C., and this mold is set in a press machine (26 ton manual compression molding machine, manufactured by Toho Press) and pressed to 100 kgf / cm ^2. did. The pressure was maintained for 15 minutes (5 minutes at the initial temperature, 10 minutes at 150 ° C.), and then cooled at 100 kgf / cm ² with a cooling press (water cooling). The obtained cured product was post-cured with a dryer at 175 ° C. for 5 hours.

(Synthesis Example 2)
In Synthesis Example 1, 9,9-bis (4-hydroxyphenyl) fluorene (BPF, manufactured by Osaka Gas Chemical Co., Ltd.) was used instead of 9,9-bis (6-hydroxy-2-naphthyl) fluorene. Except for this, a white powder (yield 90% or more) was obtained in the same manner as in Synthesis Example 1. As a result of analyzing the obtained white powder by HPLC and GPC, it was confirmed that it was a white powder containing a compound represented by the following formula with a purity of 90% or more.

(Comparative Example 1)
A cured product was obtained in the same manner as in Example 1 except that the white powder obtained in Synthesis Example 2 was used in place of the white powder obtained in Synthesis Example 1.

(Synthesis Example 3)
In Synthesis Example 1, instead of 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis [4- (2-hydroxyethoxy) phenyl] fluorene (manufactured by Osaka Gas Chemical Co., Ltd., A viscous product (yield 90% or more) was obtained in the same manner as in Synthesis Example 1 except that BPEF) was used. As a result of analyzing the obtained viscous product by HPLC and GPC, it was confirmed that the product was a viscous product having a purity of 80% or more and containing a compound represented by the following formula.

(Comparative Example 2)
In Example 1, a cured product was obtained in the same manner as in Example 1 except that the white powder obtained in Synthesis Example 3 was used instead of the white powder obtained in Synthesis Example 1.

(Synthesis Example 4)
In Synthesis Example 1, instead of 9,9-bis (6-hydroxy-2-naphthyl) fluorene, 9,9-bis (4-hydroxy-3-phenylphenyl) fluorene (Japanese Patent Laid-Open No. 2001-206863) A white powder (yield 85% or more) was obtained in the same manner as in Synthesis Example 1 except that the compound synthesized according to Example 1 was used. As a result of analyzing the obtained white powder by HPLC and GPC, it was confirmed that it was a white powder containing a compound represented by the following formula with a purity of 85% or more.

(Comparative Example 3)
In Example 1, a cured product was obtained in the same manner as in Example 1 except that the white powder obtained in Synthesis Example 4 was used instead of the white powder obtained in Synthesis Example 1.

(Comparative Example 4)
In Example 1, in place of the white powder obtained in Synthesis Example 1, bisphenol A type epoxy resin (manufactured by Mitsubishi Chemical Co., Ltd., trade name 828) was used, and cured in the same manner as in Example 1. I got a thing.

  Various physical property data of the cured products obtained in Example 1 and Comparative Examples 1 to 4 are shown in the table.

  As is apparent from the results of the table, the cured product obtained in Example 1 is not only a cured product of a general-purpose bisphenol A type epoxy resin, but also a cured product of an epoxy compound having the same fluorene skeleton. Even if it has high heat resistance and high bending elastic modulus at room temperature, the bending elastic modulus is remarkably small at high temperatures. In particular, as compared with the case of a cured product using a BOPPF epoxy compound having a rigid skeleton similar to BNF (Comparative Example 3), the result is that Tg is high and the flexural modulus at high temperature is very small. As a result, in Example 1, it was found that a unique cured product was obtained among the cured products of the epoxy compound having a fluorene skeleton.

  The curable composition of the present invention (or a cured product thereof) has excellent properties such as high heat resistance and low linear expansion coefficient, and has a characteristic that the flexural modulus at a high temperature is extremely low. Further, since it has a fluorene skeleton, it is excellent in dispersibility of additives such as pigments.

  Such a curable composition (or a cured product thereof) of the present invention is useful as an insulating material between electronic component layers, a solder resist for printed circuit boards, a resist material such as a coverlay, etc., color filters, inks, etc. (Printing inks, etc.), sealants (semiconductor sealants, etc.), paints, coating agents, adhesives, adhesives, underfills, antistatic agents, fillers, conductive members or conductive materials, laminated materials, heat sensitive materials ( Thermal paper materials, etc.), carbon materials, insulating materials, foams, pressure sensitive materials, optical materials (transparent materials) [eg lenses (reflow lenses, pickup lenses, micro lenses, etc.), polarizing films, antireflection films, touch panels Film, flexible substrate film, display film, fuel cell membrane, optical fiber, optical waveguide, hologram] Rayuru material (electric and electronic materials, optical materials) useful as.

  In particular, the curable composition of the present invention has a low flexural modulus at high temperature, and can effectively prevent cracks by stress relaxation due to a low elastic modulus at high temperature during the reflow process. is there.

Claims (7)

A curable composition comprising a compound represented by the following formula (1) and a phenol resin.

(Wherein R ¹ represents a cyano group, a halogen atom or a hydrocarbon group, R ² represents a hydrocarbon group, a group —OR ⁴ ( wherein R ⁴ represents a hydrocarbon group), a group —SR ⁴ (formula R ⁴ represents a hydrocarbon group), an acyl group, an alkoxycarbonyl group, a halogen atom, a hydroxyl group, a nitro group, a cyano group or a substituted amino group , R ³ represents a hydrogen atom or a methyl group, and k represents 0-4 integer, m is an integer of 0-6.) The curable composition according to claim 1, wherein the phenol resin is non-volatile or has a boiling point of 150 ° C or higher.   Furthermore, the curable composition of Claim 1 or 2 containing a hardening accelerator.   Hardened | cured material which the curable composition in any one of Claims 1-3 hardened | cured.   The hardened | cured material of Claim 4 whose bending elastic modulus in 200 degreeC is 12 Mpa or less.   The cured product according to claim 4 or 5, wherein the flexural modulus at 23 ° C is 3200 MPa or more and the flexural modulus at 200 ° C is 10 MPa or less.   The cured product according to any one of claims 4 to 6, having a glass transition temperature by TMA method of 180 ° C or higher, a bending elastic modulus at 23 ° C of 3400 MPa or higher, and a bending elastic modulus at 200 ° C of 8 MPa or lower.