TWI572666B - An epoxy resin mixture, an epoxy resin composition and a cured product thereof - Google Patents

Description

Epoxy resin mixture, epoxy resin composition and cured product thereof

The present invention relates to an epoxy resin mixture which provides a composition excellent in fluidity and a cured product excellent in flame retardancy and heat resistance.

Further, the present invention relates to an electronic material application requiring high functionality, particularly as a sealing agent for a semiconductor, a preferred epoxy resin mixture for a film substrate material, an epoxy resin composition, and a cured product thereof.

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

However, in recent years, in the field of electrical and electronic fields, with the development of the resin composition, high purity of the resin composition, moisture resistance, adhesion, dielectric properties, and low filling of fillers (inorganic or organic fillers) are required. Various characteristics such as viscosity and improvement in reactivity for shortening the molding cycle are further improved. In addition, as a structural material, materials which are lightweight and excellent in mechanical properties are required for use in aerospace materials, leisure, and sports equipment applications. In particular, in the field of semiconductor sealing, the substrate (the substrate itself, or its peripheral material), the semiconductor is changed to become thin, layered, systemized, and three-dimensional, and the metal wire is narrowly pitched. Thin lines continue to evolve, and without high fluidity, wire sweeps can result. Further, it adversely affects the connection portion of the metal wires.

Further, in the flip chip type package, a method of not performing underfill for the inexpensive manufacturing method and sealing the MUF at one time is attracting attention. In this application, the resin must pass through a very narrow gap between the wafer and the package substrate, and the fineness of the filler becomes important. Due to the miniaturization, the viscosity of the system rises and becomes a void.

Further, in a sealing resin for a rewiring layer such as a wafer level package, or an associated insulating film for a build-up layer, etc., since the thickness of the layer is thin, and in order to reduce the linear expansion ratio, Fine fillers must be filled. Therefore, in this application, as in the above, the low viscosity of the resin composition is required.

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

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

A method of lowering the viscosity of various resin compositions can be used. Generally, as a method of lowering the viscosity of the resin composition, a low molecular weight of an epoxy resin can be used, and when the epoxy resin is made low in molecular weight, heat resistance is obtained. Further, since the shape at room temperature becomes easy to have fluidity, it is difficult to operate at room temperature, and further, the composition becomes viscous and becomes difficult to store or handle. Further, since the ratio of the epoxy portion (aliphatic chain) in the molecule is increased, it is relatively easily thermally decomposed, and it is easy to cause adverse effects on the flame retardancy.

That is, an object of the present invention is to provide an epoxy resin mixture containing an epoxy resin composition thereof and a cured product thereof, which can provide excellent fluidity, and An epoxy resin composition of a cured product excellent in heat resistance and flame retardancy can be provided.

The inventors of the present invention have made efforts to carry out research in view of the actual circumstances as described above, and have completed the present invention.

That is, the present invention provides (1) an epoxy resin mixture containing 1,1'-bis(2-glycidoxynaphthyl) and substituted (or unsubstituted) 4,4'-bicyclic ring. Oxypropoxybiphenyl (wherein the substituent has a substituent in the aromatic ring, the number of substituents is 4 or less, and the carbon number is 4 or less); (2) The epoxy resin as described in the above item (1) a mixture of 1,1'-bis(2-epoxypropoxynaphthyl)(A) and substituted (or unsubstituted) 4,4'-glycidoxybiphenyl (B) The ratio is A/B=1~10; (3) The epoxy resin mixture as described in the above item (1), which is a combination of binaphthol (BINOL) and substituted (or unsubstituted) 4,4'- Biphenol (in the case where a substituent is present in the aromatic ring, the number of substituents is 4 or less, the carbon number is 4 or less), and is obtained by reacting with epihalohydrin; (4) a ring An oxygen resin composition, which must contain the epoxy resin mixture according to any one of the above items (1) to (3), and a curing agent; (5) an epoxy resin composition which must contain the above item (1) to (3) The epoxy resin mixture and the polymerization catalyst according to any one of (3) a cured product Which the front line (4) or (5) described epoxy resin composition and cured Made.

The epoxy resin mixture of the present invention has an extremely low viscosity and contributes to the fluidity of the composition, and the cured product is excellent in heat resistance and flame retardancy. Therefore, it is useful for various composite materials, adhesives, paints, and the like which are represented by insulating materials for electronic components, laminates (printed wiring boards, build-up substrates, etc.) or CFRP. In particular, it is extremely useful for protecting semiconductor sealing materials for semiconductor components.

The epoxy resin mixture of the present invention contains 1,1'-bis(2-glycidoxynaphthyl) and substituted or unsubstituted 4,4'-diepoxypropoxybiphenyl (wherein When the aromatic ring has a substituent, the number of substituents is 4 or less, and the number of carbon atoms is 4 or less.

1,1'-bis(2-glycidoxynaphthyl) is a reaction of a binaphthol with an epihalohydrin, and further, 4,4'-diglycidoxybiphenyl (wherein, in an aromatic ring) In the case of having a substituent, the number of substituents is 4 or less, and the number of carbon atoms is 4 or less. 4,4'-biphenol (wherein, in the case of having a substituent in the aromatic ring, the number of substituents is 4) Hereinafter, the reactant having a carbon number of 4 or less and an epihalohydrin is used.

Here, the substituent is preferably an alkyl group having 1 to 4 carbon atoms or an alkoxy group, and specific examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a methoxy group, and a Oxyl, propoxy, and the like.

Specific examples of such a substituted or unsubstituted 4,4'-diglycidoxybiphenyl include the following structures.

(In the above formula, R represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group, G represents a glycidyl group, and t represents an integer of 1 to 4)

Further, the above-mentioned substituted or unsubstituted 4,4'-biphenol is specifically exemplified by the following structure.

(In the above formula, R and t have the same meaning as the above)

A stereoisomer is present in the binaphthol, and any of a chiral or racemic form can be used to obtain the epoxy resin mixture of the present invention. Further, the purity thereof is preferably 90% by area or more, more preferably 93% by area or more, still more preferably 95% by area or more, and particularly preferably 98% by area or more, as measured by GPC. The impurity may, for example, be a naphthol compound having a fluorene structure or a raw material, and these are preferably 2% by area or less, preferably 1% by area or less. Purity can be controlled by crystallization or washing. If the purity is low, the properties of the obtained epoxy resin mixture of the present invention are lowered. Further, the drying loss is preferably 0.2% or less, more preferably 0.1% or less. In the case of a large amount of drying reduction, there is a case where the production line is contaminated in the manufacturing step. The melting point is preferably from 200 to 220 ° C, more preferably from 212 to 219 ° C. As such commercial products, they are available from Aldrich and SR-CHEM.

4,4'-biphenol (wherein the substituent has a substituent in the aromatic ring, the number of substituents is 4 or less, and the carbon number is 4 or less) is a compound having 4,4'-biphenol as a basic skeleton. As a specific example thereof, 4,4'-biphenol, 3,3',5,5'-tetramethylbiphenyl-4,4'-di Alcohol, 3,3'-dimethylbiphenyl-4,4'-diol, and the like. In the present invention, 4,4'-biphenol and 3,3',5,5'-tetramethylbiphenyl-4,4'-diol are preferred in terms of ease of availability. The epoxy resin mixture is preferably 4,4'-biphenol in terms of rationality.

1,1'-bis(2-epoxypropoxynaphthyl)(A) and substituted (or unsubstituted) 4,4'-diepoxypropoxy group in the epoxy resin mixture of the present invention Biphenyl (wherein the substituent has a substituent in the aromatic ring, the number of substituents is 4 or less, the carbon number is 4 or less), and the ratio (weight ratio) of (B) is preferably A/B = 1 to 10 More preferably, it is 1.5~7.5, and the best is 2.0~6.0. In terms of the balance of heat resistance, flame retardancy, and fluidity, the present invention is preferred.

As the shape of the present epoxy resin mixture, in the case of homogeneously mixing, it is preferred to have a crystalline solid resin shape, and in this case, the softening point is preferably in terms of handleability and formability at the time of hardening. It is 70 to 140 ° C, more preferably 80 to 130 ° C.

With respect to the epoxy resin mixture of the present invention, 1,1'-bis(2-glycidoxynaphthyl) can be bonded to a substituted (or unsubstituted) 4,4'-diepoxypropoxy group. Benzene (wherein the substituent has a substituent in the aromatic ring, the number of substituents is 4 or less, the carbon number is 4 or less) is uniformly mixed, and the binaphthol can be substituted (or unsubstituted). The 4,4'-biphenol (in the case where the substituent has a substituent in the aromatic ring, the number of the substituent is 4 or less, and the number of carbon atoms is 4 or less) is mixed and obtained by reacting with an epihalohydrin. In the present invention, the latter is preferable in terms of ease of manufacture and linkage of molecules.

The method of reacting with the epihalohydrin is not particularly limited, and an example of a method for synthesizing the epoxy resin mixture of the present invention is described below.

In the reaction for obtaining the epoxy resin mixture of the present invention, by making binaphthol (AA) and 4,4'-biphenol (wherein having a substituent in the aromatic ring thereof, the number of substituents is 4 or less, the carbon number is 4 or less) (BB) simultaneously reacts with an epihalohydrin to prepare an epoxy resin mixture. Here, the ratio (weight ratio) of (AA) to (BB) is preferably AA/BB = 1 to 10, more preferably 1.5 to 7.5, and particularly preferably 2.0 to 6.0. Heat resistance, flame retardancy, and fluidity In terms of balance, it is better to be the scope. Further, in the following, a mixture of (AA) and (BB) is referred to as a phenol-based mixture of the present invention.

In the reaction for obtaining the epoxy resin mixture of the present invention, as the epihalohydrin, epichlorohydrin which is industrially easily available is preferred. The amount of the epihalohydrin used is usually from 3.0 to 15 moles, preferably from 3.0 to 10 moles, more preferably from 3.5 to 8.5 moles, more preferably 4.5, based on the hydroxyl group of the phenolic mixture of the present invention. ~8.5 m.

When it is less than 3.0 mol, the epoxy equivalent may become large, and the workability of the epoxy resin produced may deteriorate, and if it exceeds 15 mol, the amount of solvent may become large.

In the above reaction, it is preferred to use an alkali metal hydroxide in the reaction with an epihalohydrin. Examples of the alkali metal hydroxide which can be used include sodium hydroxide, potassium hydroxide, and the like, and a solid matter or an aqueous solution thereof can be used. In the present invention, in particular, in terms of moisture, solubility, and handling, It is preferred to use a solid formed into a sheet shape.

The amount of the alkali metal hydroxide used is usually from 0.90 to 1.5 moles, preferably from 0.95 to 1.25 moles, more preferably from 0.99 to 1.15 moles, per mole of the hydroxyl group of the phenolic mixture.

In order to promote the reaction, a quaternary ammonium salt such as tetramethylammonium chloride, tetramethylammonium bromide or trimethylbenzylammonium chloride may be added as a catalyst. The amount of the quaternary ammonium salt used is usually 0.1 to 15 g, preferably 0.2 to 10 g, per 1 mol of the hydroxyl group of the phenol-based mixture of the present invention.

In the reaction, it is preferred to use a nonpolar protic solvent (dimethyl sulfoxide, two in addition to the above epihalohydrin). An alkane, a dimethylimidazolidinone, etc., in the present invention, preferably a dimethyl hydrazine, two Alkane or an alcohol having 1 to 5 carbon atoms. The alcohol having 1 to 5 carbon atoms is an alcohol such as methanol, ethanol or isopropanol (in the present invention, methanol is preferred). The amount of the nonpolar protic solvent or the alcohol having 1 to 5 carbon atoms is usually 2 to 50% by weight, preferably 4 to 25% by weight based on the amount of the epihalohydrin used. Further, epoxidation may be carried out while controlling the moisture in the system by azeotropic dehydration or the like.

In the case where the amount of water in the reaction system is large, the electrical reliability of the obtained epoxy resin mixture is lowered, and it is preferred to synthesize the moisture to be controlled to 5% or less. Also, due to use When a non-polar protic solvent is used to obtain an epoxy resin mixture, an epoxy resin mixture excellent in electrical reliability can be obtained, and thus a nonpolar protic solvent can be preferably used.

The reaction temperature is usually from 30 to 90 ° C, preferably from 35 to 80 ° C. In particular, in the present invention, in order to carry out epoxidation of higher purity, it is preferably 60 ° C or more, and particularly preferably a reaction under conditions close to reflux conditions. The reaction time is usually from 0.5 to 10 hours, preferably from 1 to 8 hours, and particularly preferably from 1 to 3 hours. If the reaction time is short, the reaction may not proceed completely. If the reaction time is long, a by-product may be formed.

After the reactants of the epoxidation reaction are washed with water or without washing with water, the epihalohydrin or the solvent is removed under heating and reduced pressure. Further, in order to obtain a hydrolyzable halogen and a small epoxy resin mixture, a ketone compound having 4 to 7 carbon atoms may be used (for example, methyl isobutyl ketone, methyl ethyl ketone, cyclopentanone, or a ring) The hexanone or the like is dissolved as a solvent, and an aqueous solution of an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide is added to carry out a reaction, and the ring is reliably closed. In this case, the amount of the alkali metal hydroxide used is usually from 0.01 to 0.3 mol, preferably from 0.05 to 0.2 mol, based on 1 part by mole of the hydroxyl group of the phenol-based mixture of the present invention used for epoxidation. 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 salt formed is removed by filtration, washing with water, etc., and the solvent is distilled off under heating and reduced pressure to obtain an epoxy resin mixture of the present invention. Further, it is preferably a plate-shaped body (flat plate) which is cast and dropped or dropped to 100 ° C or lower, more preferably 80 ° C or lower, after the solvent is distilled off under heating and reduced pressure, and maintained at 110 to 170 ° C. In the shape of a sheet, a strip, or the like, it is molded into a shape such as a plate shape or a drop shape (ball shape) and taken out. Further, the stepwise cooling method may be carried out after cooling at 80 ° C or lower and further cooling at 60 ° C or lower.

In the present invention, as the appearance of the obtained epoxy resin mixture, it has a turbid color tone with crystallinity (specifically, it is cloudy and not amorphous).

In the epoxy resin mixture of the present invention, as long as 1,1'-bis(2-glycidoxynaphthyl) and substituted (or unsubstituted) 4,4'-digoxypropoxy biphenyl (Where, when the substituent has a substituent in the aromatic ring, the number of the substituent is 4 or less, and the number of carbon atoms is 4 or less) is not particularly limited, and the reaction is carried out under the preferred conditions as described above. There is also a structure (C) in which a binaphthol structure and a biphenol structure are bonded via a -CH ₂ CH(OH)CH ₂ - structure. In the case of simply epoxidizing only binaphthol, the structure (D) which is similarly bonded is formed, and since the molecular weight is large, the viscosity is likely to be high, but if it is as described above, In the case of epoxidation, the structure (D) is not produced, and the structure (C) is produced, whereby the viscosity is relatively low, and it is preferable to improve the fluidity as the object of the present invention.

Preferred resin characteristics of the epoxy resin mixture of the present invention are preferably epoxy equivalents (1,1'-bis(2-glycidoxynaphthyl) as a mixture of the obtained epoxy resins of the present invention. , the average of the epoxy equivalents of 4,4'-bisgoxypropoxybiphenyl (and the above structure (C) in the case of the above structure (C)) is 190 to 350 g/eq. More preferably 200~300g/eq. When the epoxy equivalent is within the above range, an epoxy resin having excellent heat resistance and electrical reliability of the cured product can be obtained. In the case where the epoxy equivalent exceeds 350 g/eq., there are cases where a large amount of a compound containing an epoxy ring is not completely closed without a functional group, and there is a case where the epoxy equivalent is not lowered. Further, in many cases, a large amount of these compounds which are not completely closed are contained in chlorine, and as an electronic material, there is a case where chlorine ions are released under high temperature and high humidity conditions, and corrosion of the wiring is caused.

Further, the total chlorine remaining in the epoxy resin is preferably 5,000 ppm or less, more preferably 3,000 ppm or less, and particularly preferably 2,000 ppm or less. Further, the chloride ion and the sodium ion are each preferably 5 ppm or less, more preferably 3 ppm or less. Chloride ions are described above, and of course, cations such as sodium ions are also a very important factor particularly in power device applications, and are a cause of poor mode when a high voltage is applied.

The epoxy resin mixture of the present invention has a form of a resin having a softening point. Here, as the softening point, it is preferably 55 to 130 ° C, more preferably 60 to 120 ° C. Softening point If it is too low, there is a case where blocking occurs during storage. On the other hand, when the softening point is too high, there is a case where the handleability is lowered when kneading with other resins. Further, the melt viscosity is preferably 2 Pa. s (ICI, melt viscosity, 150 ° C, cone and plate method) below. When it is used in the case of mixing an inorganic material (filler or the like), the fluidity is lowered, and the mesh of the glass cloth or the like is also fined, and the impregnation property is lowered.

Hereinafter, the epoxy resin composition of the present invention (hereinafter also referred to as a curable resin composition) containing the epoxy resin mixture of the present invention will be described.

In the curable resin composition of the present invention, a curing agent or a polymerization catalyst is used as an essential component.

The curable resin composition of the present invention can be roughly classified into two types, and is hereinafter referred to as a curable resin composition A and a curable resin composition B.

The curable resin composition A is a composition of an epoxy resin mixture and a curing agent of the present invention as essential components.

The curable resin composition B is a composition of an epoxy resin mixture and a polymerization catalyst of the present invention as essential components.

The polymerization catalyst which can be contained in the curable resin composition B of the present invention can be used without limitation as long as it is a catalyst which is polymerized by heat or light. Specifically, a curing accelerator or an acid hardening contact can be used. Media.

Specific examples of the curing accelerator which can be used include imidazoles such as 2-methylimidazole, 2-ethylimidazole and 2-ethyl-4-methylimidazole, and 2-(dimethylaminomethyl). Tertiary amines such as phenol, 1,8-diaza-bicyclo(5,4,0)undecene-7, phosphines such as triphenylphosphine, tetrabutylammonium salt, triisopropylmethylammonium a quaternary ammonium salt such as a salt, a trimethyl decyl ammonium salt or a cetyl trimethyl ammonium salt; a quaternary ammonium salt such as a triphenylbenzyl phosphonium salt, a triphenylethyl phosphonium salt or a tetrabutyl phosphonium salt; (The relative ions of the fourth-order salt are halogen, organic acid ion, hydroxide ion, etc., and are not particularly specified, and particularly preferred are organic acid ions and hydroxide ions), and metal compounds such as stannous octoate. In the case of using a hardening accelerator, 0.01 to 5.0 is used as needed with respect to 100 parts by weight of the epoxy resin. Parts by weight.

As the acid curing catalyst, a cationic polymerization initiator is preferred, and a photo or thermal cationic polymerization initiator is particularly preferred. It can be used as the following curable resin composition B by blending a cationic polymerization initiator activated by an active energy ray and/or a thermally activated cationic polymerization initiator.

Examples of the cationic polymerization initiator which initiates cationic polymerization of the curable resin composition B of the present invention by irradiation with an active energy ray include diazonium salt, strontium salt, strontium salt, selenium salt, and pyridinium. The salt, the ferrocenium salt, the phosphonium salt, and the thiopyrylium salt are preferably an onium salt and a phosphonium salt, and more preferably a diarylsulfonium salt and a dialkyl benzamidine. Methyl phosphonium salts, especially diaryl phosphonium salts, can be preferably used.

When a photocationic polymerization initiator such as a phosphonium salt or a phosphonium salt is used in the cationically curable resin composition of the present invention, examples of the anion include BF ₄ ^- , AsF ₆ ^- , SbF ₆ ^- , PF ₆ ^- , and _{B (C 6 F 5) 4} - and the like, preferably SbF ₆ ^-, PF ₆ ^-, or _{B (C 6 F 5) 4} - , particularly preferably SbF ₆ ^- or _{B (C 6 F 5) 4} - .

Specific examples of the photocationic polymerization initiator include bis(dodecylphenyl)phosphonium hexafluoroantimonate (the main component of UV-9380C manufactured by GE TOSHIBA SILICONE Co., Ltd.) and tetrakis(pentafluorophenyl). Tricumyl borohydride (PHOTOINITIATOR 2074, manufactured by Rhodia Co., Ltd.), bis(alkyl (C=10-14) phenyl fluorene hexafluoroantimonate) (photopolymerization initiator WPI-016 manufactured by Wako Pure Chemical Industries, Ltd.) )Wait.

A compound which is activated by heat and starts cationic polymerization, that is, a thermal cationic polymerization initiator can also be used for the curable resin composition B of the present invention. Examples of the thermal cationic polymerization initiator include various onium salts such as a quaternary ammonium salt, a phosphonium salt, and a phosphonium salt, or a combination of an alkoxysilane and an aluminum complex. As the available products, Adekaopton CP-66 and Adekaopton CP-77 (all trade names, manufactured by ADEKA Co., Ltd.), San-Aid SI-60L, San-Aid SI-80L, and San-Aid SI-100L can be cited. (all are trade names, Sanxin Chemical Industry Co., Ltd. The company manufactures) and the CI series (made by Japan Soda Co., Ltd.).

Hereinafter, the curable resin compositions A and B of the present invention will be respectively described.

In the curable resin composition A and the curable resin composition B, other epoxy resins may be used in combination with the epoxy resin mixture of the present invention. When used in combination, the ratio of the epoxy resin mixture of the present invention to the total epoxy resin is preferably 30% by weight or more, particularly preferably 40% by weight or more. In the case where the epoxy resin mixture of the present invention is used as a modifier of a curable resin composition, it is added in a ratio of 1 to 30% by weight.

Specific examples of the other epoxy resin include a novolac type epoxy resin, a bisphenol A type epoxy resin, a biphenyl type epoxy resin, a triphenylmethane type epoxy resin, a phenol aralkyl type epoxy resin, and the like. . Specific examples thereof include bisphenol A, bisphenol S, thiobiphenol, bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, 3,3', 5, 5'-tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl)methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) and formaldehyde, Acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)-1, 1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4-bis(chloromethyl)benzene, 1,4-bis(methoxy a polycondensate of benzene or the like and a modified substance thereof, a halogenated bisphenol such as tetrabromobisphenol A, an epoxy propyl ether derived from an alcohol, an alicyclic epoxy resin, or a glycidylamine Epoxy resin, epoxy propyl ester epoxy resin, etc., sesquioxane-based epoxy resin (chain, ring, ladder, or a mixture of at least two or more of these Ethylene oxide in the alkane structure And / or an epoxy resin of epoxy cyclohexane structure) solid or liquid epoxy resin and the like, but is not limited to such.

Hereinafter, various curable resin compositions will be described.

Thermal hardening using a hardener (curable resin composition A)

The hardener contained in the curable resin composition A of the present invention may, for example, be a phenol tree. A lipid, a phenol compound, an amine compound, an acid anhydride compound, a guanamine compound, a carboxylic acid compound, or the like.

Specific examples of the hardener which can be used are as follows.

Examples of the phenol resin and the phenol compound include bisphenol A, bisphenol F, bisphenol S, bisphenol, stilbene, 4,4'-biphenol, 2,2'-biphenol, 3,3', and 5 ,5',-Tetramethyl-[1,1'-biphenyl]-4,4'-diol, hydroquinone, resorcinol, naphthalenediol, tris-(4-hydroxyphenyl) Methane, 1,1,2,2-tetrakis(4-hydroxyphenyl)ethane, phenols (phenol, alkyl-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, dihydroxynaphthalene, etc.) Formaldehyde, acetaldehyde, benzaldehyde, p-hydroxybenzaldehyde, o-hydroxybenzaldehyde, p-hydroxyacetophenone, o-hydroxyacetophenone, dicyclopentadiene, furfural, 4,4'-bis(chloromethyl)- 1,1'-biphenyl, 4,4'-bis(methoxymethyl)-1,1'-biphenyl, 1,4'-bis(chloromethyl)benzene, 1,4'-bis ( a polycondensate of methoxymethyl)benzene or the like, a modified substance such as a halogenated bisphenol such as tetrabromobisphenol A, or a polyphenol such as a condensate of a terpene and a phenol, but is not limited thereto. . These may be used alone or in combination of two or more.

Preferred examples of the phenol resin include a phenol aralkyl resin (a resin having an aromatic alkylene structure), and particularly preferably a resin having at least one selected from the group consisting of phenol, naphthol and cresol. a structure in which the alkyl group of the linker is at least one selected from the group consisting of a benzene structure, a biphenyl structure, and a naphthalene structure (specifically, Xylok, naphthol, and Phenol-linked phenol novolak resin, cresol-linked phenol novolak resin, phenol-naphthol novolak resin, etc.).

Examples of the amine compound and the guanamine compound include diaminodiphenylmethane, diethylidene triamine, triethylidenetetramine, diaminodiphenyl hydrazine, isophorone diamine, and dicyandiamide. A nitrogen-containing compound such as a polyamide resin synthesized from a dimer of linoleic acid and ethylenediamine, but is not limited thereto. These may be used alone or in combination of two or more.

Examples of the acid anhydride-based compound and the carboxylic acid-based compound include phthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, pyrogalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, and methyltetramine. Hydrogen phthalic anhydride, methyl nadic anhydride, ceric anhydride, hexahydrophthalic anhydride, methyl hexahydrophthalic anhydride, butane tetracarboxylic anhydride, bicyclo [2, 2,1]heptane-2,3-dicarboxylic anhydride, methylbicyclo[2,2,1]heptane-2,3-dicarboxylic anhydride, cyclohexane-1,3,4-tricarboxylic acid- An acid anhydride such as 3,4-anhydride or the like, which is obtained by an addition reaction of various alcohols and methanol-modified polyfluorene oxide with the above acid anhydride, but is not limited thereto. These may be used alone or in combination of two or more.

Examples of other hardening agents which can be used together include, but are not limited to, imidazole, a trifluoroborane-amine complex, and a compound of an anthracene derivative. These may be used alone or in combination of two or more.

In the present invention, in particular, in terms of reliability, a phenol resin is preferably used.

In the curable resin composition A of the present invention, the amount of the curing agent used is preferably from 0.7 to 1.2 equivalents per equivalent of the epoxy group of the entire epoxy resin. When the amount is less than 0.7 equivalents per equivalent of the epoxy group, or when it exceeds 1.2 equivalents, the hardening is incomplete and good hardened physical properties cannot be obtained.

In the curable resin composition A of the present invention, a curing agent may be used in combination with the curing accelerator. Specific examples of the hardening accelerator which can be used include the above. In the case of using a hardening accelerator, it may be used in an amount of 0.01 to 5.0 parts by weight, based on 100 parts by weight of the epoxy resin.

The curable resin composition A of the present invention may further contain a phosphorus-containing compound as a flame retardancy imparting component. As the phosphorus-containing compound, it may be a reactive type or an additive type. Specific examples of the phosphorus-containing compound include trimethyl phosphate, triethyl phosphate, tricresyl phosphate, tris(dimethylphenyl) phosphate, cresyl diphenyl phosphate, and 2,6-di(xylene). Preference, cresyl phosphate, 1,3-phenylene bis(diphenylphosphine), 1,4-phenylphenylbis(diphenyl)phosphate, 4,4'- Phosphate such as biphenyl (di(xylenyl) phosphate); 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10(2,5-dihydroxyphenyl) )-10H a phosphine such as -9-oxa-10-phosphaphenanthrene-10-oxide; a phosphorus-containing epoxy compound obtained by reacting an epoxy resin with active hydrogen of the above phosphine, red phosphorus, etc., preferably phosphoric acid Ester, phosphine or phosphorus-containing epoxy compound, particularly preferably 1,3-phenylphenylbis(diphenylphosphine) 1,4-phenylphenylbis(diphenylphosphine) phosphate Ester), 4,4'-biphenyl (di(xylenyl) phosphate) or phosphorus-containing epoxy compound. The content of the phosphorus-containing compound is preferably a phosphorus-containing compound / all epoxy resins = 0.1 to 0.6 (weight ratio). When it is 0.1 or less, the flame retardancy is insufficient, and when it is 0.6 or more, the hygroscopic property and the dielectric property of the cured product are lowered.

Further, in the curable resin composition A of the present invention, an antioxidant may be added as needed. Examples of the antioxidant that can be used include a phenol-based, sulfur-based, and phosphorus-based antioxidant. The antioxidant may be used singly or in combination of two or more. The amount of the antioxidant to be used is usually from 0.008 to 1 part by weight, preferably from 0.01 to 0.5 part by weight, per 100 parts by weight of the resin component in the curable resin composition of the present invention.

Specific examples of the phenolic antioxidant include 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-p-ethylphenol, and β-( 3,5-di-t-butyl-4-hydroxyphenyl)propionic acid stearyl ester, 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionic acid isooctyl ester, 2,4 - bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-three a monobasic phenol such as 2,4-bis[(octylthio)methyl]o-cresol; 2,2'-methylenebis(4-methyl-6-tert-butylphenol), 2,2 '-Methylene bis(4-ethyl-6-tert-butylphenol), 4,4'-thiobis(3-methyl-6-tert-butylphenol), 4,4'-Adenine Bis(3-methyl-6-tert-butylphenol), triethylene glycol-bis[3-(3-t-butyl-5-methyl-4-hydroxyphenyl)propionate], 1,6-hexanediol-bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], N,N'-hexamethylenebis(3,5-di Third butyl-4-hydroxy-phenylpropanamide), 2,2-thio-diethylidene bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate ], 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid-diethyl ester, 3,9-bis[1,1-dimethyl-2-{β-(3-tert-butyl -4-hydroxy-5-methylphenyl)propoxycarbonyl}ethyl]2,4,8,10-tetraoxaspiro[5,5]undecane, bis (3,5-di third a bisphenol such as calcium butyl-4-hydroxybenzyl sulfonate; 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane, 1, 3,5-trimethyl-2,4,6-tris(3,5-di-t-butyl-4-hydroxybenzyl)benzene, tetra-[methylene-3-(3',5'- Di-tert-butyl-4'-hydroxyphenyl)propionate]methane, bis[3,3'- Bis-(4'-hydroxy-3'-t-butylphenyl)butyric acid]diol, tris-(3,5-di-t-butyl-4-hydroxybenzyl) isocyanurate, 1 ,3,5-tris(3',5'-di-t-butyl-4'-hydroxybenzyl)-symmetric three -2,4,6-(1H,3H,5H) triols, polymer phenols such as tocopherols.

Specific examples of the sulfur-based antioxidant include: 3,3'-dithiogallate dilaurate, 3,3'-thiodipropionate dimyristate, and 3,3'-thiodipropane. Distearyl ester and the like.

Specific examples of the phosphorus-based antioxidant include triphenyl phosphite, diphenylisodecyl phosphite, phenyl diisononyl phosphite, tris(nonylphenyl) phosphite, and diisoindole. Neopentyl pentaerythritol phosphite, tris(2,4-di-t-butylphenyl) phosphite, cyclopentane tetrakis(bis-octadecyl) phosphite, cyclopentane phosphite Tetrakis(2,4-di-t-butylphenyl) ester, cyclopentane tetrakis(bis)bis(2,4-di-tert-butyl-4-methylphenyl) phthalate, hydrogen phosphite Phosphites such as bis[2-t-butyl-6-methyl-4-{2-(octadecyloxycarbonyl)ethyl}phenyl]ester; 9,10-dihydro-9-oxygen Hetero-10-phosphaphenanthrene-10-oxide, 10-(3,5-di-t-butyl-4-hydroxybenzyl)-9,10-dihydro-9-oxa-10-phosphaphenanthrene Oxaphosphorus phenanthrene oxides such as 10-oxide, 10-decyloxy-9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide.

These antioxidants may be used alone or in combination of two or more. Particularly preferred in the present invention is a phosphorus-based antioxidant.

Further, in the curable resin composition A of the present invention, a light stabilizer may be added as needed.

As the light stabilizer, a hindered amine light stabilizer, especially HALS or the like is preferable. The HALS is not particularly limited, and as a representative, dibutylamine-1,3,5-three may be mentioned. -N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl-1,6-hexamethylenediamine and N-(2,2,6,6-tetramethyl) Polycondensate of keto-4-piperidyl)butylamine, dimethyl succinate-1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine Condensate, poly[{6-(1,1,3,3-tetramethylbutyl)amino-1,3,5-three -2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)imido}hexamethylene {(2,2,6,6-tetramethyl-) 4-piperidinyl)imido}], [[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonic acid bis (1,2 , 2,6,6-pentamethyl-4-piperidinyl), bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, azelaic acid bis(1) , 2,2,6,6-pentamethyl-4-piperidinyl), bis(1-octyloxy-2,2,6,6-tetramethyl-4-piperidinyl) sebacate Ester, 2-(3,5-di-t-butyl-4-hydroxybenzyl)-2-n-butylmalonic acid bis(1,2,2,6,6-pentamethyl-4-piperidine Ester). HALS may be used alone or in combination of two or more.

Further, in the curable resin composition A of the present invention, a binder resin may be blended as needed. Examples of the binder resin include a butyral resin, an acetal resin, an acrylic resin, an epoxy-nylon resin, an NBR-phenol resin, an epoxy-NBR resin, a polyamide resin, and a polyruthenium resin. An amine resin, a polysiloxane resin, or the like is not limited thereto. The blending amount of the binder resin is preferably in a range that does not impair the flame retardancy and heat resistance of the cured product, and is usually 0.05 to 50 parts by weight, preferably 0.05%, per 100 parts by weight of the epoxy resin component. 20 parts by weight.

In the curable resin composition A of the present invention, an inorganic filler may be added as needed. Examples of the inorganic filler include crystalline cerium oxide, molten cerium oxide, aluminum oxide, zircon, calcium silicate, calcium carbonate, cerium carbide, tantalum nitride, boron nitride, zirconium oxide, forsterite, and the like. A powder such as a block talc, a spinel, a titanium oxide or a talc, or a bead formed by spheroidizing the same, but is not limited thereto. These may be used alone or in combination of two or more. The content of the inorganic filler is from 0 to 95% by weight based on the curable resin composition of the present invention. Further, in the curable resin composition of the present invention, a release agent such as a decane coupling agent, stearic acid, palmitic acid, zinc stearate or calcium stearate, a surfactant, a dye, a pigment, or an ultraviolet ray may be added. Various additives such as a collector, and various thermosetting resins.

The curable resin composition A of the present invention is obtained by uniformly mixing the components. The curable resin composition A of the present invention can be easily made into a cured product by the same method as previously known. For example, the epoxy resin mixture of the present invention and a hardener, and optionally a hardening accelerator, a phosphorus-containing compound, a binder resin, an inorganic filler, and a blending agent can be sufficiently used, such as an extruder, a kneader, a roll, etc., as needed. The mixture is mixed until it is uniform, and a curable resin composition is obtained, and the curable resin composition is molded by pouring or melting (not melting in a liquid state) or a transfer molding machine, and further, 80 The hardened material of the present invention is obtained by heating at ~200 ° C for 2 to 10 hours.

Further, the curable resin composition A of the present invention can be dissolved in toluene, xylene, acetone, methyl ethyl ketone, methyl isobutyl ketone, dimethylformamide, dimethyl acetamide, as needed. A solvent such as N-methylpyrrolidone is used as a varnish for a curable resin composition, and is impregnated with a substrate such as glass fiber, carbon fiber, polyester fiber, polyamide fiber, alumina fiber or paper, and dried by heating. The prepreg obtained was subjected to hot press forming to thereby obtain a cured product of the curable resin composition A of the present invention. The solvent used in this case is usually used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, based on the mixture of the curable resin composition of the present invention and the solvent. Further, in the case of a liquid composition, an epoxy resin-containing cured product containing carbon fibers can be obtained, for example, by an RTM method.

Further, the curable resin composition A of the present invention can also be used as a modifier of the film type composition. Specifically, it can be used when the flexibility of the B stage or the like is improved. The resin composition of the film type can be applied to the release film by using the curable resin composition A of the present invention as the curable resin composition varnish, and the solvent is removed by heating, and then B-staged. It is obtained as a sheet-like adhesive. The sheet-like adhesive can be used as an interlayer insulating layer of a multilayer substrate or the like.

Curable resin composition B (cation hardening using an acid hardening catalyst)

The curable resin composition B of the present invention which is hardened by using an acidic hardening catalyst contains photopolymerization A starter or a thermal polymerization initiator is used as the acid hardening catalyst. Further, various known compounds, materials, and the like may be contained, such as a diluent, a polymerizable monomer, a polymerizable oligomer, a polymerization initiation aid, and a photosensitizer. Further, various known additives such as an inorganic filler, a coloring pigment, an ultraviolet absorber, an antioxidant, and a stabilizer may be contained as needed.

As the acid curing catalyst, a cationic polymerization initiator is preferred, and a photo or thermal cationic polymerization initiator is particularly preferred. The curable resin composition B can be used as a curable resin composition B by blending a cationic polymerization initiator activated by an active energy ray and/or using a thermally activated cationic polymerization initiator.

The cationic polymerization initiator which initiates cationic polymerization of the curable resin composition B of the present invention by irradiation with an active energy ray may be mentioned above.

As the active energy ray for curing the curable resin composition B of the present invention, X-ray, electron beam, ultraviolet ray, visible light or the like can be used, and ultraviolet light or visible light is preferable, and ultraviolet light is particularly preferable. In the case of using ultraviolet rays, the wavelength range thereof is not particularly limited, and is preferably 150 to 400 nm, and more preferably 200 to 380 nm. In the case of using ultraviolet rays, cationic polymerization can be started efficiently.

Further, in the curable resin composition B of the present invention, a sensitizer may be further used in combination to increase the activity of the photocationic polymerization initiator. As the sensitizer which can be used in the present invention, for example, a compound disclosed in Crivello, Adv. in Plymer Sci., 62, 1 (1984) can be used. Specifically, there are strontium, barium, acridine orange, 9-oxosulfur (thioxanthone), 2-chloro 9-oxosulfur And benzoflavin and the like. Further, a compound widely used as a photoradical polymerization initiator may be used, and specific examples thereof include benzophenone and 2,4-diethyl 9-oxosulfide. 2-isopropyl 9-oxosulfur 2,4-dichloro 9-oxosulfur 9-oxosulfur Classes, benzoin ether, benzoin ethyl ether, benzoin isopropyl ether and other benzoin ethers, 2,2-dimethoxy-1,2-diphenylethane-1-one and other diphenylethylenedione dimethyl ketal (benzil dimethyl ketal), 2-hydroxy-2-methyl-1-phenylpropan-1-one, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1- An α-hydroxyalkylphenone such as a ketone or 1-hydroxycyclohexyl phenyl ketone or an α-dicarbonyl compound such as camphorquinone. In the present invention, 9-oxygen sulfur can be particularly preferably used. Or an alpha-hydroxyalkyl phenone.

The blending amount of the photo-cationic polymerization initiator to the curable resin composition B of the present invention can be appropriately adjusted depending on the type of the active energy ray or the amount of irradiation. For example, in the case of ultraviolet rays, the total amount of the cationically curable resin composition is preferably 0.1 to 10 parts by mass, more preferably 0.5 to 5 parts, still more preferably 1 to 3 parts, per 100 parts by mass. When the blending amount of the cationic polymerization initiator is less than 0.1 part, there is a case where the hardenability is lowered, and conversely, when it is more than 10 parts by mass, the actually required component of the cured product is reduced and lowered. The case of the physical properties of the hardened material or the case where the color of the hardened material becomes severe.

When the sensitizer is added to the curable resin composition B of the present invention, the blending amount can be appropriately adjusted depending on the type of the active energy ray or the amount of irradiation. For example, in the case of ultraviolet rays, the total amount of the curable resin composition B is preferably 5 parts by mass or less, more preferably 0.2 to 2 parts, per 100 parts by mass of the curable resin composition B. When the blending amount of the sensitizer is more than 5 parts by mass, there is a case where the actually required component of the cured product is reduced to lower the physical properties of the cured product or the coloring of the cured product is severe.

When the active energy ray is ultraviolet or visible light, the cationically curable resin composition is exposed to the air. In this case, the ambient humidity is preferably low, preferably 80% RH or less, and more preferably 70. Below %RH. Here, in the case where ultraviolet rays or visible light are disposed in the production line, a method of blowing dry air in the vicinity of the light irradiation device or a method of reducing the humidity by installing the heating device may be employed.

As the compound which is activated by heat and starts cationic polymerization, the above may be mentioned.

The blend ratio of the thermal cationic polymerization initiator to the curable resin composition B of the present invention is preferably in the range of 0.01 to 10 parts by mass, more preferably 0.1 to 5 parts by mass per 100 parts by mass of the cationically curable resin composition. The fraction is further preferably 0.5 to 3 parts. At this blending ratio In the case of 0.01 parts by mass, even if it is activated by the action of heat, there is a case where the ring-opening reaction of the ring-opening polymerizable group cannot be sufficiently performed. Further, even if it is blended in an amount of more than 10 parts by mass, the effect of the polymerization is not further improved, and the physical properties of the cured product are lowered.

Further, in the curable resin composition B of the present invention, various additives such as the above-described inorganic filler, decane coupling material, mold release agent, and pigment, and various thermosetting resins may be added as needed.

The curable resin composition B of the present invention can be obtained by uniformly mixing the components. Further, it may be dissolved in an organic solvent such as polyethylene glycol monoethyl ether or cyclohexanone or γ-butyrolactone to make it uniform, and then the solvent is removed by drying and used. The solvent used in this case is usually used in an amount of 10 to 70% by weight, preferably 15 to 70% by weight, based on the mixture of the curable resin composition B of the present invention and the solvent. The curable resin composition B of the present invention can be cured by ultraviolet irradiation, and the amount of ultraviolet irradiation varies depending on the curable resin composition, and is therefore determined according to the respective curing conditions. In order to cure the photocurable curable resin composition, the curing strength of the cured product may be a good curing condition. At the time of the hardening, it is desirable that the epoxy resin mixture of the present invention and the curable resin composition B are higher in transparency in terms of light having to penetrate into the fine portion. Further, in the photocuring of the epoxy resin type, it is difficult to completely cure only by light irradiation, and in applications requiring heat resistance, it is necessary to completely complete the reaction hardening by heating after light irradiation.

The heating after the above light irradiation can be carried out in the hardening temperature region of the usual curable resin composition B. For example, it is preferably in the range of 30 minutes to 7 days at a normal temperature of -150 °C. The composition of the curable resin composition B varies, and in particular, the higher the temperature region, the more effective the curing is after the light is irradiated, and the heat treatment for a short period of time is more effective. Further, the lower the temperature, the longer the heat treatment is required. By performing such thermal post-hardening, the effect of the aging treatment is also produced.

Moreover, the shape of the cured product obtained by curing the curable resin composition B The shape may be various depending on the application, and is not particularly limited. For example, it may be in the form of a film, a sheet, or a block. The molding method varies depending on the part to be accommodated and the part. For example, a molding method such as a casting method, a casting method, a screen printing method, a spin coating method, a spray method, a transfer method, or a dispensing method can be applied, but it is not limited. In these. The forming die can be applied to a ground glass, a hard stainless steel grinding plate, a polycarbonate plate, a polyethylene terephthalate plate, a polymethyl methacrylate plate, or the like. Further, in order to improve the mold release property from the molding die, a polyethylene terephthalate film, a polycarbonate film, a polyvinyl chloride film, a polyethylene film, a polytetrafluoroethylene film, a polypropylene film, and a polyfluorene can be applied. Imine film and the like.

For example, in the case of a cationically curable resist, the photocationic curable resin composition B of the present invention which is dissolved in an organic solvent such as polyethylene glycol monoethyl ether or cyclohexanone or γ-butyrolactone The composition of the present invention is applied to a substrate such as a copper clad laminate, a ceramic substrate or a glass substrate by a method such as screen printing or spin coating, and a film thickness of 5 to 160 μm is applied to form a coating film. Further, after the coating film is pre-dried at 60 to 110 ° C, ultraviolet rays (for example, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high pressure mercury lamp, a xenon lamp, a laser beam, etc.) are irradiated through a negative film on which a desired pattern is drawn, and then, at 70 Post-exposure baking treatment was performed at ~120 °C. Thereafter, the unexposed portion is dissolved and removed (developed) by a solvent such as polyethylene glycol monoethyl ether, and further, if necessary, irradiated with ultraviolet rays and/or heated (for example, at 100 to 200 ° C for 0.5 to 3 hours). ) sufficiently hardened to obtain a cured product. A printed wiring board can also be obtained in this way.

The cured product obtained by curing the curable resin composition A and the curable resin composition B of the present invention can be used for various purposes.

The general use of the curable resin composition A or the curable resin composition B is exemplified, and examples thereof include an adhesive, a coating material, a coating agent, a molding material (including a sheet, a film, an FRP, etc.), and an insulating material (including a printed substrate). , wire coating, etc.), sealant, and other additives such as other resins. Examples of the adhesive include an adhesive for civil engineering, construction, automotive, general service, medical use, and an adhesive for electronic materials. Among these, examples of the adhesive for the electronic material include an interlayer adhesive of a multilayer substrate such as a build-up substrate, an adhesive, and an adhesive. An adhesive for a semiconductor such as a primer, an adhesive for BGA reinforcement, an anisotropic conductive film (ACF), an anisotropic conductive paste (ACP), or the like.

Examples of the sealing agent and the substrate include a capacitor, a transistor, a diode, a light-emitting diode, an IC, an LSI, etc., a immersion, a immersion molding, a transfer molding seal, an IC, an LSI type COB, a COF, a TAB, etc. Seals for infusion sealing, flip chip, etc., sealing for IC package such as QFP, BGA, CSP, etc. (including reinforcing primer) and package substrate. Moreover, it is also preferably used for a substrate requiring functional properties such as a mesh substrate or a module substrate.

Example

Next, the present invention will be specifically described by way of examples, and the parts are by weight unless otherwise specified. Furthermore, the invention is not limited to the embodiments.

The various analytical methods used in the examples are described below.

Epoxy equivalent: according to JIS K 7236 (ISO 3001)

ICI melt viscosity: according to JIS K 7117-2 (ISO 3219)

Softening point: according to JIS K 7234

GPC: pipe column (Shodex KF-603, KF-602.5, KF-602, KF-601×2)

Linked dissolving solution to tetrahydrofuran

The flow rate is 0.5ml/min.

Column temperature is 40 ° C

Detection: RI (differential refractive index detector)

Hereinafter, the present invention will be specifically described by way of examples and comparative examples.

(Example 1)

The flask equipped with a stirrer, a reflux cooling tube and a stirring device was subjected to nitrogen flushing, and 214.7 parts of binaphthol, 46.6 parts of 4,4'-biphenol, 740 parts of epichlorohydrin, and 296 parts of dimethylarylene were added thereto. It was dissolved and heated to 45 °C. Second, it takes 90 minutes to heat the flakes. After 84 parts of sodium oxide was added in portions, the reaction was further carried out at 45 ° C for 2 hours, and the reaction was carried out at 70 ° C for 75 minutes. After completion of the reaction, a solvent such as excess epichlorohydrin was distilled off from the oil layer using a rotary evaporator under reduced pressure. To the residue, 800 parts of methyl isobutyl ketone was added and dissolved, and after washing with water, the temperature was raised to 75 °C. 30 parts of a 30% by weight aqueous sodium hydroxide solution was added under stirring, and after 1 hour of reaction, the water was washed until the washing water of the oil layer became neutral, and the obtained solution was subjected to a reduced pressure using a rotary evaporator under reduced pressure. Butyl ketone or the like is distilled off, whereby 360 parts of the epoxy resin mixture (EP1) of the present invention are obtained. The obtained epoxy resin has an epoxy equivalent of 207 g/eq., a softening point of 87.5 ° C, and an ICI melt viscosity of 150 ° C of 0.03 Pa. S below.

(Synthesis Example 1)

The flask equipped with a stirrer, a reflux cooling tube and a stirring device was subjected to nitrogen purge while adding 214 parts of binaphthol, 555 parts of epichlorohydrin (4 mole equivalents, relative to phenol resin), and 55 parts of methanol, and dissolved under stirring. And heat up to 70~75 °C. Next, 60 parts of flaky sodium hydroxide was added in portions over 90 minutes, and further reacted at 75 ° C for 75 minutes. After completion of the reaction, water was washed with 400 parts of water, and a solvent such as excess epichlorohydrin was distilled off from the oil layer using a rotary evaporator under reduced pressure. 500 parts of methyl isobutyl ketone was added to the residue to dissolve, and the temperature was raised to 75 °C. 10 parts by weight of a 30% by weight aqueous sodium hydroxide solution and 10 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 decompressed using a rotary evaporator. Methyl isobutyl ketone or the like was distilled off, whereby 403 parts of an epoxy resin mixture (EP2) was obtained. The obtained epoxy resin has an epoxy equivalent of 230 g/eq., a softening point of 58 ° C, and an ICI melt viscosity of 150 ° C of 0.07 Pa. s.

(Synthesis Example 2)

Except that 214.7 parts of binaphthol and 46.6 parts of 4,4'-biphenol were changed to 242 parts of 3,3',5,5'-tetramethylbiphenyl-4,4'-diol, 1 Synthesis is performed in the same manner. As a result, 349 parts of an epoxy resin (EP3) was obtained. The obtained epoxy resin has an epoxy equivalent of 190 g/eq., a softening point of 107 ° C, and an ICI melt viscosity of 150 ° C of 0.03 Pa. s below.

Example 2 and Comparative Examples 1, 2

<heat resistance test>

The epoxy resin obtained above was blended in the ratio (parts by weight) of Table 1, and uniformly mixed and kneaded using a kneader to obtain a sealing epoxy resin composition. The epoxy resin composition was pulverized by a stirrer, and further formed into a tablet shape by a tablet press. The ingot-form epoxy resin composition was transferred (175 ° C × 60 sec), and further cured at 160 ° C × 2 hours + 180 ° C × 6 hours after demolding to obtain a test piece for evaluation.

Furthermore, the physical properties of the cured product were measured in the following points.

. Heat resistance (TMA): Measured in accordance with JIS K 7244.

. Heat resistance (HDT): Measured in accordance with JIS K 7191.

It is known that the epoxy resin of the present invention which is a mixture of the binaphthol structure and the biphenol structure and the cured product of the epoxy resin using the binaphthol structure (Comparative Example 1) and the cured product of the epoxy resin using the biphenol structure ( In Comparative Example 2), it exhibits high heat resistance and a low coefficient of linear expansion, and has a structure which can achieve both high heat resistance and dimensional stability.

Example 3 and Comparative Examples 3 and 4

<heat resistance test, flame retardancy test>

The epoxy resin obtained above was blended in the ratio (parts by weight) of Table 2, and uniformly mixed and kneaded using a kneader to obtain a sealing epoxy resin composition. The epoxy resin composition was pulverized by a stirrer, and further formed into a tablet shape by a tablet press. The ingot-form epoxy resin composition was transferred (175 ° C × 60 sec), and further cured at 160 ° C × 2 hours + 180 ° C × 6 hours after demolding to obtain a test piece for evaluation. The results of the flame retardancy test are also shown in Table 2. Further, the hardening accelerator C1 is the same as described above.

Furthermore, the physical properties of the cured product were measured in the following points.

. Flame retardant: According to UL94. Among them, the sample size was set to a width of 12.5 mm × a length of 150 mm, and the thickness was 0.8 mm.

. Residual flame time: the total of the residual flame time after 10 flames of 5 groups of samples

. Heat resistance (DMA)

Dynamic viscoelasticity tester: TA-instruments, DMA-2980

Measuring temperature range: -30~280°C

Heating rate: 2 ° C / min

Test piece size: use a cut of 5mm × 50mm (thickness of about 800μm)

Tg: set the peak point of Tan-δ to Tg

According to the results, it is known that the epoxy resin of the present invention as a mixture of a binaphthol structure and a biphenol structure and a cured product of an epoxy resin using a binaphthol structure (Comparative Example 3), an epoxy resin using a biphenol structure The cured product (Comparative Example 4) has a structure which can achieve both high heat resistance and high flame retardancy.

Example 4 and Comparative Example 5

<Liquidity test>

The epoxy resin obtained above was blended in the ratio (parts by weight) of Table 3, and uniformly mixed and kneaded using a kneader to obtain a sealing epoxy resin composition. The epoxy resin composition was pulverized by a stirrer, and further formed into a tablet shape by a tablet press. The spiral flow of the ingot-form epoxy resin composition was measured by a transfer molding machine at 175 ° C and a molding pressure of 70 kg/cm ² . Further, the curing agent P2, the curing accelerator C1, the inorganic filler, the coupling agent, and the releasing agent are the same as described above.

According to the results, it is understood that the epoxy resin of the present invention which is a mixture of a binaphthol structure and a biphenol structure has a cured product (Comparative Example 5) which is generally used as an epoxy resin having a bihydric phenol structure having a high fluidity. Higher liquidity. (Although the gel time is the same in seconds, the spiral flow is longer)

Example 5 and Comparative Examples 6, 7, 8, and 9

<Comparison with other structures in heat resistance and water absorption test>

The epoxy resin shown below was blended in the ratio (parts by weight) of Table 4, and uniformly mixed and kneaded using a kneader to obtain a sealing epoxy resin composition. The epoxy resin composition was pulverized by a stirrer, and further formed into a tablet shape by a tablet press. Making the ingot-like epoxy resin composition The material was transferred and molded (175 ° C × 60 sec.), and further cured at 160 ° C × 2 hours + 180 ° C × 6 hours after demolding to obtain a test piece for evaluation.

Furthermore, the physical properties of the cured product were measured in the following points.

. Heat resistance (TMA): Measured in accordance with JIS K 7244.

. Water absorption rate: percentage increase in weight after immersion in water at 100 ° C for 24 hours

EP4: a mixture of o-cresol novolac type epoxy resin and biphenol type epoxy resin (epoxy equivalent: 205 g/eq., softening point: 91 ° C, ICI melt viscosity: 0.03 Pa.s or less)

EP5: a mixture of a phenol aralkyl type epoxy resin and a biphenol type epoxy resin (epoxy equivalent: 214 g/eq., softening point 102 ° C, ICI melt viscosity 0.09 Pa.s)

EP6: a mixture of a biphenyl type phenol aralkyl type epoxy resin and a biphenol type epoxy resin (epoxy equivalent: 240 g/eq., softening point: 93 ° C, ICI melt viscosity: 0.03 Pa.s)

The structural formula of the phenol aralkyl type epoxy resin is represented by the following formula (A), and the structural formula of the biphenyl type phenol aralkyl type epoxy resin is represented by the following formula (B).

According to the results, it is understood that the epoxy resin of the present invention is superior in heat resistance to the same modified resin of the other structure, and if the heat resistance is increased, the general water absorption rate is deteriorated, but the water absorption property is not compared with the other. It is large and therefore excellent in heat resistance and water resistance.

Example 6

<Mechanical strength, coefficient of linear expansion, moisture absorption rate, crack resistance, impact resistance, molding shrinkage, gel time>

207 parts of epoxy resin EP1, 103 parts of P1, and 2 parts of C1 were blended, and uniformly mixed and kneaded using a kneading machine to obtain a sealing epoxy resin composition. The epoxy resin composition was pulverized by a stirrer, and further formed into a tablet shape by a tablet press. The ingot-form epoxy resin composition was transferred (175 ° C × 60 sec), and further cured at 160 ° C × 2 hours + 180 ° C × 6 hours after demolding to obtain a test piece for evaluation.

Furthermore, the physical properties of the cured product were measured in the following points.

. Mechanical strength: bending test, bending strength of 120 ° C according to JIS K 6911

. Linear expansion ratio: TMA was measured in accordance with JIS K 7244, and its α ₁ was measured.

. Moisture absorption rate: It was allowed to stand in a constant temperature and humidity chamber at 85 ° C and 85% for 24 hours, and the weight increase amount was measured.

. Crack resistance characteristics: determination of K1c, according to ASTM E-399

. Impact resistance: Ehrlich impact test according to JIS K 6911

. Molding shrinkage: the difference between the measurement and the mold, according to JIS K 6911

. Gel time: measured on a hot plate at 175 ° C

. Mechanical strength: 82MPa

. Linear expansion rate: 57ppm

. Moisture absorption rate: 0.75%

. Crack resistance characteristics: 19Nmm ^-1.5

. Impact resistance: 5.7kJ/m ²

. Molding shrinkage: 1.75%

. Gel time: 59 seconds

Example 7 and Comparative Examples 10 and 11

<Liquidity test>

The epoxy resin obtained above was blended in the ratio (parts by weight) of Table 5, and uniformly mixed and kneaded using a kneader to obtain a sealing epoxy resin composition. The epoxy resin composition was pulverized by a stirrer, and further formed into a tablet shape by a tablet press. The spiral flow of the ingot-shaped epoxy resin composition was measured by a transfer molding machine at 175 ° C and a molding pressure of 70 kg/cm ² . Further, the curing agent P2, the curing accelerator C1, the inorganic filler, the coupling agent, and the releasing agent are the same as described above.

From the results, it is understood that the epoxy resin of the present invention which is a mixture of a binaphthol structure and a biphenol structure has higher fluidity than a cured product of an epoxy resin having another structure. (Although the gel time is the same in seconds, the spiral flow is longer)

According to the above results, it is understood that the composition of the epoxy resin mixture of the present invention is excellent in fluidity, and further, the cured product is particularly excellent in flame retardancy and heat resistance, and it is known that a semiconductor sealing material requiring high functionality or a request is required. A high filler-filled film substrate material (including an interlayer insulating film) is useful.

The present invention has been described in detail with reference to the specific embodiments of the present invention. It is understood that various changes or 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. 8, 2012 (Japanese Patent Application No. 2012-246258). Further, all of the references cited herein are hereby incorporated by reference in their entirety.

[Industrial availability]

The epoxy resin composition containing the epoxy resin mixture of the present invention is useful for various composite materials, adhesives, paints, and the like which are represented by an insulating material for electronic parts, a laminate (printed wiring board, a build-up substrate, etc.) or CFRP.

Claims (5)

An epoxy resin mixture, wherein binaphthol (BINOL) and substituted or unsubstituted 4,4'-biphenol (wherein having a substituent in an aromatic ring, the number of substituents is 4 or less) , having a carbon number of 4 or less), which is obtained by reacting with epihalohydrin, which contains 1,1'-bis(2-glycidoxynaphthyl) and substituted or not The substituted 4,4'-bisglycidoxybiphenyl (wherein the substituent has a substituent in the aromatic ring, the number of substituents is 4 or less, and the number of carbon atoms is 4 or less). An epoxy resin mixture according to claim 1, wherein 1,1'-bis(2-glycidoxynaphthyl)(A) and substituted or unsubstituted 4,4'-epoxy The ratio of propoxybiphenyl (B) is A/B = 1 to 10. An epoxy resin composition comprising the epoxy resin mixture of claim 1 or 2 and a hardener. An epoxy resin composition comprising the epoxy resin mixture of claim 1 or 2 and a polymerization catalyst. A cured product obtained by hardening an epoxy resin composition of claim 3 or 4.