JP6492621B2 - Active ester compound, active ester resin, method for producing active ester compound, curable resin composition, cured product thereof, build-up adhesive film, semiconductor sealing material, prepreg, and circuit board - Google Patents

Description

  The present invention relates to an active ester compound, an active ester resin, a method for producing an active ester compound, and a curable resin composition having a low dielectric constant and dielectric loss tangent in the obtained cured product and excellent in heat resistance, heat decomposition resistance, and flame retardancy. Product, its cured product, build-up adhesive film, semiconductor sealing material, prepreg, and circuit board.

  A curable resin composition comprising an epoxy resin and a curing agent as an essential component exhibits excellent heat resistance and insulation in the cured product, and is therefore widely used in electronic component applications such as semiconductors and multilayer printed boards. Yes. Among these electronic component applications, in the technical field of multilayer printed circuit board insulating materials, in recent years, signal speed and frequency have been increasing in various electronic devices. However, with the increase in signal speed and frequency, it is becoming difficult to obtain a low dielectric loss tangent while maintaining a sufficiently low dielectric constant.

  Therefore, it is desired to develop a cured product that can exhibit a low dielectric constant and a low dielectric loss tangent even for a signal having a higher speed and a higher frequency. Patent Document 1 describes that an active ester compound obtained by arylesterifying a phenolic hydroxyl group in a phenol novolac resin is used as a curing agent for an epoxy resin in order to realize a low dielectric constant and a low dielectric loss tangent. ing.

  However, when the active ester compound described in Patent Document 1 is used as a curing agent for an epoxy resin, a cured product having a lower dielectric constant and dielectric loss tangent than conventional ones can be obtained, but the level has been increasing more and more recently. It did not meet the level. Furthermore, due to the trend toward higher frequency and smaller size in electronic parts, multilayer printed circuit board insulation materials are required to exhibit extremely high heat resistance and high flame resistance without using halogen flame retardants. When the active ester compound described in Literature 1 is used as a curing agent for epoxy resins, the active ester compound has an ester structure introduced therein, so that the crosslink density of the cured product is reduced, and thus obtained from the active ester compound. The cured product obtained was insufficient in heat resistance and heat decomposability and inferior in flame retardancy.

JP 7-82348 A

  Therefore, the problem to be solved by the present invention is an active ester compound, an active ester resin, and an active ester compound that have a low dielectric constant and dielectric loss tangent in the obtained cured product and are excellent in heat resistance, heat decomposition resistance, and flame retardancy. It is in providing the manufacturing method of this, a curable resin composition, its hardened | cured material, the adhesive film for buildup, a semiconductor sealing material, a prepreg, and a circuit board.

  As a result of intensive studies to solve the above problems, the inventors of the present invention have a diarylene [b, d] furan structure, and at least one arylene among two arylene groups forming the diarylene [b, d] furan structure. An active ester compound in which the group has a naphthylene skeleton and at least one of the two arylene groups has an ester structure site (z1) on the aromatic ring thereof is obtained in a dielectric product in the obtained cured product. The inventors have found that the ratio and dielectric loss tangent are low, and are excellent in heat resistance, heat decomposition resistance, and flame retardancy, and have completed the present invention.

  That is, the present invention has a diarylene [b, d] furan structure, and at least one of the arylene groups forming the diarylene [b, d] furan structure has a naphthylene skeleton, In addition, at least one of the two arylene groups is a benzoyloxy group, a naphthoyloxy group, or an alkyl group having 1 to 4 carbon atoms on the aromatic ring as a substituent on the aromatic ring. A benzoyloxy group having 1 to 7 carbon atoms, a naphthoyloxy group having 1 to 7 carbon atoms as a substituent on the aromatic ring, or an acyloxy group having 2 to 6 carbon atoms. The present invention relates to an active ester compound having an ester structure site (z1).

  The present invention further relates to an active ester resin containing the active ester compound.

  The present invention comprises a step of obtaining a phenol compound by reacting a compound (Q) having a quinone structure in the molecular structure with a compound (P) having a phenolic hydroxyl group in the molecular structure in the presence of an acid catalyst; And a step of reacting the phenol compound obtained in step 1 with a monocarboxylic acid or a halide thereof, and at least one of the compound (Q) having the quinone structure and the compound (P) having a phenolic hydroxyl group in the molecular structure. The compound relates to a method for producing an active ester compound having a naphthalene ring in the molecule.

  The present invention further relates to a curable resin composition containing the active ester compound or the active ester resin and a curable resin as essential components.

  The present invention further relates to a cured product obtained by curing the curable resin composition.

  The present invention further relates to a build-up adhesive film obtained by applying the curable resin composition onto a support film and drying it.

  The present invention further includes a curable resin composition and an inorganic filler, and the content of the inorganic filler is in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition. About.

  The present invention further relates to a prepreg obtained by semi-curing an impregnated substrate obtained by impregnating a reinforcing substrate with a varnished curable resin composition.

  The present invention further relates to a circuit board obtained by laminating a varnish obtained by diluting the curable resin composition in an organic solvent into a plate shape and laminating it with a copper foil, followed by heating and pressing.

  According to the present invention, an active ester compound, an active ester resin, a method for producing an active ester compound, and a curability that have a low dielectric constant and dielectric loss tangent and are excellent in heat resistance, heat decomposition resistance, and flame retardancy in the obtained cured product. A resin composition, a cured product thereof, a build-up adhesive film, a semiconductor sealing material, a prepreg, and a circuit board can be provided.

1 is a GPC chart of the phenol resin (A) obtained in Example 1. FIG. FIG. 2 is a GPC chart of the phenol resin (B) obtained in Example 2. FIG. 3 is a GPC chart of the phenol resin (C) obtained in Example 3. FIG. 4 is a GPC chart of the phenol resin (D) obtained in Example 4.

Hereinafter, the present invention will be described in detail.
The active ester compound of the present invention has a diarylene [b, d] furan structure, and at least one of the arylene groups forming the diarylene [b, d] furan structure has a naphthylene skeleton. It is a feature.

  As described above, since the active ester compound of the present invention has a diarylene [b, d] furan structure, the molecular structure is rigid and the aromatic ring concentration is high. Since the active ester compound of the present invention has a rigid molecular structure as described above, the molecular motion is suppressed, and the dielectric constant and dielectric constant of the cured product are low. Furthermore, since the active ester compound of the present invention has a characteristic of having a high aromatic ring concentration in addition to the rigid molecular structure as described above, it has excellent heat resistance, heat decomposition resistance, and flame retardancy in the cured product. It has excellent characteristics.

  In general, in order to improve the heat resistance of a cured product, a method of polyfunctionalizing an aromatic ring with a nodule group such as formaldehyde is known. However, a compound polyfunctionalized by such a method is aromatic. Since the rings are knotted by only one knot group, the knot group is easily cleaved during combustion, and the flame retardancy is low. In contrast, the active ester compound of the present invention has a diarylene [b, d] furan structure in which aromatic rings are fixed by two bonds of an ether bond and a direct bond. These bonded bonds are not easily cleaved and exhibit high flame retardancy in the cured product. Furthermore, since at least one of the two arylene groups has a naphthalene skeleton, the aromatic ring concentration is further increased, and the resulting cured product exhibits extremely excellent flame retardancy.

  Since the active ester compound of the present invention is further excellent in reactivity and excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product, the two arylene groups forming the diarylene [b, d] furan structure Of these, at least one arylene group has a naphthylene skeleton, each of the two arylene groups has an ester structure site (z1) on the aromatic ring, and at least one of the two arylene groups is an arylene group Preferably have an ester structure site (z1) or a hydroxyl group (z2) at the para position of the carbon atom bonded to the oxygen atom forming the furan ring.

  As such an active ester compound, for example, it has a molecular structure represented by the following structural formula (I) or the following structural formula (II), and at least one of the portions represented by OZ in the molecular structure. The compound whose one is the said ester structure site | part (z1) is mentioned.

In formulas (I) and (II), each R ¹ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group. It is. Z is a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as substituents on the aromatic ring, and an alkyl group having 1 to 4 carbon atoms substituted on the aromatic ring It is an ester-forming structure site (z1 ′) or a hydrogen atom (z2 ′) selected from any one of a naphthoyl group having 1 to 7 groups or an acyl group having 2 to 6 carbon atoms. Ar ¹ is a structural moiety represented by the following structural formula (i), and Ar ² is a structural moiety represented by the following structural formula (i) or (ii).

In formulas (i) and (ii), each R ² is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, m is an integer of 0 to 4, and n is an integer of 0 to 3. When m or n is 2 or more, R ² may be the same or different from each other. Z is a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as substituents on the aromatic ring, and an alkyl group having 1 to 4 carbon atoms substituted on the aromatic ring It is an ester-forming structure site (z1 ′) or a hydrogen atom (z2 ′) selected from any one of a naphthoyl group having 1 to 7 groups or an acyl group having 2 to 6 carbon atoms. x and y each represent a bonding point with the naphthalene ring and represent that they are bonded to adjacent carbon atoms of the naphthalene ring so as to form a furan ring with the oxygen atom. In formula (i), the group represented by R ² or O—Z bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings constituting the naphthalene ring.

  As described above, Z in the general formulas (I), (II), (i), and (ii) represents a benzoyl group, a naphthoyl group, or an alkyl group having 1 to 4 carbon atoms as a substituent on the aromatic ring. As a benzoyl group having 1 to 5 carbon atoms, a naphthoyl group having 1 to 7 carbon atoms as a substituent on an aromatic ring, or an acyl group having 2 to 6 carbon atoms The selected ester-forming structural site (z1 ′) or hydrogen atom (z2 ′).

  Examples of the benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as substituents on the aromatic ring include 2,4-dimethylbenzoyl group, 2,6-dimethylbenzoyl group, 2,4,4, 6-trimethylbenzoyl group, 2-ethylbenzoyl group, 4-ethylbenzoyl group 2-t-butyl-4-ethylbenzoyl group, 4-i-propylbenzoyl group, 4-t-butylbenzoyl group, 2,6-di -T-butylbenzoyl group etc. are mentioned.

  Examples of the naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms as substituents on the aromatic ring include 2-methyl-1-naphthol group, 4-methyl-1-naphthoyl group, 2- Ethyl-1-naphthoyl group, 3-methyl-4-ethyl-2-naphthoyl group, 2-propyl-1-naphthoyl group, 2-propyl-4-ethyl-1-naphthoyl group, 6-propyl-2-naphthoyl group 2-t-butyl-1-naphthyl group, 3-t-butyl-1-naphthyl group, 4-t-butyl-1-naphthyl group, and the like. Examples of the acyl group having 2 to 6 carbon atoms include acetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, caproyl group and the like.

  Examples of the acyl group having 2 to 6 carbon atoms include acetyl group, propionyl group, butanoyl group, pentanoyl group and hexanoyl group.

  Among the above-mentioned structures, the ester-forming structure site (z1 ′) is particularly excellent in dielectric characteristics at the time of curing, and from the point that reactivity when an epoxy resin is used as a curable resin is good. An acetyl group, a benzoyl group, or a naphthoyl group is preferable, and a benzoyl group is particularly preferable.

  In addition, in the active ester resin containing the active ester compound of the present invention, a cured product having a lower dielectric constant and dielectric loss tangent can be obtained. Therefore, the presence of the ester-forming structure site (z1 ′) and the hydrogen atom (z2 ′) The proportion is preferably such that the ester-forming structure portion (z1 ′) is 40% or more with respect to the total of the ester-forming structure portion (z1 ′) and the hydrogen atom (z2 ′), and 65% It is more preferable that the ratio is as described above. That is, the ratio of the carbonyloxy group and the phenolic hydroxyl group in the active ester resin is preferably 40% or more and 65% or more with respect to the total number of functional groups. Is more preferable. Thus, all of Z in the active ester resin may be the ester-forming structure site (z1 ′), but a part of Z is a hydrogen atom (z2 ′), that is, a phenolic hydroxyl group. By having a part of it, curability becomes good and the effect of improving heat resistance becomes remarkable.

  In the active ester resin of the present invention, the functional group equivalent based on the total number of functional groups of the carbonyloxy group and the phenolic hydroxyl group in the active ester resin is excellent in curability, and is in the range of 110 to 310 g / eq. It is preferable that

  The active ester compounds represented by the structural formulas (I) and (II) include, for example, a compound (Q) having a quinone structure in the molecular structure and a compound (P) having a phenolic hydroxyl group in the molecular structure. A step of reacting in a temperature range of 40 to 180 ° C. under non-catalytic or acid catalyst conditions to obtain a phenol compound or a phenol resin, and the phenol compound or phenol resin obtained in the above step and a monocarboxylic acid or a halide thereof. A reaction method, wherein at least one of the compound (Q) having the quinone structure and the compound (P) having a phenolic hydroxyl group in the molecular structure has a naphthalene ring in the molecule. It is manufactured by the manufacturing method which is a compound having. When the active ester compound of the present invention is obtained by such a method, an arbitrary component can be selectively obtained depending on the reaction conditions, or an active ester resin that is a mixture of plural kinds of active ester compounds can be obtained. In addition, when obtaining an active ester compound, you may obtain by isolating only arbitrary components from the active ester resin which is a mixture.

  Examples of the compound (Q) having a quinone structure include compounds represented by the following structural formula (Q1) or (Q2).

In formula (Q1) or (Q2), each R ¹ is independently a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group. It is.

  Specific examples of the compound represented by the structural formula (Q1) or (Q2) include parabenzoquinone, 2-methylbenzoquinone, 2,3,5-trimethyl-benzoquinone, naphthoquinone, and these benzoquinones and naphthoquinones. Examples thereof include compounds in which one to a plurality of alkyl groups having 1 to 4 carbon atoms, alkoxy groups having 1 to 4 carbon atoms, aryl groups, or aralkyl groups are substituted. These may be used alone or in combination of two or more. Among these, naphthoquinone is preferably used because an active ester compound having excellent heat resistance, heat decomposition resistance, and flame retardancy in the cured product can be obtained.

  Examples of the compound (P) having a phenolic hydroxyl group include compounds represented by the following structural formula (P1) or (P2).

In formula (P1) or (P2), each R ² is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, m is an integer of 0 to 4, n is an integer of 0 to 3, and p and q are integers of 2 or more. When m or n is 2 or more, R ² may be the same or different from each other. In the formula (P2), the OH group bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings constituting the naphthalene ring.

  Specific examples of the compound represented by the structural formula (P1) or (P2) include 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene, and these dihydroxybenzenes, dihydroxynaphthalene, alkyl groups having 1 to 4 carbon atoms, carbon atoms Examples include compounds in which one to plural alkoxy groups, aryl groups, or aralkyl groups of formulas 1 to 4 are substituted. These may be used alone or in combination of two or more. Among them, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, an active ester compound excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product or an active ester resin containing the active ester compound can be obtained. Any of 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene and 2,7-dihydroxynaphthalene is preferable, and 2,7-dihydroxynaphthalene is particularly preferable.

  The reaction between the compound (Q) having a quinone structure and the compound (P) having a phenolic hydroxyl group proceeds under non-catalytic conditions because of its high reactivity, but is preferably performed using an acid catalyst as appropriate. . Examples of the acid catalyst used here include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid, boron trifluoride, anhydrous aluminum chloride, and zinc chloride. And Lewis acid. When these acid catalysts are used, they should be used in an amount of 5.0% by mass or less based on the total mass of the compound (Q) having the quinone structure and the compound (P) having a phenolic hydroxyl group in the molecular structure. Is preferred.

  The reaction is preferably performed under solvent-free conditions, but may be performed in an organic solvent as necessary. Examples of the organic solvent used here include methyl cellosolve, isopropyl alcohol, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. When these organic solvents are used, since the reaction efficiency is improved, the organic solvent is used for 100 parts by mass in total of the compound (Q) having a quinone structure and the compound (P) having a phenolic hydroxyl group in the molecular structure. It is preferable to use it in the ratio which becomes the range of 50-200 mass parts.

  After completion of the reaction between the compound (Q) having a quinone structure in the molecular structure and the compound (P) having a phenolic hydroxyl group in the molecular structure, a phenol compound or a phenol resin can be obtained by drying under reduced pressure. I can do it.

  As a phenol compound contained in such a phenol compound or a phenol resin, the compound etc. which are represented with the following structures can be mentioned, for example.

In formulas (a1) to (a4), each R ² is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, m is an integer of 0 to 4, and n is an integer of 0 to 3. When m or n is 2 or more, R ² may be the same or different from each other. x and y each represent a bonding point with the naphthalene ring and represent that they are bonded to adjacent carbon atoms of the naphthalene ring so as to form a furan ring with the oxygen atom. In formulas (a1) to (a3), the R ² and OH groups bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings constituting the naphthalene ring.

  In the reaction, in addition to the compounds represented by the structural formulas (a1) to (a4), for example, compounds represented by the following structural formulas (a1-1) to (a4-1) are generated.

  In formulas (a1-1) to (a4-1), k and i each represent an integer of 1 to 2. x and y each represent a bonding point with the naphthalene ring and represent bonding to adjacent carbons so as to form a furan ring.

  In Structural Formula (a1-1), (a3-1), or (a4-1), k is an integer of 1 to 2. Here, a compound corresponding to the case where the value of k is 1 (hereinafter abbreviated as “binuclear compound (α1)”) reacts with a monocarboxylic acid compound or a halide thereof, thereby causing a dielectric constant in the cured product. And an active ester compound having a low dielectric loss tangent and excellent heat resistance, heat decomposition resistance, and flame retardancy. On the other hand, in the compound represented by the structural formula (a1-1), (a3-1), or (a4-1), a compound corresponding to the case where the value of k is 2 (hereinafter referred to as “trinuclear compound (α2 ) ”Is abbreviated as“. ”Is a cyanate ester that is more excellent in heat resistance in a cured product by reacting with a monocarboxylic acid compound or its halide because the molecular structure is more rigid and has a higher aromatic ring concentration. Give compound.

  In addition, when a phenol resin contains the binuclear compound (α1) or the trinuclear compound (α2) represented by the structure as described above, the binuclear compound (α1) or the trinuclear compound (α2) Is maintained in the subsequent reaction, and in the finally obtained active ester resin, the content of the binuclear active ester compound (β1) and the trinuclear active ester compound β2) is approximately the same. Become. Therefore, when it is desired to obtain an active ester resin having excellent heat resistance, heat decomposition resistance, flame retardancy and dielectric properties in a cured product, a dinuclear compound (α1) or a trinuclear compound (α2) contained in a phenol resin. The content of is important.

  The monocarboxylic acid compound to be reacted with the obtained phenol compound or phenol resin or its halide is specifically an alkyl having 1 to 4 carbon atoms as a substituent on the phenyl group, naphthyl group or aromatic ring. Having a hydrocarbon structure selected from the group consisting of phenyl groups having 1 to 5 groups, naphthyl groups, and naphthyl groups having 1 to 7 alkyl groups having 1 to 4 carbon atoms as substituents on the aromatic ring Aromatic monocarboxylic acid or its halide (hereinafter abbreviated as “aromatic monocarboxylic acid or its halide”), or a saturated fatty acid having 2 to 5 carbon atoms or its halide (hereinafter referred to as “saturated”). Abbreviated as “fatty acid or a halide thereof”).

  Specific examples of the aromatic monocarboxylic acid or its halide include benzoic acid, methylbenzoic acid, 2,4-dimethylbenzoic acid, 2,6-dimethylbenzoic acid, and 2,4,6-trimethylbenzoic acid. Alkyl benzoic acid such as 2-ethylbenzoic acid, 4-ethylbenzoic acid, 2-t-butyl-4-ethylbenzoic acid, 4-i-propylbenzoic acid and 4-t-butylbenzoic acid, 1-naphthoic acid 2-naphthoic acid, 2-methyl-1-naphthoic acid, 4-methyl-1-naphthoic acid, 2-ethyl-1-naphthoic acid, 3-methyl-4-ethyl-2-naphthoic acid, 2-propyl- 1-naphthoic acid, 2-propyl-4-ethyl-1-naphthoic acid, 6-propyl-2-naphthoic acid, 2-t-butyl-1-naphthoic acid, 3-t-butyl-1-naphthoic acid, 4 -T-butyl-1-naphth Et acid, as well as their acid fluorides, acid chlorides, acid bromides, acid halides such as acid iodide and the like.

  In addition, the saturated fatty acid or its halide specifically includes ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, and their acid fluorides, acid chlorides, acid bromides, and acid iodides. And acid halides.

  Among these, an acid chloride of benzoic acid or ethanoic acid is particularly preferable from the viewpoint of excellent dielectric properties.

  Specific examples of the reaction between the phenol compound or the phenol resin and the monocarboxylic acid compound or a halide thereof include a method of reacting them with a basic catalyst.

  The reaction ratio between the phenol compound or phenol resin and the monocarboxylic acid compound or halide thereof is the ratio of the phenolic hydroxyl group in the phenol compound or phenol resin to the carboxyl group or acid halide group in the monocarboxylic acid compound or halide. Equivalent ratio [OH in phenolic compound or phenolic resin / carboxyl compound in its halide or carboxyl group or acid halide group in its halide] is a ratio of 1.0 / 0.40 to 1.0 / 1.0. However, it is preferable from the point that the solvent solubility of the obtained active ester resin is good.

  Examples of the alkali catalyst that can be used here include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Of these, sodium hydroxide and potassium hydroxide are particularly preferred because they can be used in the form of an aqueous solution and the productivity is good.

  In the reaction of the phenol compound or phenol resin with the carboxylic acid compound or its halide, it is preferable to use each raw material component dissolved in an organic solvent for the reaction. Examples of the organic solvent used here include toluene, dichloromethane and the like. It is done.

  After completion of the reaction, an appropriate amount of water is added to the reaction solution to dissolve the produced salt. Thereafter, washing with water is repeated to remove the generated salt in the system, and then the product is further purified by dehydration and filtration, and the organic solvent is removed by distillation to obtain the target active ester compound or the active ester resin containing the active ester compound Can be obtained.

  Note that the active ester compound of the present invention has a dielectric constant, dielectric constant, and dielectric constant in the cured product obtained in any case as long as it has a structure represented by the general formulas (I) and (II). It is characterized by low tangent and excellent heat resistance, heat decomposition resistance, and flame retardancy. Below, the more preferable aspect of the active ester compound which has a structure represented by the said general formula (I) and (II) is demonstrated.

  Specific examples of the active ester compounds represented by the structural formulas (I) and (II) include those having a molecular structure represented by any of the following structural formulas (1) to (4).

In the formulas (1) to (4), Z is a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic ring, and 1 to 5 carbon atoms. A naphthoyl group having 1 to 7 alkyl groups as substituents on the aromatic ring, or an ester-forming structural site (z1 ′) selected from an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (Z2 ′), and at least one of Z is an ester-forming structural site (z1 ′). R ² is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, m is an integer of 0 to 4, and n is It is an integer of 0-3. When m or n is 2 or more, R ² may be the same or different from each other. x and y each represent a bonding point with the naphthalene ring and represent that they are bonded to adjacent carbon atoms of the naphthalene ring so as to form a furan ring with the oxygen atom. In the formulas (1) to (3), the group represented by R ² or OZ bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings constituting the naphthalene ring. Good.

  More specifically, the active ester compound represented by the structural formula (1) includes active ester compounds represented by the following structural formulas (1-1) to (1-9).

  In formulas (1-1) to (1-9), Z represents a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic ring, a carbon atom Ester-forming structural site (z1 ′) selected from either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 alkyl groups as substituents on the aromatic ring or an acyl group having 2 to 6 carbon atoms Or a hydrogen atom (z2 ′), and at least one of Z is an ester-forming structural site (z1 ′).

  The active ester compound represented by the above (1) represented by the structural formulas (1-1) to (1-9) includes, for example, parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure. The compound (P) having a phenolic hydroxyl group in the molecular structure can be produced by the above-described method using various dihydroxynaphthalenes. At this time, since the reaction ratio of parabenzoquinone and dihydroxynaphthalene can produce the compound represented by the structural formula (1) with high efficiency, the amount of dihydroxynaphthalene is 0.1 to 10.0 mol per 1 mol of parabenzoquinone. It is preferable that it is the ratio used as a range.

  Among the active ester compounds represented by any one of the structural formulas (1-1) to (1-9), since the cured product is superior in heat resistance, heat decomposition resistance, and flame retardancy, the structural formula ( The compound represented by 1-8) or (1-9) is preferred. That is, an active ester compound obtained by using 2,7-dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group in the molecular structure is preferable.

  The active ester resin containing the active ester compound represented by the structural formula (1) may further contain an active ester compound other than these. Especially, since it becomes active ester resin with high heat resistance, it is preferable to contain the polyfunctional compound represented by following Structural formula (1 ').

  In the formula (1 ′), Z is a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic ring, and an alkyl having 1 to 4 carbon atoms. An ester-forming structure site (z1 ′) selected from either a naphthoyl group having 1 to 7 groups as substituents on the aromatic ring, or an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2 ′) And at least one of Z is an ester-forming structural site (z1 ′). k is an integer of 1-2. Note that the group represented by OZ bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings constituting the naphthalene ring.

  In this case, the content of each component in the active ester resin is such that the content of the dinaphtho [b, d] furan compound represented by the structural formula (1) is in the range of 5 to 60% as an area ratio in GPC measurement. In addition, it is preferable that the content of the polyfunctional compound represented by the structural formula (1 ′) is in the range of 10 to 70% in terms of area ratio in GPC measurement.

In addition, in this invention, the content rate of each component in active ester resin is a ratio of the peak area of each said component with respect to the total peak area of active ester resin computed from the GPC measurement data by the following conditions.
<GPC measurement conditions>
Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Used polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

  More specifically, the active ester compound represented by the structural formula (2) includes an active ester compound represented by any one of the following structural formulas (2-1) to (2-9).

  In formulas (2-1) to (2-9), Z represents a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic ring, a carbon atom Ester-forming structural site (z1 ′) selected from either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 alkyl groups as substituents on the aromatic ring or an acyl group having 2 to 6 carbon atoms Or a hydrogen atom (z2 ′), and at least one of Z is an ester-forming structural site (z1 ′).

  The active ester compound represented by the structural formula (2) represented by the structural formulas (2-1) to (2-9) is, for example, 2 as the compound (Q) having a quinone structure in the molecular structure. , 3,5-trimethyl-parabenzoquinone can be produced by the aforementioned method using various dihydroxynaphthalenes as the compound (P) having a phenolic hydroxyl group in the molecular structure. At this time, since the reaction ratio of 2,3,5-trimethyl-parabenzoquinone and dihydroxynaphthalene can produce the compound represented by the structural formula (2) with high efficiency, 2,3,5-trimethyl-parabenzoquinone 1 It is preferable that the ratio of dihydroxynaphthalene is in the range of 0.1 to 10.0 moles per mole.

  Among the active ester compounds represented by any one of the structural formulas (2-1) to (2-9), the cured product is superior in heat resistance, heat decomposition resistance, and flame retardancy. The compound represented by 2-8) or (2-9) is preferred. That is, an active ester compound obtained by using 2,7-dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group in the molecular structure is preferable.

  The active ester resin containing the active ester compound represented by the structural formula (2) may further contain an active ester compound other than these. Especially, since it becomes active ester resin with high heat resistance, it is preferable to contain the polyfunctional compound represented by following Structural formula (2 ').

  In the formula (2 ′), Z represents a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 carbon atoms as a substituent on the aromatic ring, and an alkyl having 1 to 4 carbon atoms. An ester-forming structure site (z1 ′) selected from either a naphthoyl group having 1 to 7 groups as substituents on the aromatic ring, or an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2 ′) And at least one of Z is an ester-forming structural site (z1 ′). Note that the group represented by OZ bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings constituting the naphthalene ring.

  In this case, the content of each component in the active ester resin is such that the content of the dinaphtho [b, d] furan compound represented by the structural formula (2) is in the range of 50 to 95% in terms of the area ratio in GPC measurement. In addition, it is preferable that the content of the polyfunctional compound represented by the structural formula (2 ′) is in the range of 1 to 50% in terms of area ratio in GPC measurement.

  More specifically, the active ester compound represented by the structural formula (3) includes an active ester compound represented by any one of the following structural formulas (3-1) to (3-9).

  In formulas (3-1) to (3-9), Z represents a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic ring, a carbon atom Ester-forming structural site (z1 ′) selected from either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 alkyl groups as substituents on the aromatic ring or an acyl group having 2 to 6 carbon atoms Or a hydrogen atom (z2 ′), and at least one of Z is an ester-forming structural site (z1 ′).

  The active ester compound represented by the structural formula (3) represented by the structural formulas (3-1) to (3-9) is, for example, 1 as the compound (Q) having a quinone structure in the molecular structure. , 4-naphthoquinone can be produced by the above-described method using various dihydroxynaphthalenes as the compound (P) having a phenolic hydroxyl group in the molecular structure. At this time, since the reaction rate of 1,4-naphthoquinone and dihydroxynaphthalene can produce the compound represented by the structural formula (1) with high efficiency, the amount of dihydroxynaphthalene is 0.1 with respect to 1 mol of 1,4-naphthoquinone. The ratio is preferably in the range of ˜10.0 mol.

  Among the active ester compounds represented by any one of the structural formulas (3-1) to (3-9), since the cured product is superior in heat resistance, heat decomposition resistance, and flame retardancy, the structural formula ( The compound represented by 3-8) or (3-9) is preferred. That is, an active ester compound obtained by using 2,7-dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group in the molecular structure is preferable.

  The active ester resin containing the active ester compound represented by the structural formula (3) may contain other active ester compounds other than these. When the active ester resin contains another active ester compound other than the dinaphtho [b, d] furan compound represented by the structural formula (3), the dinaphtho represented by the structural formula (3) in the active ester resin The content of the [b, d] furan compound is preferably in the range of 5 to 70% in terms of area ratio in GPC measurement.

  Specific examples of other active ester compounds are polyfunctional compounds represented by the following structural formula (3 ′) or (3 ″) because they are active ester resins having high heat resistance.

  In formulas (3 ′) to (3 ″), Z represents a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic ring, and the number of carbon atoms An ester-forming structure site (z1 ′) selected from either a naphthoyl group having 1 to 7 alkyl groups as substituents on the aromatic ring, or an acyl group having 2 to 6 carbon atoms, or It is a hydrogen atom (z2 ′), and at least one of Z is an ester-forming structural site (z1 ′), k is an integer of 1 to 2, and is represented by OZ bonded to the naphthalene ring. The group may be bonded to any aromatic ring among the aromatic rings constituting the naphthalene ring. X and y in the formula (3 ″) indicate the point of attachment to the naphthalene ring and form a furan ring. To bond to adjacent carbons.

  When the active ester resin contains the polyfunctional compound represented by the structural formula (3 ′), the content is preferably in the range of 2 to 60% as an area ratio in GPC measurement. Moreover, when the active ester resin contains the polyfunctional compound represented by the structural formula (3 ″), the content is preferably in the range of 2 to 40% in terms of area ratio in GPC measurement.

  More specifically, the active ester compound represented by the structural formula (4) includes an active ester compound represented by any one of the following structural formulas (4-1) to (4-4).

  In formulas (4-1) to (4-4), Z represents a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic ring, a carbon atom Ester-forming structural site (z1 ′) selected from either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 alkyl groups as substituents on the aromatic ring or an acyl group having 2 to 6 carbon atoms Or a hydrogen atom (z2 ′), and at least one of Z is an ester-forming structural site (z1 ′).

  The active ester compound represented by the structural formula (4) represented by the structural formulas (4-1) to (4-9) is, for example, 1 as the compound (Q) having a quinone structure in the molecular structure. , 4-naphthoquinone can be produced by the above-described method using various dihydroxybenzenes as the compound (P) having a phenolic hydroxyl group in the molecular structure. At this time, since the reaction rate of 1,4-naphthoquinone and dihydroxybenzene can produce the compound represented by the structural formula (1) with high efficiency, the amount of dihydroxybenzene is 0.1 per mol of 1,4-naphthoquinone. The ratio is preferably in the range of ˜10.0 mol.

  Among the active ester compounds represented by any one of the structural formulas (4-1) to (4-4), since the cured product is superior in heat resistance, heat decomposition resistance, and flame retardancy, the structural formula ( The compound represented by 4-2) or (4-3) is preferred. That is, an active ester compound obtained by using 1,3-dihydroxybenzene as the compound (P) having a phenolic hydroxyl group in the molecular structure is preferable.

  The active ester resin containing the active ester compound represented by the structural formula (4) may further contain an active ester compound other than these. Especially, since it becomes active ester resin with high heat resistance, it is preferable to contain the polyfunctional compound represented by following Structural formula (4 ').

  In the formula (4 ′), Z is a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 carbon atoms as a substituent on the aromatic ring, and an alkyl having 1 to 4 carbon atoms. An ester-forming structure site (z1 ′) selected from either a naphthoyl group having 1 to 7 groups as substituents on the aromatic ring, or an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2 ′) And at least one of Z is an ester-forming structural site (z1 ′). k and i are integers of 1 to 2, respectively.

  In this case, the content of each component in the active ester resin is such that the content of the dinaphtho [b, d] furan compound represented by the structural formula (4) is in the range of 5 to 70% in terms of the area ratio in GPC measurement. In addition, the content of the polyfunctional compound represented by the structural formula (4 ′) is preferably in the range of 1 to 60% in terms of the area ratio in GPC measurement.

  Among these exemplified active ester compounds, the active ester compound represented by any one of the structural formulas (1) to (3) has excellent balance with heat resistance, heat decomposition resistance, and flame retardancy in a cured product. The active ester compound represented by the structural formula (3) is particularly preferable.

  Since the active ester resin containing the active ester compound of the present invention is excellent in curability, the ester equivalent is preferably in the range of 100 to 350 g / eq.

  Next, the curable resin composition of the present invention will be described. The curable resin composition of the present invention comprises the active ester compound or active ester resin of the present invention described in detail above and a curable resin as essential components. Examples of the curable resin include an epoxy resin.

  The epoxy resin used here is bisphenol A type epoxy resin, bisphenol F type epoxy resin, biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, Tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co Denatured novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin, biphenyl modified novolak type epoxy resin Resins. Among these epoxy resins, it is preferable to use a tetramethyl biphenol type epoxy resin, a biphenyl aralkyl type epoxy resin, or a novolac type epoxy resin from the viewpoint that a cured product having excellent flame retardancy can be obtained.

  The compounding quantity of the said active ester compound in the curable resin composition of this invention or the said active ester resin, and an epoxy resin is a thing in the said active ester resin from the point from which sclerosis | hardenability and various physical properties of hardened | cured material become favorable. It is preferable that the ratio of the epoxy group in the epoxy resin is 0.8 to 1.2 equivalents with respect to a total of 1 equivalent of the carbonyloxy group and the phenolic hydroxyl group.

  In addition to the above-mentioned active ester resin and epoxy resin, the curable resin composition of the present invention may be used in combination with another curing agent for epoxy resin. As the curing agent for epoxy resin that can be used here, for example, curing agents such as amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like can be used. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, and guanidine derivatives. Examples of the amide compound include dicyandiamide, Examples include polyamide resins synthesized from dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride. , Methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resins, cresol novolac resins, Aromatic hydrocarbon formaldehyde resin modified phenolic resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol -Cresol-condensed novolak resin, biphenyl-modified phenolic resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified Examples thereof include polyhydric phenol compounds such as phenol resins (polyhydric phenol compounds in which phenol nuclei are linked with melamine or benzoguanamine).

  Among these, those containing a large amount of an aromatic skeleton in the molecular structure are preferable from the viewpoint of flame retardancy, and specifically, phenol novolac resins, cresol novolac resins, aromatic hydrocarbon formaldehyde resin-modified phenol resins, phenol aralkyls. Resins, naphthol aralkyl resins, naphthol novolak resins, naphthol-phenol co-condensed novolak resins, naphthol-cresol co-condensed novolak resins, biphenyl-modified phenol resins, biphenyl-modified naphthol resins, and aminotriazine-modified phenol resins are preferred because of their excellent flame retardancy. .

  In the case of using the epoxy resin curing agent described above in combination, the amount used thereof is fully cured including the active ester resin since the effect of the present invention is excellent in low dielectric constant and low dielectric loss tangent. It is preferable that it is the range of 10-50 mass% in an agent component.

  Moreover, a hardening accelerator can also be suitably used together with the curable resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a semiconductor encapsulating material, it is excellent in curability, heat resistance, electrical characteristics, moisture resistance reliability, etc., so that triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo is used for tertiary amines. -[5.4.0] -undecene (DBU) is preferred.

  Since the curable resin composition of the present invention described in detail above is excellent in solvent solubility, it can be used after diluted with an organic solvent. Examples of the organic solvent that can be used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The amount used can be appropriately selected depending on the application. For example, in printed wiring board applications, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, dimethylformamide, and the non-volatile content of 40 to 80% by mass. It is preferable to use in the ratio which becomes. On the other hand, in build-up adhesive film applications, as organic solvents, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, It is preferable to use carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like, and the nonvolatile content is 30 to 60% by mass. It is preferable to use in proportions.

  Further, the curable resin composition is made of a non-halogen flame retardant that substantially does not contain a halogen atom, for example, in the field of printed wiring boards, in order to exhibit flame retardancy, as long as reliability is not lowered. You may mix | blend.

  Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organic metal salt flame retardants. The flame retardants may be used alone or in combination, and a plurality of flame retardants of the same system may be used, or different types of flame retardants may be used in combination.

  As the phosphorus flame retardant, either inorganic or organic can be used. Examples of the inorganic compounds include red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphates such as ammonium polyphosphate, and inorganic nitrogen-containing phosphorus compounds such as phosphate amide. .

  The red phosphorus is preferably subjected to a surface treatment for the purpose of preventing hydrolysis and the like. Examples of the surface treatment method include (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, water A method of coating with an inorganic compound such as titanium oxide, bismuth oxide, bismuth hydroxide, bismuth nitrate or a mixture thereof; (ii) an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide; and A method of coating with a mixture of a thermosetting resin such as a phenol resin, (iii) thermosetting of a phenol resin or the like on a coating of an inorganic compound such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, or titanium hydroxide For example, a method of double coating with a resin may be used.

  Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7- Examples thereof include cyclic organophosphorus compounds such as dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected according to the type of phosphorus-based flame retardant, other components of the curable resin composition, and the desired degree of flame retardancy. For example, active ester resins, epoxy resins, In 100 parts by mass of the curable resin composition containing all of the non-halogen flame retardant and other fillers and additives, 0.1 to 2.0 parts by mass when red phosphorus is used as the non-halogen flame retardant In the case of using an organophosphorus compound, it is preferably blended in the range of 0.1 to 10.0 parts by mass, particularly in the range of 0.5 to 6.0 parts by mass. It is preferable to mix.

  In addition, when using the phosphorous flame retardant, the phosphorous flame retardant may be used in combination with hydrotalcite, magnesium hydroxide, boric compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, etc. Good.

  Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable.

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, (i) guanylmelamine sulfate, melem sulfate, sulfate (Iii) co-condensates of phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol with melamines such as melamine, benzoguanamine, acetoguanamine and formguanamine and formaldehyde, (iii) (Ii) a mixture of a co-condensate of (ii) and a phenolic resin such as a phenol formaldehyde condensate, (iv) those obtained by further modifying (ii) and (iii) with tung oil, isomerized linseed oil, etc It is.

  Specific examples of the cyanuric acid compound include cyanuric acid and cyanuric acid melamine.

  The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, the active ester resin It is preferable to mix in the range of 0.05 to 10 parts by mass in 100 parts by mass of the curable resin composition containing all of epoxy resin, non-halogen flame retardant and other fillers and additives. It is preferable to mix | blend in 1-5 mass parts.

  Moreover, when using the said nitrogen-type flame retardant, you may use together a metal hydroxide, a molybdenum compound, etc.

  The silicone flame retardant is not particularly limited as long as it is an organic compound containing a silicon atom, and examples thereof include silicone oil, silicone rubber, and silicone resin.

  The amount of the silicone-based flame retardant is appropriately selected depending on the type of the silicone-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, the active ester resin It is preferable to mix in the range of 0.05 to 20 parts by mass in 100 parts by mass of the curable resin composition containing all of epoxy resin, non-halogen flame retardant and other fillers and additives. Moreover, when using the said silicone type flame retardant, you may use a molybdenum compound, an alumina, etc. together.

  Examples of the inorganic flame retardant include metal hydroxide, metal oxide, metal carbonate compound, metal powder, boron compound, and low melting point glass.

  Specific examples of the metal hydroxide include aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide and the like.

  Specific examples of the metal oxide include, for example, zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, and cobalt oxide. Bismuth oxide, chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

  Specific examples of the metal carbonate compound include zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, and titanium carbonate.

  Specific examples of the metal powder include aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, and tin.

  Specific examples of the boron compound include zinc borate, zinc metaborate, barium metaborate, boric acid, and borax.

Specific examples of the low-melting-point glass include, for example, Ceeley (Bokusui Brown), hydrated glass SiO ₂ —MgO—H ₂ O, PbO—B ₂ O ₃ system, ZnO—P ₂ O ₅ —MgO system, P ₂ O ₅ —B ₂ O ₃ —PbO—MgO, P—Sn—O—F, PbO—V ₂ O ₅ —TeO ₂ , Al ₂ O ₃ —H ₂ O, lead borosilicate, etc. The glassy compound can be mentioned.

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, the active ester resin , Epoxy resin, non-halogen flame retardant, and other fillers and additives, etc. are preferably blended in the range of 0.05 to 20 parts by mass, especially in the range of 0.05 to 20 parts by mass. It is preferable to mix | blend in 5-15 mass parts.

  Examples of the organic metal salt flame retardant include ferrocene, acetylacetonate metal complex, organic metal carbonyl compound, organic cobalt salt compound, organic sulfonic acid metal salt, metal atom and aromatic compound or heterocyclic compound or an ionic bond or Examples thereof include a coordinated compound.

  The amount of the organic metal salt flame retardant is appropriately selected depending on the type of the organic metal salt flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. , Active ester resins, epoxy resins, non-halogen flame retardants and other fillers and additives, etc., in 100 parts by mass of curable resin composition may be blended in the range of 0.005 to 10 parts by mass. preferable.

  An inorganic filler can be mix | blended with the curable resin composition of this invention as needed. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. When particularly increasing the blending amount of the inorganic filler, it is preferable to use fused silica. The fused silica can be used in either a crushed shape or a spherical shape. However, in order to increase the blending amount of the fused silica and suppress an increase in the melt viscosity of the molding material, it is preferable to mainly use a spherical shape. In order to further increase the blending amount of the spherical silica, it is preferable to appropriately adjust the particle size distribution of the spherical silica. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 20% by mass or more with respect to the total amount of the curable resin composition. Moreover, when using for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  Various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, an emulsifier, can be added to the curable resin composition of this invention as needed.

  The curable resin composition of the present invention can be obtained by uniformly mixing the above-described components and can be easily cured by heating to obtain a cured product. Specifically, it is obtained by uniformly mixing the above-described components, and is easily cured by heating the curable resin composition at a temperature of about 100 ° C. or higher, preferably 20 to 250 ° C. It can be. Examples of the cured product thus obtained include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Examples of uses in which the curable resin composition of the present invention is used include hard printed wiring board materials, flexible wiring board resin compositions, insulating materials for circuit boards such as build-up board interlayer insulating materials, semiconductor sealing materials, Examples include conductive pastes, build-up adhesive films, resin casting materials, and adhesives. Among these various applications, in hard printed wiring board materials, insulating materials for electronic circuit boards, and adhesive film for build-up, passive parts such as capacitors and active parts such as IC chips are embedded in so-called electronic parts. It can be used as an insulating material for a substrate. Among these, circuits such as hard printed wiring board materials, flexible wiring board resin compositions, build-up board interlayer insulation materials, etc., taking advantage of the characteristics of high heat resistance, especially low dielectric constant and low dielectric loss tangent It is preferably used for a substrate material and a semiconductor sealing material.

  Here, the circuit board of the present invention is manufactured by obtaining a varnish obtained by diluting a curable resin composition in an organic solvent, laminating a varnish formed in a plate shape with a copper foil, and heating and pressing. Is. Specifically, for example, to produce a hard printed wiring board, the varnish-like curable resin composition containing the organic solvent is further varnished by adding an organic solvent, and this is impregnated into a reinforcing base material. A method of obtaining the prepreg of the present invention produced by semi-curing, and laminating a copper foil on the prepreg and heating and press-bonding may be mentioned. Examples of the reinforcing substrate that can be used here include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. If this method is described in further detail, first, the varnish-like curable resin composition is heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C., thereby being a prepreg which is a cured product. Get. At this time, the mass ratio of the curable resin composition to be used and the reinforcing substrate is not particularly limited, but it is usually preferable that the resin content in the prepreg is 20 to 60% by mass. Next, the prepreg obtained as described above is laminated by a conventional method, and a copper foil is appropriately stacked, and then subjected to thermocompression bonding at 170 to 250 ° C. for 10 minutes to 3 hours under a pressure of 1 to 10 MPa, A target circuit board can be obtained.

In order to produce a flexible wiring board from the curable resin composition of the present invention, an active ester resin, an epoxy resin, and an organic solvent are blended, and using a coating machine such as a reverse roll coater or a comma coater, electrical insulation Apply to film. Subsequently, it heats at 60-170 degreeC for 1 to 15 minutes using a heating machine, volatilizes a solvent, and B-stages an adhesive composition. Next, the metal foil is thermocompression bonded to the adhesive using a heating roll or the like. At that time, the pressure is preferably ^{2 to} 200 N / cm ² and the pressure is 40 to 200 ° C. If sufficient adhesive performance can be obtained, the process may be completed here. However, when complete curing is required, it is preferably post-cured at 100 to 200 ° C. for 1 to 24 hours. The thickness of the adhesive composition film after finally curing is preferably in the range of 5 to 100 μm.

  In order to produce a semiconductor encapsulating material from the curable resin composition of the present invention, compounding agents such as an active ester resin, an epoxy resin, and an inorganic filler may be used as necessary, such as an extruder, a kneader, a roll, etc. And a method of sufficiently melt-mixing until uniform. At that time, fused silica is usually used as the inorganic filler, but when used as a high thermal conductive semiconductor encapsulant for power transistors and power ICs, crystalline silica, alumina, nitridation having higher thermal conductivity than fused silica. High filling such as silicon, or fused silica, crystalline silica, alumina, silicon nitride, or the like may be used. The content of the inorganic filler is preferably in the range of 30 to 95 parts by mass per 100 parts by mass of the curable resin composition, and among them, improvement in flame retardancy, moisture resistance and solder crack resistance, and linear expansion In order to reduce the coefficient, the amount is more preferably 70 to 95 parts by mass, and still more preferably 80 to 95 parts by mass.

  The method for producing an adhesive film for buildup from the curable resin composition of the present invention includes, for example, applying the curable resin composition of the present invention on a support film and then drying the curable resin composition. The method of forming the resin composition layer on a support film and making it the adhesive film for multilayer printed wiring boards is mentioned.

  When the curable resin composition of the present invention is used for an adhesive film for buildup, the film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and at the same time as laminating the circuit board, It is important to show fluidity (resin flow) capable of filling a resin in the via hole or through hole existing in the substrate, and it is preferable to blend the above-described components so as to exhibit such characteristics.

  Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. It is usually preferable to allow resin filling in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like curable resin composition of the present invention, coating the varnish-like composition on the surface of the support film (Y), Further, it can be produced by drying the organic solvent by heating or blowing hot air to form the layer (X) of the curable resin composition.

  The thickness of the formed layer (X) is usually not less than the thickness of the conductor layer. Since the thickness of the conductor layer of the circuit board is usually in the range of 5 to 70 μm, the thickness of the resin composition layer is preferably 10 to 100 μm.

  In addition, the layer (X) in this invention may be protected with the protective film mentioned later. By protecting with a protective film, it is possible to prevent dust and the like from being attached to the surface of the resin composition layer and scratches.

  The above-mentioned support film and protective film are made of polyolefin such as polyethylene, polypropylene and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyester such as polyethylene naphthalate, polycarbonate, polyimide, and further. Examples thereof include metal foil such as pattern paper, copper foil, and aluminum foil. In addition, the support film and the protective film may be subjected to a release treatment in addition to the mud treatment and the corona treatment.

  Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

  The support film (Y) described above is peeled off after being laminated on a circuit board or after forming an insulating layer by heat curing. If the support film (Y) is peeled after the adhesive film is heat-cured, adhesion of dust and the like in the curing process can be prevented. In the case of peeling after curing, the support film is usually subjected to a release treatment in advance.

  Next, the method for producing a multilayer printed wiring board using the adhesive film obtained as described above is, for example, when the layer (X) is protected with a protective film, after peeling these layers ( X) is laminated on one side or both sides of the circuit board so as to be in direct contact with the circuit board, for example, by a vacuum laminating method. The laminating method may be a batch method or a continuous method using a roll. Further, the adhesive film and the circuit board may be heated (preheated) as necessary before lamination.

The laminating conditions are preferably a pressure bonding temperature (laminating temperature) of 70 to 140 ° C., a pressure bonding pressure of preferably 1 to 11 kgf / cm ² (9.8 × 10 ^{4 to} 107.9 × 10 ⁴ N / m 2), Lamination is preferably performed under reduced pressure with an air pressure of 20 mmHg (26.7 hPa) or less.

  Next, the present invention will be specifically described with reference to Examples and Comparative Examples. In the following, “parts” and “%” are based on mass unless otherwise specified. GPC was measured under the following conditions.

Measuring device: “HLC-8220 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ Tosoh Corporation “TSK-GEL G4000HXL”
Detector: RI (differential refractometer)
Data processing: “GPC-8020 Model II version 4.10” manufactured by Tosoh Corporation
Measurement conditions: Column temperature 40 ° C
Developing solvent Tetrahydrofuran
Flow rate: 1.0 ml / min Standard: The following monodisperse polystyrene having a known molecular weight was used in accordance with the measurement manual of “GPC-8020 Model II version 4.10”.
(Used polystyrene)
“A-500” manufactured by Tosoh Corporation
"A-1000" manufactured by Tosoh Corporation
"A-2500" manufactured by Tosoh Corporation
"A-5000" manufactured by Tosoh Corporation
“F-1” manufactured by Tosoh Corporation
"F-2" manufactured by Tosoh Corporation
“F-4” manufactured by Tosoh Corporation
“F-10” manufactured by Tosoh Corporation
“F-20” manufactured by Tosoh Corporation
“F-40” manufactured by Tosoh Corporation
“F-80” manufactured by Tosoh Corporation
“F-128” manufactured by Tosoh Corporation
Sample: A 1.0 mass% tetrahydrofuran solution filtered in terms of resin solids and filtered through a microfilter (50 μl).

Example 1 Production of Active Ester Resin (A-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 160 g (1.0 mol) of 2,7-dihydroxynaphthalene, 1, 158 g (1.0 mol) of 4-naphthoquinone, 6 g of paratoluenesulfonic acid, and 318 g of methyl isobutyl ketone were charged, and the temperature was raised from room temperature to 120 ° C. with stirring. After reaching 120 ° C., the reaction was allowed to stir for 3 hours. After completion of the reaction, the reaction mixture was neutralized and washed 3 times with 200 g of water. Then, it heated to 150 degreeC and dried under reduced pressure, and obtained 300 g of phenol resins (A). The GPC chart of the obtained phenol resin (A) is shown in FIG. The hydroxyl equivalent of the phenol resin (A) was 137 g / eq. The content of the component corresponding to the dinaphthofuran compound represented by the following structural formula (a) calculated from the GPC chart is 55.3%, represented by the following structural formula (b), and the value of k is 1. The content of a component corresponding to a compound corresponding to a certain binuclear compound was 9.7%, and the content of a component corresponding to a trinuclear compound represented by the following structural formula (c) was 22.0%. It was.

  Next, while purging a flask equipped with a thermometer, a condenser and a stirrer with nitrogen gas purge, 137 g of the phenol resin (A) obtained above (hydroxyl 1 eq) and 270 g of methyl isobutyl ketone were charged, and the system was purged with nitrogen under reduced pressure. Dissolved. Next, 127 g (0.9 mol) of benzoyl chloride was charged, and then 0.55 g of tetrabutylammonium bromide was dissolved, and the inside of the system was controlled to 60 ° C. or lower while applying a nitrogen gas purge. Was added dropwise over 3 hours. Thereafter, stirring was continued for 1 hour under these conditions. After completion of the reaction, the solution was allowed to stand for separation, and the aqueous layer was removed. Further, water was added to the methyl isobutyl ketone phase in which the reaction product was dissolved, and the mixture was stirred and mixed for about 15 minutes, followed by stationary separation to remove the aqueous layer. This operation was repeated until the pH of the water tank reached 7. Thereafter, water was removed by decanter dehydration, and methyl isobutyl ketone was subsequently removed by dehydration under reduced pressure to obtain 260 g of an active ester resin (A-1). The functional group equivalent of this active ester resin (A-1) was 264 g / eq from the charged ratio. Moreover, the ratio of the carbonyloxy group with respect to the total number of functional groups of the carbonyloxy group and phenolic hydroxyl group of (A-1) in active ester resin was 90%.

Example 2 Production of Active Ester Resin (B-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 160 g (1.0 mol) of 2,7-dihydroxynaphthalene, 1, 158 g (1.0 mol) of 4-naphthoquinone, 6 g of paratoluenesulfonic acid, and 333 g of isopropyl alcohol were charged, and the temperature was raised from room temperature to 80 ° C. with stirring. After reaching 80 ° C., the reaction was allowed to stir for 3 hours. After completion of the reaction, the reaction mixture was neutralized and washed 3 times with 200 g of water. Then, it heated to 150 degreeC and dried under reduced pressure, and obtained 295g of phenol resins (B). The GPC chart of the obtained phenol resin (B) is shown in FIG. The hydroxyl equivalent of the phenol resin (B) was 119 g / eq. The content of the component corresponding to the dinaphtho [b, d] furan compound represented by the structural formula (a) calculated from the GPC chart is 50.2%, represented by the structural formula (b). The content of the component corresponding to the binuclear compound having a value of 1 is 14.8%, and the content of the component corresponding to the trinuclear compound represented by the structural formula (c) is 24.2%. there were.

  Next, the activity was the same as in Example 1 except that the phenol resin (B) obtained above was changed to 119 g (hydroxyl group 1 eq), benzoyl chloride 98.4 g (0.7 mol), and 20% aqueous sodium hydroxide solution 135 g. 215 g of ester resin (B-1) was obtained. The functional group equivalent of this active ester resin (B-1) was 217 g / eq from the charged ratio. Moreover, the ratio of the carbonyloxy group with respect to the total number of functional groups of the carbonyloxy group and phenolic hydroxyl group of (B-1) in active ester resin was 70%.

Example 3 Production of Active Ester Resin (C-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 160 g (1.0 mol) of 2,7-dihydroxynaphthalene, 2, 150 g (1.0 mol) of 3,5-trimethyl-parabenzoquinone, 6 g of paratoluenesulfonic acid, and 310 g of methyl isobutyl ketone were charged, and the temperature was raised from room temperature to 120 ° C. with stirring. After reaching 120 ° C., the reaction was allowed to stir for 3 hours. After completion of the reaction, the reaction mixture was neutralized and the precipitated crystals were washed with 200 g of water three times and dried under reduced pressure to obtain 290 g of a phenol resin (C). The GPC chart of the obtained phenol resin (C) is shown in FIG. The hydroxyl equivalent of the phenol resin (C) was 148 g / eq. Further, the content of the component corresponding to the diarylene [b, d] furan compound represented by the structural formula (2) calculated from the GPC chart was 100%.

  Next, the activity was the same as in Example 1 except that the phenol resin (C) obtained above was changed to 148 g (hydroxyl group 1 eq), benzoyl chloride 98.4 g (0.7 mol), and 20% aqueous sodium hydroxide solution 135 g. 240 g of ester resin (C-1) was obtained. The functional group equivalent of this active ester resin (C-1) was 246 g / eq from the charged ratio. Moreover, the ratio of the carbonyloxy group with respect to the total number of functional groups of the carbonyloxy group and phenolic hydroxyl group of (C-1) in active ester resin was 70%.

Example 4 Production of Active Ester Resin (D-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 160 g (1.0 mol) of 1,5-dihydroxynaphthalene, 1, 158 g (1.0 mol) of 4-naphthoquinone, 6 g of paratoluenesulfonic acid, and 333 g of isopropyl alcohol were charged, and the temperature was raised from room temperature to 80 ° C. with stirring. After reaching 80 ° C., the reaction was allowed to stir for 3 hours. After completion of the reaction, the reaction mixture was neutralized and washed 3 times with 200 g of water. Then, it heated to 150 degreeC and dried under reduced pressure, and obtained 292g of phenol resins (D). A GPC chart of the obtained phenol resin (D) is shown in FIG. The hydroxyl equivalent of the phenol resin (D) was 132 g / eq. The content of the component corresponding to the dinaphtho [b, d] furan compound represented by the structural formula (a) calculated from the GPC chart was 24.1%.

  Next, activity was carried out in the same manner as in Example 1 except that 132 g (hydroxyl group 1 eq) of the phenol resin (D) obtained above, 98.4 g (0.7 mol) of benzoyl chloride, and 135 g of 20% aqueous sodium hydroxide solution were used. 227 g of ester resin (D-1) was obtained. The functional group equivalent of this active ester resin (D-1) was 230 g / eq from the charged ratio. Moreover, the ratio of the carbonyloxy group with respect to the total number of functional groups of the carbonyloxy group and phenolic hydroxyl group of (D-1) in active ester resin was 70%.

Comparative Synthesis Example 1 Production of Active Ester Resin (A′-1) Active ester in the same manner as in Example 1 except that phenol resin (A) was changed to phenol novolac resin (“TD-2090” manufactured by DIC Corporation). 180 g of resin (A′-1) was obtained. The functional group equivalent of this active ester resin (A′-1) was 199 g / eq from the charged ratio.

Examples 5-8, Comparative Example 1
In accordance with the formulation shown in Table 1 below, “850-S” manufactured by DIC (bisphenol A type epoxy resin, epoxy equivalent: 187 g / eq) as an epoxy resin, and the active ester (A-1), (B-1) as a curing agent ), (C-1), (D-1), (A′-1), 0.5 phr of dimethylaminopyridine is added as a curing accelerator, and finally the nonvolatile content (N.V. .) Was adjusted by blending methyl ethyl ketone so as to be 58% by mass. Next, a laminate was prepared by curing under the following conditions, and heat resistance, heat decomposition resistance, dielectric properties and flame retardancy were evaluated by the following methods. The results are shown in Table 1.

<Laminate production conditions>
Base material: Nitto Boseki Co., Ltd. glass cloth “# 2116” (210 × 280 mm)
Number of plies: 6 Condition of prepreg: 160 ° C
Curing conditions: 200 ° C., 40 kg / cm ² for 1.5 hours, post-molding plate thickness: 0.8 mm

<Measurement of heat resistance>
Measured using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device RSAII manufactured by Rheometric Co., Rectangular Tension Method; frequency 1 Hz, temperature rising rate 3 ° C./min), the change in elastic modulus is maximized (tan δ change rate) Was the glass transition temperature.

<Measurement of thermal decomposition resistance>
A test piece obtained by cutting a laminate of 0.8 mm thick cured product into a width of 5 mm and a length of 54 mm was held at 250 ° C. for 72 hours, and then the mass reduction rate when compared with the initial mass was evaluated. did.

<Measurement of flame retardancy>
In accordance with the UL-94 test method, flame retardancy was measured using five test pieces.

<Measurement of dielectric constant and dissipation factor>
In accordance with JIS-C-6481, the dielectric at 1 GHz of the test piece after being stored in a room at 23 ° C. and 50% humidity for 24 hours after being completely dried by an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. The rate and dielectric loss tangent were measured.

Claims (13)

A diarylene [b, d] furan structure, wherein at least one of the two arylene groups forming the diarylene [b, d] furan structure has a naphthylene skeleton, and the two arylenes A benzoyloxy group in which at least one arylene group is a benzoyloxy group, a naphthoyloxy group, or an alkyl group having 1 to 4 carbon atoms as a substituent on the aromatic ring on the aromatic ring; An ester structure moiety (z1) selected from either a naphthoyloxy group having 1 to 7 alkyl groups having 1 to 4 carbon atoms as substituents on the aromatic ring or an acyloxy group having 2 to 6 carbon atoms A curable resin composition comprising an active ester compound having) and a curable resin as essential components . At least one of the arylene group of said two arylene groups of the active ester compound, the ester structure portion (z1) in the para position of the carbon atom to which the oxygen atom bonded to form a furan ring or those having a hydroxyl group (z2) The curable resin composition according to claim 1. The active ester compound has a molecular structure represented by the following structural formula (I) or the following structural formula (II), and at least one portion represented by OZ in the molecular structure is the ester structure site. The curable resin composition according to claim 2, which is (z1).

[In formulas (I) and (II), each R ¹ independently represents a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group. Either. Z is a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as substituents on the aromatic ring, and an alkyl group having 1 to 4 carbon atoms substituted on the aromatic ring It is an ester-forming structure site (z1 ′) or a hydrogen atom (z2 ′) selected from any one of a naphthoyl group having 1 to 7 groups or an acyl group having 2 to 6 carbon atoms. Ar ¹ is a structural moiety represented by the following structural formula (i), and Ar ² is a structural moiety represented by the following structural formula (i) or (ii). ]

[In the formulas (i) and (ii), each R ² is independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group. m is an integer of 0 to 4, and n is an integer of 0 to 3. When m or n is 2 or more, R ² may be the same or different from each other. Z is a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as substituents on the aromatic ring, and an alkyl group having 1 to 4 carbon atoms substituted on the aromatic ring It is an ester-forming structure site (z1 ′) or a hydrogen atom (z2 ′) selected from any one of a naphthoyl group having 1 to 7 groups or an acyl group having 2 to 6 carbon atoms. x and y each represent a bonding point with the naphthalene ring and represent that they are bonded to adjacent carbon atoms of the naphthalene ring so as to form a furan ring with the oxygen atom. In formula (i), the group represented by R ² or O—Z bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings constituting the naphthalene ring. ] The active ester compound, the following structural formula (1) to (4) The curable resin composition according to claim 2, wherein those having a molecular structure represented by any one of the.

[In the formulas (1) to (4), Z represents a benzoyl group, a naphthoyl group, a benzoyl group having 1 to 5 carbon atoms as a substituent on the aromatic ring, and 1 carbon atom. An ester-forming structure site (z1 ′) selected from either a naphthoyl group having 1 to 7 alkyl groups as a substituent on the aromatic ring or a acyl group having 2 to 6 carbon atoms, or hydrogen An atom (z2 ′), and at least one of Z is an ester-forming structural site (z1 ′). R ² is each independently an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an aryl group, or an aralkyl group, m is an integer of 0 to 4, and n is It is an integer of 0-3. When m or n is 2 or more, R ² may be the same or different from each other. x and y each represent a bonding point with the naphthalene ring and represent that they are bonded to adjacent carbon atoms of the naphthalene ring so as to form a furan ring with the oxygen atom. In formulas (1) to (3), the group represented by R2 and O—Z bonded to the naphthalene ring may be bonded to any aromatic ring among the aromatic rings constituting the naphthalene ring. . ] Furthermore, the curable resin composition of any one of Claims 1-4 containing another active ester compound. Curing functional group equivalent relative to the functional groups of the sum of the carbonyl group and the phenolic hydroxyl group of the active ester compound in the total amount of the curable resin composition of claim 5 in the range of 110~310g / eq Resin composition. The curable resin composition according to claim 5, wherein the ratio of the carbonyloxy group to the total number of functional groups of the carbonyloxy group and the phenolic hydroxyl group in the total amount of the active ester compound in the curable resin composition is 40% or more . . The curable resin composition according to claim 1, wherein the curable resin is an epoxy resin. Hardened | cured material formed by hardening | curing the curable resin composition of any one of Claims 1-8 . The adhesive film for buildup formed by apply | coating the curable resin composition of any one of Claims 1-8 on a support film, and drying. The curable resin composition according to any one of claims 1 to 8 and an inorganic filler, wherein the content of the inorganic filler is 30 to 95 parts by mass per 100 parts by mass of the curable resin composition. Semiconductor sealing material in range. A prepreg obtained by semi-curing an impregnated base material obtained by impregnating a reinforcing base material with a varnished curable resin composition according to any one of claims 1 to 8 . A circuit board obtained by laminating a varnish obtained by diluting the curable resin composition according to any one of claims 1 to 8 with an organic solvent into a plate shape, and laminating it with a copper foil, followed by heat and pressure molding.

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