JP6376395B2 - Active ester compound, active ester resin, curable composition, cured product thereof, buildup film, semiconductor sealing material, prepreg, circuit board, and method for producing active ester resin - Google Patents

Description

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

  A curable composition comprising an epoxy resin and a curing agent as an essential component exhibits excellent heat resistance and insulation in the resulting cured product, and is therefore widely used in electronic component applications such as semiconductors and multilayer printed boards. ing. In the technical field of multilayer printed circuit board insulating materials among electronic parts, development of insulating materials having a low dielectric constant and a low dielectric loss tangent has been demanded in recent years with the increase in signal speed and frequency.

  In Patent Document 1, in order to obtain a cured product having a low dielectric constant and a low dielectric loss tangent, 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. Is described.

  However, when the active ester compound described in Patent Document 1 is used as a curing agent for epoxy resins, a cured product having a lower dielectric constant and dielectric loss tangent than conventional ones can be obtained. It did not meet the level. Furthermore, due to the trend toward higher frequency and smaller size in electronic components, multilayer printed circuit board insulation materials are required to have extremely high heat resistance and heat decomposition resistance and to exhibit high flame resistance without using halogen flame retardants. It has been. However, since the active ester compound described in Patent Document 1 has a structure in which a phenolic hydroxyl group in a phenol novolac resin is esterified, when used as a curing agent for an epoxy resin, the resulting cured product has a low crosslinking density. The cured product obtained from the active ester compound was insufficient in heat resistance and heat decomposability, and was inferior in flame retardancy.

JP 7-82348 A

  Therefore, the problem to be solved by the present invention is that the obtained cured product contains an active ester compound, an active ester resin, and a low dielectric constant and dielectric loss tangent, and excellent heat resistance, heat decomposition resistance, and flame retardancy. An object of the present invention is to provide a method for producing a curable composition, a cured product, a build-up film, a semiconductor sealing material, a prepreg, a circuit board, and an active ester resin.

  As a result of intensive studies to solve the above problems, the present inventors have found that an active ester compound represented by the following structural formula (I) has a rigid molecular structure in which aromatic nuclei are directly bonded to each other. It has been found that the resulting cured product has a low dielectric constant and dielectric loss tangent, and is excellent in heat resistance, heat decomposition resistance, and flame retardancy, because it has a higher active ester group concentration or hydroxyl group concentration than other resins. The present invention has been completed.

  That is, the present invention has a molecular structure represented by the following general formula (I), and at least one of Z in the molecule has 1 to 4 carbon atoms as a substituent on the benzoyl group or aromatic nucleus. A benzoyl group having 1 to 5 alkyl groups, a naphthoyl group, a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, or 2 to 6 carbon atoms The present invention relates to an active ester compound, which is an active ester-forming structural site (z1) which is any of acyl groups.

  In formula (I), Z is the active ester-forming structural site (z1) or hydrogen atom (z2). X is a structural moiety represented by the following structural formula (x1) or (x2).

In formula (x1) or (x2), R ¹ and R ² are each 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, and l is An integer from 0 to 3, n is an integer from 0 to 4. When l or n is an integer of 2 or more, a plurality of R ¹ or R ² may be the same or different from each other. k is an integer of 1 to 3, m is an integer of 1 to 2, and * 1 represents a bonding point with an O atom in the general formula (I). Furthermore, Ar is a structural site represented by the following structural formula (Ar1) or (Ar2). When k or m is an integer of 2 or more, the plurality of Ars may be the same or different.

In the formula (Ar1) or (Ar2), Z is the active ester-forming structure site (z1) or hydrogen atom (z2), and p and r are integers of 1 to 2, respectively. When p and r are 2, two Zs may be the same or different. R ³ and R ⁴ are each 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, and R ⁴ and OZ in the formula (Ar2) May be bonded to either of the two aromatic nuclei. q is an integer of 0 to 4, s is an integer of 0 to 6, and when q or s is an integer of 2 or more, a plurality of R ³ or R ⁴ may be the same or different from each other. good. * 2 represents the point of attachment to the carbon atom on the aromatic nucleus in the structural formula (x1) or (x2).

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

  The present invention further provides a phenol intermediate (a) 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, and then the obtained phenol. The present invention relates to a method for producing an active ester resin, comprising reacting an intermediate (a) with a monocarboxylic acid compound or a halide (b) thereof.

  The present invention further relates to a curable composition comprising the active ester compound or the active ester resin and an epoxy resin.

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

  The present invention further relates to a build-up film, wherein the curable composition diluted with an organic solvent is applied onto a substrate film and dried.

  The present invention further relates to a semiconductor sealing material containing the curable composition and an inorganic filler, wherein the content of the inorganic filler is in the range of 70 to 95% by mass.

  The present invention further relates to a prepreg obtained by impregnating a reinforcing substrate with a solution obtained by diluting the curable composition in an organic solvent, and semi-curing the resulting impregnated substrate.

  The present invention further relates to a circuit board obtained by obtaining a varnish obtained by diluting the curable composition in an organic solvent, and heating and press-molding a varnish shaped into a plate shape and a copper foil.

  According to the present invention, the obtained cured product has a low dielectric constant and dielectric loss tangent, and has an active ester compound, an active ester resin excellent in heat resistance, heat decomposition resistance, and flame retardancy, a curable composition containing these, The manufacturing method of hardened | cured material, a buildup film, a semiconductor sealing material, a prepreg, a circuit board, and active ester resin can be provided.

2 is a GPC chart of the phenol intermediate (A) obtained in Example 1. 2 is a ¹³ C NMR chart of the phenol intermediate (A) obtained in Example 1. FIG. 2 is an MS spectrum of a phenol intermediate (A) obtained in Example 1. 2 is a GPC chart of a phenol intermediate (B) obtained in Example 2. 3 is a ¹³ C NMR chart of the phenol intermediate (B) obtained in Example 2. FIG. 2 is an MS spectrum of a phenol intermediate (B) obtained in Example 2. 4 is a GPC chart of a phenol intermediate (C) obtained in Example 3. 4 is a GPC chart of a phenol intermediate (D) obtained in Example 4. 4 is an MS spectrum of a phenol intermediate (D) obtained in Example 4. 6 is a GPC chart of a phenol intermediate (E) obtained in Example 5. 6 is a ¹³ C NMR chart of a phenol intermediate (E) obtained in Example 5. FIG. 4 is an MS spectrum of a phenol intermediate (E) obtained in Example 5. 6 is a GPC chart of a phenol intermediate (F) obtained in Example 6. 6 is a ¹³ C NMR chart of a phenol intermediate (F) obtained in Example 6. 4 is an MS spectrum of a phenol intermediate (F) obtained in Example 6. 4 is a GPC chart of a phenol intermediate (G) obtained in Example 7. 4 is an MS spectrum of a phenol intermediate (G) obtained in Example 7.

Hereinafter, the present invention will be described in detail.
The active ester compound of the present invention has a molecular structure represented by the following general formula (I), and at least one of Z in the molecule is a benzoyl group, and has 1 to 1 carbon atoms as a substituent on the aromatic nucleus. A benzoyl group having 1 to 5 alkyl groups, a naphthoyl group, a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, or 2 to 6 carbon atoms It is characterized in that it is an active ester-forming structural site (z1) that is any of the acyl groups.

  In formula (I), Z is the active ester-forming structural site (z1) or hydrogen atom (z2). X is a structural moiety represented by the following structural formula (x1) or (x2).

In formula (x1) or (x2), R ¹ and R ² are each 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, and l is An integer from 0 to 3, n is an integer from 0 to 4. When l or n is an integer of 2 or more, a plurality of R ¹ or R ² may be the same or different from each other. k is an integer of 1 to 3, m is an integer of 1 to 2, and * 1 represents a bonding point with an O atom in the general formula (I). Furthermore, Ar is a structural site represented by the following structural formula (Ar1) or (Ar2). When k or m is an integer of 2 or more, the plurality of Ars may be the same or different.

In the formula (Ar1) or (Ar2), Z is the active ester-forming structure site (z1) or hydrogen atom (z2), and p and r are integers of 1 to 2, respectively. When p and r are 2, two Zs may be the same or different. R ³ and R ⁴ are each 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, and R ⁴ and OZ in the formula (Ar2) May be bonded to either of the two aromatic nuclei. q is an integer of 0 to 4, s is an integer of 0 to 6, and when q or s is an integer of 2 or more, a plurality of R ³ or R ⁴ may be the same or different from each other. good. * 2 represents the point of attachment to the aromatic nucleus in the structural formula (x1) or (x2).

  As described above, the active ester compound of the present invention has a structure in which aromatic nuclei are bonded to each other without a methylene chain (structure represented by structural formulas (x1) and (x2)) in an active ester-forming structural site (z1 ) In the basic skeleton or a hydroxyl group having a hydrogen atom (z2) in the basic skeleton. A compound having a rigid molecular structure in which aromatic nuclei are bonded to each other without using a methylene chain suppresses molecular motion as compared with a long-chain resin such as a general novolak resin, and has a high aromatic ring. Since it has a concentration, the obtained cured product is characterized by low dielectric constant and dielectric loss tangent, and high heat decomposition temperature.

  Furthermore, it has an active ester forming structure site (z1) in the basic skeleton in the structure as described above (structure represented by the structural formulas (x1) and (x2) in which aromatic nuclei are bonded without using a methylene chain). A compound into which a hydroxyl group having an ester group or a hydrogen atom (z2) in the basic skeleton is introduced has a higher active ester group concentration or hydroxyl group concentration than a general resin, and has a high crosslinking density in a cured product. The obtained cured product is characterized by high heat resistance.

  In general, a compound having a high active ester group concentration tends to be inferior in flame retardancy of a cured product because a flammable active ester group is present in close proximity. Having a structure in which aromatic nuclei are bonded to each other without using a methylene chain, and two activities introduced in the para position of the aromatic nuclei and having excellent reactivity in the structural formula (x1) or (x2) Since it has an ester-forming structural site or a phenolic hydroxyl group, it has a feature of having excellent flame retardancy in a cured product.

  In Structural Formula (x1) or (x2), k is an integer of 1 to 3, and m is an integer of 1 to 2. A compound corresponding to the case where the value of k or m is 1 (hereinafter abbreviated as “binuclear compound (α1)”) has low molecular weight and low viscosity, but the resulting cured product has heat resistance and heat decomposition. It has the characteristic that it is excellent in property and a flame retardance. On the other hand, a compound corresponding to a value of k or m of 2 (hereinafter abbreviated as “trinuclear compound (α2)”) or a compound corresponding to a value of k of 3 (hereinafter “tetranuclear compound”). Compound (α3) ”) has a higher molecular skeleton rigidity and a higher aromatic ring concentration, so that the obtained cured product is more excellent in heat resistance, heat decomposition resistance, and flame retardancy. Have

  Z in the general formula (I) is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, or a carbon as a substituent on the aromatic nucleus. An active ester forming structure site (z1) or a hydrogen atom (z2) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 atoms or an acyl group having 2 to 6 carbon atoms is there.

  Here, the benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus is, for example, 2,4-dimethylbenzoyl group, 2,6-dimethylbenzoyl group, 2, 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-butyl benzoyl group etc. are mentioned.

  The naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus includes, for example, 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, Examples include 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.

  The active ester-forming structural site (z1) is an acetyl group, a benzoyl group, or a naphthoyl group from the viewpoint of excellent dielectric properties at the time of curing and good reactivity with an epoxy resin, among the structures described above. Among them, a benzoyl group is particularly preferable.

  Moreover, in the active ester resin containing the active ester compound represented by the general formula (I), the existence ratio of the active ester forming structure site (z1) and the hydrogen atom (z2) is lower than the dielectric constant and the dielectric loss tangent. Since a cured product is obtained, the active ester forming structure site (z1) may be contained in a ratio of 40% or more with respect to the total of the active ester forming structure site (z1) and the hydrogen atom (z2). Preferably, it is contained at a ratio of 65% or more. 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. In this way, all of the active ester compounds Z contained in the active ester resin may be active ester-forming structural sites (z1), but some of them are hydrogen atoms (z2). In the active ester compound contained in the active ester resin, when the active ester compound partially contains a phenolic hydroxyl group, the curability of the active ester resin becomes good, and the effect of improving heat resistance is remarkable. Become.

  Furthermore, 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 60 to 300 g / eq. It is preferable that

  The active ester compound represented by the general formula (I) is, for example, a compound (Q) having a quinone structure and a compound (P) having a phenolic hydroxyl group at 40 to 180 ° C. under no catalyst or acid catalyst conditions. To obtain a phenol intermediate (a), and then reacting the obtained phenol intermediate (a) with a monocarboxylic acid compound or a halide (b) thereof. When an active ester compound is produced by such a method, an arbitrary component can be selectively produced depending on reaction conditions, or an active ester resin that is a mixture of a plurality of types of active ester compounds can be produced. Furthermore, only an arbitrary active ester compound can be isolated from the active ester resin.

  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), R ¹ and R ² are each 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, and l is An integer from 0 to 3, n is an integer from 0 to 4. When l or n is an integer of 2 or more, a plurality of R ¹ or R ² may be the same or different from each other.

  Specific examples of the compound (Q) having a quinone structure include parabenzoquinone, 2-methylbenzoquinone, 2,3,5-trimethyl-benzoquinone, naphthoquinone, and the like. These may be used alone or in combination of two or more.

  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), R ³ and R ⁴ are each 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, and q is Integer of 0-4, s is an integer of 0-6. When q or s is an integer of 2 or more, a plurality of R ³ or R ⁴ may be the same or different from each other. P and r are integers of 1 to 2, respectively.

  Specific examples of the compound (P) having a phenolic hydroxyl group include phenol, orthocresol, metacresol, paracresol, 2,6-dimethylphenol, 2,5-dimethylphenol, 2,4-dimethylphenol, 3, 5-dimethylphenol, 2,3,4-trimethylphenol, 2,3,5-trimethylphenol, 2,3,6-trimethylphenol, 2,4,5-trimethylphenol, 3,4,5-trimethylphenol, 4-isopropylphenol, 4-tert-butylphenol, 2-methoxyphenol, 3-methoxyphenol, 4-methoxyphenol, 2-methoxy-4-methylphenol, 2-tert-butyl-4-methoxyphenol, 2,6- Dimethoxyphenol, 3,5-dimethoxyph Nord, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 4-benzylphenol, 1,2-dihydroxybenzene, 1,3-dihydroxybenzene 1,4-dihydroxybenzene, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene Etc. These may be used alone or in combination of two or more.

  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 may be appropriately performed using an acid catalyst. 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, it is preferably used in an amount of 5.0% by mass or less based on the total mass of the compound (Q) having a quinone structure and the compound (P) having a phenolic hydroxyl group.

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 50 to 200 masses with respect to a total of 100 mass parts of the compound (Q) having a quinone structure and the compound (P) having a phenolic hydroxyl group. It is preferable to use it in a ratio that falls within the range of parts.
, Preferably in an amount of 5.0% by mass or less.

  Thus, the phenol intermediate (a) represented by the following general formula (II) can be obtained by reacting the compound (Q) having a quinone structure with the compound (P) having a phenolic hydroxyl group. .

  In formula (II), X ′ is a structural moiety represented by the following structural formula (x3) or (x4).

In formula (x3) or (x4), R ¹ and R ² are each 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, and l is An integer from 0 to 3, n is an integer from 0 to 4. When l or n is an integer of 2 or more, a plurality of R ¹ or R ² may be the same or different from each other. k is an integer of 1 to 3, m is an integer of 1 to 2, and * 3 represents a bonding point with the O atom in the general formula (II). Furthermore, Ar is a structural site represented by the following structural formula (Ar3) or (Ar4). When k or m is an integer of 2 or more, the plurality of Ars may be the same or different.

In the formula (Ar3) or (Ar4), p and r are each an integer of 1 to 2. q is an integer of 0 to 4, and s is an integer of 0 to 6. R ³ and R ⁴ are each 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. In the formula (Ar4), R ⁴ and OH may be bonded to any one of the two aromatic nuclei. * 4 represents the point of attachment to the carbon atom on the aromatic nucleus in the formula (x3) or (x4).

  In the formula (x3) or (x4), the phenol intermediate (a) corresponding to the case where the value of k or m is 1 reacts with the following monocarboxylic acid compound or a halide (b) thereof, The binuclear compound (α1) is produced in the active ester resin. Similarly, by reacting with the following monocarboxylic acid compound or its halide (b), the phenol intermediate corresponding to the case where the value of k or m is 2, produces the trinuclear compound (α2), The phenol intermediate corresponding to the case where the value of k is 3 produces the tetranuclear compound (α3). That is, in the formula (x3) or (x4), the compound in which the value of k or m is 1 is a precursor of the binuclear compound (α1) in the active ester resin, and the value of k or m is 2 The compound in this case is a precursor of the trinuclear compound (α2), and the compound having a k value of 3 is a precursor of the tetranuclear compound (α3). The ratio of the binuclear compound (α1), the trinuclear compound (α2), and the tetranuclear compound (α3) contained in the active ester resin is included in the phenol intermediate (a). Depending on the proportion of the precursor, the proportion is maintained and does not change even after reacting with the monocarboxylic acid compound or its halide (b).

  Next, the obtained phenol intermediate (a) is reacted with a monocarboxylic acid compound or a halide (b) thereof.

  Specific examples of monocarboxylic acid compounds or halides (b) thereof include phenyl groups, naphthyl groups, phenyl groups having 1 to 5 alkyl groups having 1 to 4 carbon atoms as substituents on the aromatic nucleus, and naphthyl. An aromatic monocarboxylic acid having a hydrocarbon structure selected from the group consisting of a naphthyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, or a halide thereof (b -1) (hereinafter abbreviated as "aromatic monocarboxylic acid or its halide (b-1)"), or saturated fatty acid having 2 to 5 carbon atoms or its halide (b-2) (hereinafter referred to as This is abbreviated as “saturated fatty acid or its halide (b-2)”).

  The aromatic monocarboxylic acid or its halide (b-1) is specifically benzoic acid, methylbenzoic acid, 2,4-dimethylbenzoic acid, 2,6-dimethylbenzoic acid, 2,4,6 -Alkylbenzoic acids such as trimethylbenzoic acid, 2-ethylbenzoic acid, 4-ethylbenzoic acid, 2-t-butyl-4-ethylbenzoic acid, 4-i-propylbenzoic acid, 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 Naphthoic acid, as well as their acid fluorides, acid chlorides, acid bromides, acid halides such as acid iodide and the like.

  Further, the saturated fatty acid or its halide (b-2) specifically includes ethanoic acid, propanoic acid, butanoic acid, pentanoic acid, hexanoic acid, and their acid fluorides, acid chlorides, acid bromides, and And acid halides such as acid iodide.

  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 intermediate (a) and the monocarboxylic acid compound or its halide (b) include a method in which these are reacted under a basic catalyst.

  The reaction ratio between the phenol intermediate (a) and the monocarboxylic acid compound or its halide (b) is the same as the phenolic hydroxyl group in the phenol intermediate (a) and the carboxyl in the monocarboxylic acid compound or its halide (b). The ratio of the equivalent ratio with the group or acid halide group [OH in (a) / carboxyl group or acid halide group in (b)] is 1.0 / 0.40 to 1.0 / 1.0. 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 intermediate (a) with the monocarboxylic acid compound or its halide (b), it is preferable to dissolve each raw material component in an organic solvent and use it for the reaction. As the organic solvent used here, toluene, dichloromethane Etc.

  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 further purification is performed by dehydration or filtration, and the organic solvent is removed by distillation to obtain the intended active ester resin.

  In addition, the active ester compound of the present invention has a low dielectric constant and dielectric loss tangent in a cured product obtained in any case as long as it has a structure represented by the general formula (I). It has the characteristics that it is excellent in heat resistance, thermal decomposition resistance, and flame retardancy. Hereinafter, the more preferable thing of the active ester compound which has a structure represented with the said general formula (I) is explained in full detail.

  A typical active ester compound represented by the general formula (I) has a molecular structure represented by any of the following structural formulas (I-1) to (I-3), At least one of Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a substituent on the aromatic nucleus having 1 carbon atom A naphthoyl group having 1 to 7 alkyl groups of ˜4, or an active ester forming structure site (z1) which is either an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (z2), in the molecule An active ester compound in which at least one of Z in the formula is an active ester-forming structural site (z1).

  In formulas (I-1) to (I-3), Z is the active ester-forming structural site (z1) or a hydrogen atom (z2). k is an integer of 1 to 3, m is an integer of 1 to 2, and Ar is a structural moiety represented by the following structural formula (Ar1) or (Ar2). When k or m is an integer of 2 or more, the plurality of Ars may be the same or different.

In the formula (Ar1) or (Ar2), Z is the active ester-forming structure site (z1) or hydrogen atom (z2), and p and r are integers of 1 to 2, respectively. When p and r are 2, two Zs may be the same or different. R ³ and R ⁴ are each 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, and R ⁴ and OZ in the formula (Ar2) May be bonded to either of the two aromatic nuclei. q is an integer of 0 to 4, s is an integer of 0 to 6, and when q or s is an integer of 2 or more, a plurality of R ³ or R ⁴ may be the same or different from each other. good. * 2 represents the point of attachment to the aromatic nucleus in the structural formula (x1) or (x2).

  More specifically, the active ester compound represented by the structural formula (I-1) includes an active ester compound having a molecular structure represented by any one of the following structural formulas (1) to (7). . Each will be described in detail below.

In the formulas (1) to (7), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, a substituent on the aromatic nucleus As an active ester-forming structure site (z1) or a hydrogen atom (z2) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms. And at least one of Z in the molecule is an active ester-forming structural site (z1). k is an integer of 1 to 3, R ⁵ is 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, and u is 1 to 4 It is an integer. When u is an integer of 2 or more, the plurality of R ⁵ may be the same or different from each other.

  The active ester compound represented by the following structural formula (1) has a particularly low melt viscosity among the active ester compounds of the present invention represented by the general formula (I), and has a heat resistance and difficulty in a cured product. It has a feature that it is particularly excellent in balance between flammability and dielectric properties.

  In the formula (1), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). k is an integer of 1 to 3.

  The active ester resin containing the compound represented by the structural formula (1) has a low melt viscosity and is excellent in dielectric properties, heat resistance, heat decomposition resistance, and flame retardancy in a cured product. Among them, a binuclear compound (α1) having a k value of 1 in the structural formula (1) because the melt viscosity is lower and the cured product exhibits further excellent heat resistance, heat decomposition resistance, and flame retardancy. ) And a trinuclear compound (α2) having a k value of 2 is preferable. Among them, the content of the dinuclear compound (α1) in the active ester resin is an area in GPC measurement. More preferred is an active ester resin having a ratio of 2 to 50% and a content ratio of the trinuclear compound (α2) of 10 to 95% in terms of area ratio in GPC measurement.

  In particular, in addition to the binuclear compound (α1) and the trinuclear compound (α2), in addition to the binuclear compound (α1) and the trinuclear compound (α2), a k value of 3 is obtained in that heat resistance, thermal decomposition resistance, and flame retardancy are obtained. And an active ester resin containing a tetranuclear compound (α3 ′) represented by the following structural formula (1 ′) is preferable. Among them, the tetranuclear compound (α3) is preferable. And an active ester resin in which the total content of the tetranuclear compound (α3 ′) is in the range of 2 to 30% in terms of area ratio in GPC measurement.

  In the formula (1 ′), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, a carbon atom as a substituent on the aromatic nucleus It is an active ester-forming structure site (z1) or a hydrogen atom (z2) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 alkyl groups, or an acyl group having 2 to 6 carbon atoms. .

In the present invention, the content of the binuclear compound (α1), the trinuclear compound (α2), the tetranuclear compound (α3), and the tetranuclear compound (α3 ′) in the active ester resin The ratio of the peak area of each component to the total peak area of the active ester resin, calculated from GPC measurement data under 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).

  The active ester compound represented by the structural formula (1) is produced by the above-described method using, for example, parabenzoquinone as the compound (Q) having a quinone structure and phenol as the compound (P) having a phenolic hydroxyl group. I can do it. At this time, the reaction rate of parabenzoquinone and phenol can adjust the content of the binuclear compound (α1) and the trinuclear compound (α2) in the obtained active ester resin to the above-described preferable range. Since it is easy, it is preferable to make it react with the ratio which becomes the range of 0.1-10.0 mol of phenol with respect to 1 mol of para benzoquinone.

  Examples of the compound represented by the structural formula (1) include an active ester compound represented by any of the following structural formulas (1-1) to (1-9).

  In formulas (1-1) to (1-9), Z represents a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  The active ester compound represented by the following structural formula (2) has a particularly low melt viscosity among the active ester compounds of the present invention represented by the general formula (I), and has a dielectric property, heat resistance and heat resistance in a cured product. It is characterized by excellent decomposability and flame retardancy.

  In formula (2), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). k is an integer of 1 to 3.

  The active ester resin containing the compound represented by the structural formula (2) has a low melt viscosity and is excellent in dielectric properties, heat resistance, heat decomposition resistance, and flame retardancy in a cured product. Among them, since the cured product is further excellent in heat resistance, heat decomposition resistance, and flame retardancy, the binuclear compound (α1) having a k value of 1 in the structural formula (2) and the structural formula ( In 2), an active ester resin containing a trinuclear compound (α2) having a k value of 2 is preferable. Among them, the content of the dinuclear compound (α1) in the active ester resin is an area in GPC measurement. An active ester resin having a ratio in the range of 2 to 50% and a content ratio of the trinuclear compound (α2) in the range of 10 to 95% in terms of area ratio in GPC measurement is more preferable. Furthermore, among them, the content of the binuclear compound (α1) in the active ester resin is in the range of 2 to 35% in terms of area ratio in GPC measurement, and the content of the trinuclear compound (α2) is GPC. An active ester resin having an area ratio of 25 to 90% in the measurement is even more preferable.

  In particular, in terms of obtaining a cured product having further excellent heat resistance, in addition to the binuclear compound (α1) and the trinuclear compound (α2), tetranuclear having a value of k of 3 in the structural formula (2). Active ester resin containing a tetranuclear compound (α3) and a tetranuclear compound (α3 ′) represented by the following structural formula (2 ′) is preferable, and among them, a tetranuclear compound (α3) in the active ester resin And the active ester resin in which the total content of the tetranuclear compound (α3 ′) is in the range of 2 to 20% in terms of area ratio in GPC measurement.

  In the formula (2 ′), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, a carbon atom as a substituent on the aromatic nucleus It is an active ester-forming structure site (z1) or a hydrogen atom (z2) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 alkyl groups, or an acyl group having 2 to 6 carbon atoms. .

  The active ester compound represented by the structural formula (2) is produced by the above-described method using, for example, parabenzoquinone as the compound (Q) having a quinone structure and cresol as the compound (P) having a phenolic hydroxyl group. I can do it. At this time, the reaction ratio of parabenzoquinone and cresol is easy to adjust the content of the binuclear compound (α1) and trinuclear compound (α2) in the obtained active ester resin to the preferred range described above. For this reason, it is preferable to react with 1 mol of parabenzoquinone at a ratio such that cresol is in the range of 0.1 to 10.0 mol.

  The cresol used here may be any of ortho-cresol, meta-cresol, and para-cresol, and a plurality of types may be used in combination. Among them, orthocresol is preferable because an active ester resin having a low melt viscosity and excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained.

  Examples of the compound represented by the structural formula (2) include an active ester compound represented by any one of the following structural formulas (2-1) to (2-31).

  In formulas (2-1) to (2-31), Z represents a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1) or a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure It is a part (z1).

  The active ester compound represented by the following structural formula (3) has a particularly low melt viscosity among the active ester compounds of the present invention represented by the general formula (I), and has a dielectric property, heat resistance and heat resistance in a cured product. It is characterized by excellent decomposability and flame retardancy.

  In formula (3), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). k is an integer of 1 to 3.

  The active ester resin containing the compound represented by the structural formula (3) has a low melt viscosity and is excellent in dielectric properties, heat resistance, heat decomposition resistance, and flame retardancy in a cured product. Among them, since the cured product is excellent in heat resistance, heat decomposition resistance, and flame retardancy, the binuclear compound (α1) having a value of k of 1 in the structural formula (2) and the structural formula (2) ) Is preferably an active ester resin containing a trinuclear compound (α2) having a k value of 2. Among these, the content ratio of the dinuclear compound (α1) in the active ester resin is an area ratio in GPC measurement. An active ester resin in which the content ratio of the trinuclear compound (α2) is in the range of 10 to 95% in terms of the area ratio in the GPC measurement is more preferable. Furthermore, among them, the content of the binuclear compound (α1) in the active ester resin is in the range of 2 to 35% in terms of area ratio in GPC measurement, and the content of the trinuclear compound (α2) is GPC. An active ester resin having an area ratio of 30 to 95% in the measurement is even more preferable.

  In particular, in terms of obtaining a cured product having further excellent heat resistance, in addition to the binuclear compound (α1) and the trinuclear compound (α2), tetranuclear having a value of k of 3 in the structural formula (3). Active ester resin containing a tetranuclear compound (α3) and a tetranuclear compound (α3 ′) represented by the following structural formula (3 ′), among which a tetranuclear compound (α3) in the active ester resin is preferable. And an active ester resin in which the total content of the tetranuclear compound (α3 ′) is in the range of 0.5 to 20% in terms of area ratio in GPC measurement.

  In the formula (3 ′), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, a carbon atom as a substituent on the aromatic nucleus It is an active ester-forming structure site (z1) or a hydrogen atom (z2) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms. , At least one of Z in the molecule is an active ester forming structure site (z1).

  The active ester compound represented by the structural formula (3) is produced by the above-described method using, for example, parabenzoquinone as the compound (Q) having a quinone structure and dimethylphenol as the compound (P) having a phenolic hydroxyl group. I can do it. At this time, the reaction ratio of parabenzoquinone and dimethylphenol can easily adjust the content of the binuclear compound (α1) and the trinuclear compound (α2) in the obtained active ester resin to the preferred range described above. Therefore, it is preferable to react with 1 mol of parabenzoquinone at a ratio such that dimethylphenol is in the range of 0.1 to 10.0 mol.

  The dimethylphenol used here may be any positional isomer such as 2,6-dimethylphenol, 2,5-dimethylphenol, 2,4-dimethylphenol, 3,5-dimethylphenol. Among them, 2,6-dimethylphenol is preferable because an active ester resin having a low melt viscosity and excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained.

  Examples of the compound represented by the structural formula (3) include an active ester compound represented by any of the following structural formulas (3-1) to (3-3).

  In formulas (3-1) to (3-3), Z represents a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  The active ester compound represented by the following structural formula (4) is produced by the above-described method using, for example, parabenzoquinone as the compound (Q) having a quinone structure and dihydroxybenzene as the compound (P) having a phenolic hydroxyl group. I can do it. At this time, since the reaction ratio of parabenzoquinone and dihydroxybenzene is an active ester resin having a low melt viscosity and further excellent heat resistance, heat decomposition resistance and flame retardancy in the cured product, dihydroxy with respect to 1 mol of parabenzoquinone. It is preferable that the proportion of benzene is in the range of 0.1 to 10.0 mol.

  In the formula (4), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). k is an integer of 1 to 3.

  The dihydroxybenzene used here may be any positional isomer such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene and the like. Among them, 1,3-dihydroxybenzene is preferable because an active ester resin having a low melt viscosity and excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained.

  Examples of the compound represented by the structural formula (4) include an active ester compound represented by any of the following structural formulas (4-1) to (4-3).

  In formulas (4-1) to (4-3), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  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. Examples of such active ester compounds include active ester compounds represented by any one of the following structural formulas (4′-1) to (4′-8).

  In formulas (4′-1) to (4′-8), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, Active ester forming structure site (z1) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms or an acyl group having 2 to 6 carbon atoms as a substituent on the aromatic nucleus Or a hydrogen atom (z2), and at least one of Z in the molecule is an active ester-forming structural site (z1). i and j are integers of 1 to 2, respectively.

  The active ester resin containing the active ester compound represented by the structural formula (4) and the other active ester compound has a low melt viscosity and is excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product. Have. Among them, an active ester resin containing a binuclear compound (α1) having a k value of 1 in the structural formula (4) and a trinuclear compound (α2) having a k value of 2 is more preferable, Among them, the content of the binuclear compound (α1) in the active ester resin is in the range of 2 to 50% in terms of area ratio in GPC measurement, and the content of the trinuclear compound (α2) is measured by GPC. An active ester resin having an area ratio of 10 to 95% is even more preferable.

  In particular, the value of k is 3 in addition to the binuclear compound (α1) and the trinuclear compound (α2) in that a cured product that is more excellent in heat resistance, thermal decomposition resistance, and flame retardancy can be obtained. An active ester resin containing a tetranuclear compound (α3) or a tetranuclear compound (α3 ′) represented by the following structural formulas (4 ″ -1) and (4 ″ -2) is preferable, among them. Further, the active ester resin in which the total content of the tetranuclear compound (α3) and the tetranuclear compound (α3 ′) in the active ester resin is in the range of 5 to 40% in terms of the area ratio in the GPC measurement is even more. preferable.

  In the formulas (4 ″ -1) to (4 ″ -2), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, Active ester forming structure site (z1) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms or an acyl group having 2 to 6 carbon atoms as a substituent on the aromatic nucleus Or a hydrogen atom (z2), and at least one of Z in the molecule is an active ester-forming structural site (z1).

  The active ester compound represented by the following structural formula (5) is produced by the above-described method using, for example, parabenzoquinone as the compound (Q) having a quinone structure and naphthol as the compound (P) having a phenolic hydroxyl group. I can do it. At this time, the reaction rate of parabenzoquinone and naphthol is low in melt viscosity, and an active ester resin having further excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. Is preferably in the range of 0.1 to 10.0 mol.

  In formula (5), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). k is an integer of 1 to 3.

  The active ester resin containing the compound represented by the structural formula (5) has a low melt viscosity and is excellent in dielectric properties, heat resistance, heat decomposition resistance, and flame retardancy in a cured product. Among these, since it is particularly excellent in heat resistance, heat decomposition resistance, and flame retardancy in the cured product, the binuclear compound (α1) having a k value of 1 in the structural formula (5), and the structural formula ( 5) An active ester resin containing a trinuclear compound (α2) having a k value of 2 is preferable, and among them, the content of the dinuclear compound (α1) in the active ester resin is an area in GPC measurement. An active ester resin in which the ratio is in the range of 5 to 70% and the content of the trinuclear compound (α2) is in the range of 5 to 50% in terms of the area ratio in the GPC measurement is more preferable.

  Examples of the compound represented by the structural formula (5) include an active ester compound represented by any of the following structural formulas (5-1) to (5-10).

  In formulas (5-1) to (5-10), Z represents a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  The active ester compound represented by the following structural formula (6) is particularly excellent in heat resistance, thermal decomposition resistance, and flame retardancy in a cured product among the active ester compounds represented by the general formula (I). Have

  In formula (6), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). k is an integer of 1 to 3.

  The active ester resin containing the compound represented by the structural formula (6) has a low melt viscosity and is excellent in dielectric properties, heat resistance, heat decomposition resistance, and flame retardancy in a cured product. Among them, a binuclear compound (α1) having a k value of 1 in the structural formula (6) because the melt viscosity is low and the cured product is excellent in heat resistance, heat decomposability, and flame retardancy, An active ester resin containing a trinuclear compound (α2) having a k value of 2 in the structural formula (6) is more preferable, and the content of the dinuclear compound (α1) in the active ester resin is measured by GPC. Even more preferable is an active ester resin in which the content ratio of the trinuclear compound (α2) is in the range of 5 to 50% in terms of the area ratio in GPC measurement.

  The active ester compound represented by any one of the structural formula (6) uses, for example, parabenzoquinone as the compound (Q) having a quinone structure and dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group, It can be manufactured by a method. At this time, since the reaction ratio of parabenzoquinone and dihydroxynaphthalene is low in melt viscosity and an active ester resin having further excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product is obtained, 1 mol of parabenzoquinone, It is preferable that the dihydroxynaphthalene is in a proportion in the range of 0.1 to 10.0 mol.

  The dihydroxynaphthalene used here may be any positional isomer such as 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like. good. Among these, 2,7-dihydroxynaphthalene is more preferable because an active ester resin having a low melt viscosity and excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained.

  Examples of the compound represented by the structural formula (6) include an active ester compound represented by any one of the following structural formulas (6-1) to (6-30).

  In formulas (6-1) to (6-30), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  The active ester compound represented by the following structural formula (7) is produced by the above-described method using, for example, parabenzoquinone as the compound (Q) having a quinone structure and phenylphenol as the compound (P) having a phenolic hydroxyl group. I can do it. At this time, since the reaction ratio of parabenzoquinone and phenylphenol has a low melt viscosity and an active ester resin having further excellent heat resistance, heat decomposition resistance, and flame retardancy in the cured product is obtained, 1 mol of parabenzoquinone is obtained. It is preferable that the amount of phenylphenol is in the range of 0.1 to 10.0 mol.

In formula (7), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). R ⁵ is any one of 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, and u is an integer of 1 to 4. When u is an integer of 2 or more, the plurality of R ⁵ may be the same or different from each other. k is an integer of 1 to 3.

  Examples of the compound represented by the structural formula (7) include an active ester compound represented by any of the following structural formulas (7-1) to (7-12).

  In the formulas (7-1) to (7-12), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  More specifically, the active ester compound represented by the structural formula (I-2) includes an active ester compound represented by any one of the following structural formulas (8) to (11). Each will be described in detail below.

In formulas (8) to (11), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, a substituent on the aromatic nucleus As an active ester-forming structure site (z1) or a hydrogen atom (z2) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms. And at least one of Z in the molecule is an active ester forming structure site (z1), q is an integer of 0-4, and r is an integer of 1-2. R ⁵ is any one of 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, and u is an integer of 1 to 4. When u is an integer of 2 or more, the plurality of R ⁵ may be the same or different from each other.

  The active ester compound represented by the following structural formula (8) is, for example, 2,4,6-trimethyl-parabenzoquinone as the compound (Q) having a quinone structure, phenol as the compound (P) having a phenolic hydroxyl group, Using cresol, dimethylphenol or the like, it can be produced by the method described above. At this time, the reaction ratio between 2,4,6-trimethyl-parabenzoquinone and the compound (P) having a phenolic hydroxyl group has a low melt viscosity, and is further improved in heat resistance, heat decomposition resistance, and flame retardancy in the cured product. Since an excellent active ester resin is obtained, the compound (P) having a phenolic hydroxyl group is reacted at a ratio of 0.1 to 10.0 mol with respect to 1 mol of 2,4,6-trimethyl-parabenzoquinone. Is preferred.

  In the formula (8), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structure site (z1), and q is an integer of 0-4.

  Examples of the compound represented by the structural formula (8) include active ester compounds represented by any of the following structural formulas (8-1) to (8-9).

  In formulas (8-1) to (8-9), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  The active ester compound represented by the following structural formula (9) is, for example, 2,4,6-trimethyl-parabenzoquinone as the compound (Q) having a quinone structure, and dihydroxybenzene as a compound (P) having a phenolic hydroxyl group. Can be produced by the method described above. At this time, the reaction rate of 2,4,6-trimethyl-parabenzoquinone and dihydroxybenzene has a low melt viscosity, and an active ester resin having further excellent heat resistance, heat decomposition resistance and flame retardancy in a cured product can be obtained. Therefore, it is preferable that the amount of dihydroxybenzene is in the range of 0.1 to 10.0 mol with respect to 1 mol of 2,4,6-trimethyl-parabenzoquinone.

  In formula (9), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1).

  Examples of the compound represented by the structural formula (9) include an active ester compound represented by the following structural formula (9-1).

  In formula (9-1), Z represents a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon as a substituent on the aromatic nucleus. An active ester forming structure site (z1) or a hydrogen atom (z2) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 atoms or an acyl group having 2 to 6 carbon atoms And at least one of Z in the molecule is an active ester-forming structural site (z1).

  The active ester compound represented by the following structural formula (10) is, for example, 2,4,6-trimethyl-parabenzoquinone as the compound (Q) having a quinone structure, and dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group. Or it can manufacture by the above-mentioned method using naphthol. At this time, the reaction ratio of 2,4,6-trimethyl-parabenzoquinone and the compound (P) having a phenolic hydroxyl group has a low melt viscosity, and is further excellent in heat resistance, heat decomposition resistance and flame retardancy in the cured product. Since an active ester resin can be obtained, the ratio is preferably in the range of 0.1 to 10.0 mol of the compound (P) having a phenolic hydroxyl group with respect to 1 mol of 2,4,6-trimethyl-parabenzoquinone.

  In the formula (10), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester-forming structural site (z1), and r is an integer of 1 to 2.

  Examples of the compound represented by the structural formula (10) include an active ester compound represented by any one of the following structural formulas (10-1) to (10-12).

  In formulas (10-1) to (10-12), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  The active ester compound represented by the following structural formula (11) is, for example, 2,4,6-trimethyl-parabenzoquinone as the compound (Q) having a quinone structure, and phenylphenol as the compound (P) having a phenolic hydroxyl group. Using a compound, it can be produced by the method described above. At this time, the reaction ratio of 2,4,6-trimethyl-parabenzoquinone and the phenylphenol compound is an active ester resin having a low melt viscosity and further excellent heat resistance, heat decomposition resistance and flame retardancy in the cured product. Therefore, it is preferable that the phenylphenol compound is in a range of 0.1 to 10.0 mol with respect to 1 mol of 2,4,6-trimethyl-parabenzoquinone.

In formula (11), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). R ⁵ is any one of 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, and u is an integer of 1 to 4. When u is an integer of 2 or more, the plurality of R ⁵ may be the same or different from each other.

  Examples of the compound represented by the structural formula (11) include an active ester compound represented by any one of the following structural formulas (11-1) to (11-3).

  In formulas (11-1) to (11-3), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  More specifically, the active ester compound represented by the structural formula (I-3) includes an active ester compound represented by any one of the following structural formulas (12) to (16). Each will be described in detail below.

In formulas (12) to (16), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, a substituent on the aromatic nucleus As an active ester-forming structure site (z1) or a hydrogen atom (z2) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms. And at least one of Z in the molecule is an active ester-forming structural site (z1). q is an integer of 0-4, m is an integer of 1-2. R ⁵ is any one of 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, and u is an integer of 1 to 4. When u is an integer of 2 or more, the plurality of R ⁵ may be the same or different from each other.

  The active ester compound represented by the following structural formula (12) uses, for example, naphthoquinone as the compound (Q) having a quinone structure, and phenol, cresol, dimethylphenol or the like as the compound (P) having a phenolic hydroxyl group. It can be manufactured by a method. At this time, since the reaction rate of naphthoquinone and the compound (P) having a phenolic hydroxyl group is low in melt viscosity, an active ester resin having further excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. It is preferable that the ratio of the compound (P) having a phenolic hydroxyl group to be in the range of 0.1 to 10.0 mol with respect to 1 mol of naphthoquinone.

  In the formula (12), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). q is an integer of 0-4, m is an integer of 1-2.

  Examples of the compound represented by the structural formula (12) include active ester compounds represented by any of the following structural formulas (12-1) to (12-9).

  In formulas (12-1) to (12-9), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  The active ester compound represented by the following structural formula (13) is produced by the above-described method using, for example, naphthoquinone as the compound (Q) having a quinone structure and dihydroxybenzene as the compound (P) having a phenolic hydroxyl group. I can do it. At this time, the reaction ratio of 2,4,6-trimethyl-parabenzoquinone and 1,3-dihydroxybenzene has a low melt viscosity, and an active ester resin that is further excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product Therefore, it is preferable that dihydroxybenzene is in a range of 0.1 to 10.0 mol with respect to 1 mol of 2,4,6-trimethyl-parabenzoquinone.

  In formula (13), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). Moreover, m is an integer of 1-2.

  Examples of the compound represented by the structural formula (13) include an active ester compound represented by the following structural formula (13-1).

  In formula (13-1), Z represents a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon as a substituent on the aromatic nucleus. An active ester forming structure site (z1) or a hydrogen atom (z2) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 atoms or an acyl group having 2 to 6 carbon atoms And at least one of Z in the molecule is an active ester-forming structural site (z1).

  The active ester compound represented by the following structural formula (14) is produced by the above-described method using, for example, naphthoquinone as the compound (Q) having a quinone structure and naphthol as the compound (P) having a phenolic hydroxyl group. I can do it. At this time, the reaction ratio between naphthoquinone and naphthol is low in melt viscosity, and an active ester resin having further excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. Therefore, naphthol is 0 with respect to 1 mol of naphthoquinone. It is preferable that it is the ratio used as the range of 0.1-10.0 mol.

  In the formula (14), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). Moreover, m is an integer of 1-2.

  Examples of the compound represented by the structural formula (14) include active ester compounds represented by any of the following structural formulas (14-1) to (14-4).

  In formulas (14-1) to (14-4), Z represents a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  The active ester compound represented by the following structural formula (15) is particularly excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product among the active ester compounds represented by the general formula (I). Has characteristics. The active ester compound represented by the structural formula (15) is produced by the above-described method using, for example, naphthoquinone as the compound (Q) having a quinone structure and dihydroxynaphthalene as the compound (P) having a phenolic hydroxyl group. I can do it. At this time, since the reaction rate of naphthoquinone and dihydroxynaphthalene is an active ester resin having a low melt viscosity and further excellent heat resistance, heat decomposability and flame retardancy in the cured product, dihydroxynaphthalene is contained in 1 mol of naphthoquinone. The ratio is preferably in the range of 0.1 to 10.0 mol.

  In formula (15), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). Moreover, m is an integer of 1-2.

  The dihydroxynaphthalene used here may be any positional isomer such as 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxynaphthalene and the like. good. Among them, 2,7-dihydroxynaphthalene is preferable because an active ester resin having a low melt viscosity and excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained.

  Examples of the compound represented by the structural formula (15) include active ester compounds represented by any of the following structural formulas (15-1) to (15-8).

  In formulas (15-1) to (15-8), Z represents a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  The active ester resin containing the active ester compound represented by the structural formula (15) may further contain an active ester compound other than these. Among these, since it is excellent in the flame retardance in the cured product, it is preferable to contain a dinaphthofuran type compound represented by the following structural formula (15 ′). In this case, the content ratio of each component in the active ester resin is 2 to 60 in terms of the area ratio in the GPC measurement where the content ratio of the binuclear compound (α1) in which m is 1 in the structural formula (15). It is more preferable that the content of the dinaphthofuran compound is in the range of 1 to 60%.

  In the formula (15 ′), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, a carbon atom as a substituent on the aromatic nucleus It is an active ester-forming structure site (z1) or a hydrogen atom (z2) which is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 alkyl groups, or an acyl group having 2 to 6 carbon atoms. .

  The active ester compound represented by the following structural formula (16) is produced by the above-described method using, for example, naphthoquinone as the compound (Q) having a quinone structure and a phenylphenol compound as the compound (P) having a phenolic hydroxyl group. I can do it. At this time, the reaction ratio between naphthoquinone and the phenylphenol compound is an active ester resin having a low melt viscosity and further excellent heat resistance, thermal decomposition resistance, and flame retardancy in the cured product. Is preferably in the range of 0.1 to 10.0 mol.

In the formula (16), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, and a carbon atom number as a substituent on the aromatic nucleus. Is an active ester forming structure site (z1) or a hydrogen atom (z2), which is either a naphthoyl group having 1 to 7 alkyl groups of 1 to 4 or an acyl group having 2 to 6 carbon atoms, At least one of Z in the molecule is an active ester forming structural site (z1). m is an integer of 1-2. R ⁵ is any one of 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, and u is an integer of 1 to 4. When u is an integer of 2 or more, the plurality of R ⁵ may be the same or different from each other.

  Examples of the compound represented by the structural formula (16) include an active ester compound represented by any one of the following structural formulas (16-1) to (16-7).

  In formulas (16-1) to (16-7), Z is a benzoyl group, a benzoyl group having 1 to 5 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, a naphthoyl group, an aromatic nucleus An active ester forming structure site (z1) that is either a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms, or an acyl group having 2 to 6 carbon atoms, as the above substituent, or It is a hydrogen atom (z2), and at least one of Z in the molecule is an active ester forming structure site (z1).

  Among these exemplified active ester compounds, any one of the structural formulas (1) to (3) is used in that the melt viscosity is low and the cured product has an excellent balance of dielectric properties, heat resistance, heat decomposition resistance, and flame retardancy. An active ester compound represented by the structural formula (1) is more preferable because of its particularly low melt viscosity.

  Next, the curable composition of this invention is demonstrated. The curable composition of the present invention comprises the active ester compound or active ester resin of the present invention described in detail above and an epoxy resin as essential components.

  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 amount of the active ester resin and the epoxy resin in the curable composition of the present invention is that the carbonyloxy group and the phenolic hydroxyl group in the active ester resin are good in terms of curability and various physical properties of the cured product. It is preferable that the epoxy group in the epoxy resin has a ratio of 0.8 to 1.2 equivalents per 1 equivalent in total.

  In addition to the above-mentioned active ester resin and epoxy resin, the curable composition of the present invention may be used in combination with another epoxy resin curing agent other than the active ester resin. Examples of other curing agents for epoxy resin that can be used here include curing agents such as amine compounds, amide compounds, acid anhydride compounds, and phenol compounds. 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. .

  When the above-mentioned curing agent for epoxy resin is used in combination, the amount used is sufficient to exhibit the effect of excellent low dielectric constant and low dielectric loss tangent exhibited by the present invention. Therefore, the total curing agent including the active ester resin It is preferable that it is the range of 10-50 mass% in a component.

  Moreover, a hardening accelerator can also be suitably used together with the curable 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 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.

  In addition, the curable composition is blended with a non-halogen flame retardant that substantially does not contain a halogen atom in the range of, for example, the printed wiring board, in order to exhibit flame retardancy, as long as the reliability is not lowered. May be.

  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 depending on the type of the phosphorus-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. For example, the active ester resin, epoxy resin, In 100 parts by mass of curable composition containing all of halogen-based flame retardant and other fillers and additives, the range of 0.1-2.0 parts by mass when red phosphorus is used as a 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.

  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 compounding 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 composition, and the desired degree of flame retardancy. For example, an 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 composition in which all of epoxy resin, non-halogen flame retardant and other fillers and additives are compounded. It is preferable to mix in the range of ˜5 parts by mass.

  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 composition, and the desired degree of flame retardancy. For example, an 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 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 amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. For example, an 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 composition containing all of epoxy resin, non-halogen flame retardant and other fillers and additives, and in particular 0.5. It is preferable to mix in the range of ˜15 parts by mass.

  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-based flame retardant is appropriately selected depending on the type of the organic metal salt-based flame retardant, the other components of the curable composition, and the desired degree of flame retardancy. It is preferable to mix in the range of 0.005 to 10 parts by mass in 100 parts by mass of the curable composition containing all of the active ester resin, epoxy resin, non-halogen flame retardant and other fillers and additives.

  An inorganic filler can be mix | blended with the curable 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 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 composition of this invention as needed.

  The curable composition of this invention is obtained by mixing each above-mentioned component uniformly. The curable composition of the present invention in which the active ester resin of the present invention, the epoxy resin, and, if necessary, the curing accelerator is blended can be easily made into a cured product by a method similar to a conventionally known method. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Applications of the curable composition of the present invention include hard printed wiring board materials, resin compositions for flexible wiring boards, insulating materials for circuit boards such as build-up board interlayer insulating materials, semiconductor sealing materials, conductive materials Examples thereof include 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. Below, the method to obtain circuit boards, such as a hard printed wiring board, a flexible wiring board, a buildup board | substrate, is demonstrated using the curable composition of this invention.

  In order to obtain the circuit board from the curable composition of the present invention, a varnish obtained by diluting the curable composition in an organic solvent is obtained, and this is formed into a plate shape and laminated with a copper foil, and heated and pressed. A method of molding is mentioned.

  Specifically, as a method of obtaining a hard printed wiring board from the curable composition of the present invention, a varnish-like curable composition containing an organic solvent is further varnished using an organic solvent, and this is reinforced. Examples include a method of impregnating a material and semi-curing to obtain a prepreg, and superimposing a copper foil on the prepreg and then thermocompression bonding. 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. More specifically, the varnish-like curable composition described above is first heated at a heating temperature corresponding to the solvent type used, preferably 50 to 170 ° C., so that a prepreg as a cured product is obtained. obtain. At this time, the mass ratio of the curable 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.

  As a method of obtaining a flexible wiring board from the curable composition of the present invention, an electrically insulating film is prepared by using a coating machine such as a reverse roll coater or a comma coater with a compound containing an active ester resin, an epoxy resin, and an organic solvent. Then, it is heated at 60 to 170 ° C. for 1 to 15 minutes using a heater to volatilize the solvent, and the adhesive composition is B-staged. Then, the method of thermocompression bonding metal foil to an adhesive using a heating roll etc. is mentioned. The pressure for pressure bonding during thermocompression is preferably 2 to 200 N / cm, and the temperature for pressure bonding is preferably 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.

  As a method for obtaining a build-up substrate from the curable composition of the present invention, for example, the curable composition appropriately blended with rubber, filler, etc. is applied to a wiring substrate on which a circuit is formed by a spray coating method, a curtain coating method or the like. After applying and curing, the step of treating with a roughening agent, washing the surface with hot water to form irregularities, and plating a metal such as copper is repeated sequentially as desired, resin A method of alternately building up insulating layers and conductor layers having a predetermined circuit pattern is exemplified. As the plating method, electroless plating or electrolytic plating treatment is preferable. Examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent.

  As a method for obtaining a semiconductor encapsulating material from the curable composition of the present invention, an active ester resin, an epoxy resin, and a compounding agent such as an inorganic filler, if necessary, an extruder, a kneader, a roll, etc. The method of melt-mixing sufficiently until it is uniform is used. At that time, silica is usually used as the inorganic filler. In that case, a semiconductor sealing material is obtained by blending the inorganic filler in a ratio of 70 to 95% by mass in the curable composition. Can do.

  Furthermore, a semiconductor device can also be obtained from the curable composition of the present invention. As a method for obtaining a semiconductor device from the curable composition of the present invention, the curable composition is cast or molded using a transfer molding machine, an injection molding machine, etc., and further at 50 to 200 ° C. for 2 to 10 hours. The method of heating is mentioned.

  As a method for obtaining an adhesive film for buildup from the curable composition of the present invention, for example, the curable composition of the present invention is applied on a support film to form a curable composition layer to obtain an adhesive film. A method is mentioned. When the build-up adhesive film produced from the curable composition of the present invention is used, the adhesive film is softened under the lamination temperature condition (usually 70 ° C. to 140 ° C.) in the vacuum laminating method, and simultaneously with the circuit board lamination. It is important to exhibit fluidity (resin flow) that allows resin filling in via holes or through holes present in a circuit board, and it is preferable to blend the above-described components so as to exhibit such characteristics. The diameter of the through hole is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm. Usually, it is preferable that the resin can be filled in this range. When laminating both surfaces of the circuit board, it is desirable to fill about 1/2 of the through hole.

  The method for obtaining the adhesive film will be described more specifically. The curable composition of the present invention prepared in the form of a varnish is applied to the surface of the support film, and the organic solvent is dried by heating or hot air blowing. And a method of forming a layer of the curable composition (curable composition layer).

  In general, the thickness of the curable composition layer formed on the support film is preferably equal to or greater than the thickness of the conductor layer. Since the thickness of the conductor layer which the circuit board has is usually in the range of 5 to 70 μm, the thickness of the curable composition layer is preferably 10 to 100 μm.

  In addition, the curable composition layer 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 support film and the protective film include polyolefins such as polyethylene, polypropylene, and polyvinyl chloride, polyethylene terephthalate (hereinafter sometimes abbreviated as “PET”), polyesters such as polyethylene naphthalate, polycarbonate, polyimide, release paper, Examples of the metal foil include 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 is peeled off after being laminated on the circuit board or after the insulating layer is formed by heat curing. If the support film 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.

  In addition, a multilayer printed wiring board can also be obtained using the adhesive film obtained above. As such a method, for example, when the curable composition layer is protected with a protective film, after peeling off the curable composition layer, one side or both sides of the circuit board so that the curable composition layer is in direct contact with the circuit board. For example, a method of laminating by a vacuum laminating method may be mentioned. 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.

Lamination 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), and air pressure. Lamination is preferably performed under a reduced pressure of 20 mmHg (26.7 hPa) or less.

  As a method for obtaining a cured product from the curable composition of the present invention, a method based on a general curable composition curing method, for example, a heating temperature condition, may be appropriately selected depending on the type and use of the curing agent to be combined. Although it is possible, the method of heating in the temperature range of about 20-250 degreeC is mentioned, for example.

  As described above, the cured product obtained in this manner has excellent dielectric properties, and can realize high-speed operation speed of the high-frequency device.

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, ¹³ C-NMR, and MS were measured under the following conditions.

GPC: Measurement conditions are as follows.
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).

<Measurement conditions for ¹³ C-NMR>
The measurement conditions for ¹³ C-NMR were as follows.
Device: AL-400 manufactured by JEOL Ltd.
Measurement mode: SGNNE (1H complete decoupling method of NOE elimination),
Solvent: dimethyl sulfoxide,
Pulse angle: 45 ° pulse,
Sample concentration: 30 wt%
Integration count: 1000 times

<MS measuring device>
The following apparatus was used as the MS measurement apparatus.
Apparatus: Double convergence type mass spectrometer AX505H (FD505H) manufactured by JEOL Ltd.

Example 1 Production of Active Ester Resin (A-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 282 g (3 mol) of phenol and 3 g of paratoluenesulfonic acid and stirred. The temperature was raised from room temperature to 80 ° C. After reaching 80 ° C., 162 g (1.5 mol) of parabenzoquinone was added over 1 hour, and then the temperature was further raised to 130 ° C. and stirred for 1 hour to react. After completion of the reaction, the reaction product was dried under reduced pressure to obtain 250 g of a phenol intermediate (A). FIG. 1 shows a GPC chart of the obtained phenol intermediate (A), FIG. 2 shows a ¹³ CNMR spectrum, and FIG. 3 shows an MS spectrum. The hydroxyl equivalent of the phenol intermediate (A) was 88 g / eq, and the softening point was 95 ° C. From the MS spectrum, 202 peaks corresponding to the binuclear compound (a-1), 294 peaks corresponding to the trinuclear compound (b-1), and 386 corresponding to the tetranuclear compound (c-1) A peak was detected. The content of the binuclear compound (a-1) equivalent component in the phenol intermediate (A) calculated from the GPC chart is 37.3%, and the content of the trinuclear compound (b-1) equivalent component is 30. The content of the 7% tetranuclear compound (c-1) equivalent component was 10.3%.

  Next, 88 g (hydroxyl group: 1 eq) of the phenol intermediate (A) obtained in the above reaction and 270 g of methyl isobutyl ketone were charged into a flask equipped with a thermometer, a condenser and a stirrer while purging with nitrogen gas, and the system was depressurized. It was purged with nitrogen and 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, and 182 g of 20% aqueous sodium hydroxide solution was added. The solution 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 then methyl isobutyl ketone was removed by vacuum dehydration to obtain 205 g of an active ester resin (A-1). The functional group equivalent of the active ester resin (A-1) was 215 g / eq from the charging ratio. In the active ester resin (A-1), the carbonyloxy group was contained at a ratio of 90% with respect to the total number of functional groups of the carbonyloxy group and the phenolic hydroxyl group.

Example 2 Production of Active Ester Resin (B-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 649 g (6.0 mol) of orthocresol, 162 g of parabenzoquinone (1.5 mol) ), 8 g of paratoluenesulfonic acid was charged, and the temperature was raised from room temperature to 120 ° C. with stirring. After reaching 120 ° C., the mixture was stirred for 2 hours. After completion of the reaction, the precipitated crystal was separated and washed twice with 200 g of water. Thereafter, it was dried under heating under reduced pressure to obtain 117 g of phenol intermediate (B). FIG. 4 shows a GPC chart of the obtained phenol intermediate (B), FIG. 5 shows a ¹³ CNMR spectrum, and FIG. 6 shows an MS spectrum. The hydroxyl equivalent of the phenol intermediate (B) is 81 g / eq, and from the MS spectrum, 216 peaks corresponding to the binuclear compound (a-2), and 322 peaks corresponding to the trinuclear compound (b-2). 428 peaks corresponding to the tetranuclear compound (c-2) were detected. The content of the binuclear compound (a-2) equivalent component in the phenol intermediate (B) calculated from the GPC chart is 4.6%, and the content of the trinuclear compound (b-2) equivalent component is 88. The content of 0.0%, tetranuclear compound (c-2) equivalent component was 5.1%.

  Subsequently, the active ester resin (B) was obtained in the same manner as in Example 1 except that 81 g (hydroxyl group: 1 eq) of the phenol intermediate (B), 98.4 g (0.7 mol) of benzoyl chloride, and 135 g of a 20% aqueous sodium hydroxide solution were used. -1) 175 g was obtained. The functional group equivalent of the active ester resin (B-1) was 180 g / eq based on the charging ratio. In the active ester resin (B-1), the carbonyloxy group was contained at a ratio of 70% with respect to the total number of functional groups of the carbonyloxy group and the phenolic hydroxyl group.

Example 3 Production of Active Ester Resin (C-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 649 g (6.0 mol) of orthocresol and 3 g of paratoluenesulfonic acid. The temperature was raised from room temperature to 80 ° C. with stirring. After reaching 80 ° C., 162 g (1.5 mol) of parabenzoquinone was added over 1 hour, and then the temperature was further raised to 130 ° C. and stirred for 1 hour to react. After completion of the reaction, it was dried under reduced pressure to obtain 260 g of a phenol intermediate (C). A GPC chart of the obtained phenol intermediate (C) is shown in FIG. The hydroxyl equivalent of the phenol intermediate (C) was 97 g / eq. The content of the binuclear compound (α1) equivalent component in the phenol intermediate (C) calculated from the GPC chart is 25.8%, the content of the trinuclear compound (α2) equivalent component is 51.7%, The content of the tetranuclear compound (α3) equivalent component was 10.0%.

  Subsequently, the active ester resin (C) was obtained in the same manner as in Example 1 except that 97 g (hydroxyl group: 1 eq) of the phenol intermediate (C), 98.4 g (0.7 mol) of benzoyl chloride, and 135 g of a 20% aqueous sodium hydroxide solution were used. -1) 190 g was obtained. The functional group equivalent of the active ester resin (C-1) was 195 g / eq from the charged ratio. In the active ester resin (C-1), the carbonyloxy group was contained at a ratio of 70% with respect to the total number of functional groups of the carbonyloxy group and the phenolic hydroxyl group.

Example 4 Production of Active Ester Resin (D-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 733 g (6.0 mol) of 2,6-dimethylphenol and 216 g of parabenzoquinone (2.0 mol) and 9 g of paratoluenesulfonic acid were charged, and the temperature was raised from room temperature to 120 ° C. with stirring. After reaching 120 ° C., the mixture was stirred for 2 hours. After completion of the reaction, the precipitated crystal was separated and washed twice with 200 g of water. Thereafter, it was dried under heating under reduced pressure to obtain 123 g of a phenol intermediate (D). The GPC chart of the obtained phenol intermediate (D) is shown in FIG. 8, and the MS spectrum is shown in FIG. The hydroxyl equivalent of the phenol intermediate (D) is 88 g / eq, and the peak of 230 corresponding to the compound represented by the following structural formula (a-3) from the MS spectrum, represented by the following structural formula (b-3). 350 peaks corresponding to the above compound and 470 peaks corresponding to the compound represented by the following structural formula (c-3) were detected.

  Subsequently, an active ester resin (D) was obtained in the same manner as in Example 1 except that 88 g (hydroxyl group: 1 eq) of the phenol intermediate (D), 98.4 g (0.7 mol) of benzoyl chloride, and 135 g of a 20% aqueous sodium hydroxide solution were used. -1) 180 g was obtained. The functional group equivalent of the active ester resin (D-1) was 186 g / eq from the charged ratio. In the active ester resin (D-1), the carbonyloxy group was contained at a ratio of 70% with respect to the total number of functional groups of the carbonyloxy group and the phenolic hydroxyl group.

Example 5 Production of Active Ester Resin (E-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, resorcin 165 g (1.5 mol), parabenzoquinone 162 g (1.5 mol) Was heated from room temperature to 120 ° C. with stirring. After reaching 120 ° C., the mixture was stirred for 2 hours. After completion of the reaction, the mixture was heated to 180 ° C. and dried under reduced pressure to obtain 280 g of a phenol intermediate (E). FIG. 10 shows a GPC chart of the obtained phenol intermediate (E), FIG. 11 shows a ¹³ C-NMR spectrum, and FIG. 12 shows an MS spectrum. The hydroxyl equivalent of the phenol intermediate (E) was 60 g / eq, and the softening point was 98 ° C. From MS spectrum, 202, 218 peaks corresponding to the binuclear compound (α1), 310, 326 peaks corresponding to the trinuclear compound (α2), 418, 434 peaks corresponding to the tetranuclear compound (α3) Was detected. The content of the binuclear compound (α1) equivalent component in the phenol intermediate (E) calculated from the GPC chart is 20.0%, the content of the trinuclear compound (α2) equivalent component is 20.8%, The content of the tetranuclear compound (α3) equivalent component was 13.0%.

  Subsequently, an active ester resin (E) was obtained in the same manner as in Example 1 except that the phenol intermediate (E) was changed to 60 g (hydroxyl group: 1 eq), benzoyl chloride 98.4 g (0.7 mol), and 20% aqueous sodium hydroxide solution 135 g. -1) 155 g was obtained. The functional group equivalent of the active ester resin (E-1) was 158 g / eq from the charged ratio. In the active ester resin (E-1), the carbonyloxy group was contained at a ratio of 70% with respect to the total number of functional groups of the carbonyloxy group and the phenolic hydroxyl group.

Example 6 Production of Active Ester Resin (F-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 240 g (1.5 mol) of 2,7-dihydroxynaphthalene and 162 g of parabenzoquinone (1.5 mol), 268 g of isopropyl alcohol and 8 g of oxalic acid 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 2 hours. After completion of the reaction, the mixture was heated to 180 ° C. and dried under reduced pressure to obtain 359 g of a phenol intermediate (F). FIG. 13 shows a GPC chart of the obtained phenol intermediate (F), FIG. 14 shows a ¹³ CNMR spectrum, and FIG. 15 shows an MS spectrum. The hydroxyl equivalent of the phenol intermediate (F) was 68 g / eq, and the softening point was 126 ° C. From the MS spectrum, 268 peaks corresponding to the binuclear compound (a-4) and 426 peaks corresponding to the trinuclear compound (b-4) were detected. The content of the binuclear compound (a-4) equivalent component in the phenol intermediate (F) calculated from the GPC chart is 43.6%, and the content of the trinuclear compound (b-4) equivalent component is 30. 0.7%.

  Subsequently, an active ester resin (F) was obtained in the same manner as in Example 1 except that the phenol intermediate (F) was changed to 68 g (hydroxyl group: 1 eq), benzoyl chloride 98.4 g (0.7 mol), and 20% aqueous sodium hydroxide solution 135 g. -1) 160 g was obtained. The functional group equivalent of the active ester resin (F-1) was 166 g / eq based on the charging ratio. In the active ester resin (F-1), the carbonyloxy group was contained at a ratio of 70% with respect to the total number of functional groups of the carbonyloxy group and the phenolic hydroxyl group.

Example 7 Production of Active Ester Resin (G-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 160 g (1.0 mol) of 2,7-dihydroxynaphthalene, 158 g of naphthoquinone ( 1.0 mol) and 318 g of methyl isobutyl ketone were charged and the temperature was raised from room temperature to 150 ° C. with stirring. After reaching 150 ° C., the reaction was allowed to stir for 3 hours. After completion of the reaction, the mixture was heated to 180 ° C. and dried under reduced pressure to obtain 300 g of a phenol intermediate (G). The GPC chart of the obtained phenol intermediate (G) is shown in FIG. 16, and the MS spectrum is shown in FIG. The obtained phenol intermediate (G) had a hydroxyl group equivalent of 101 g / eq and a softening point of 130 ° C. From the MS spectrum, 318 peaks corresponding to the compound represented by the following structural formula (a-5) and 300 peaks corresponding to the compound represented by the following structural formula (d) were detected. The content of the binuclear compound (α1) equivalent component in the phenol intermediate (G) calculated from the GPC chart is 49.7%, and the content of the next naphthofuran compound represented by the following structural formula (d) is 6 0.0%.

  Subsequently, an active ester resin (G) was prepared in the same manner as in Example 1 except that 101 g of phenol intermediate (G) (hydroxyl group: 1 eq), 98.4 g (0.7 mol) of benzoyl chloride, and 135 g of 20% aqueous sodium hydroxide solution were used. -1) 195 g was obtained. The functional group equivalent of this active ester resin (G-1) was 199 g / eq from the charged ratio. Moreover, the esterification rate with respect to the phenolic hydroxyl group in the used phenol intermediate (G) was 70%.

Comparative Synthesis Example 1 Production of Active Ester Resin (A′-1) Activity was carried out in the same manner as in Example 1 except that the phenol intermediate (A) was changed to a phenol novolac resin (“TD-2090” manufactured by DIC Corporation). 180 g of ester 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 8-14, Comparative Example 1
In accordance with the formulation shown in Table 1 below, “850-S” (bisphenol A type epoxy resin, epoxy equivalent: 187 g / eq) made by DIC as an epoxy resin, and the active ester resin (A-1), (B-1) as a curing agent ), (C-1), (D-1), (E-1), (F-1), (G-1), (A′-1), and dimethylaminopyridine 0 as a curing accelerator. 0.5 phr was added, and methyl ethyl ketone was blended and adjusted so that the nonvolatile content (NV) of each composition was finally 58 mass%.

  Next, the laminate was cured under the following conditions to produce a prototype, and dielectric properties, heat resistance, heat decomposition resistance, 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 dielectric constant and dissipation factor>
In accordance with JIS-C-6481, the dielectric material at 1 GHz of the test piece after being stored in an indoor room at 23 ° C. and 50% humidity for 24 hours after absolutely dry using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. The rate and dielectric loss tangent were measured.

<Heat resistance (glass transition temperature)>
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.

<Evaluation of thermal decomposition resistance>
A cured product having a thickness of 0.8 mm was cut into a size of 5 mm in width and 54 mm in length, and the test piece was held at 250 ° C. for 72 hours, and then the weight reduction rate when compared with the initial mass was evaluated.

<Flame retardance>
In accordance with the UL-94 test method, a combustion test was performed using five laminated plates having a thickness of 0.8 mm.

Claims (11)

It has a molecular structure represented by the following general formula (I), and at least one of Z in the molecule is a benzoyl group or an alkyl group having 1 to 4 carbon atoms as a substituent on the aromatic nucleus. A benzoyl group having five, a naphthoyl group, a naphthoyl group having 1 to 7 alkyl groups having 1 to 4 carbon atoms as a substituent on the aromatic nucleus, or an acyl group having 2 to 6 carbon atoms An active ester compound characterized by being an active ester-forming structural site (z1).

[In Formula (1), Z is the said active ester formation structure site | part (z1) or a hydrogen atom (z2). X is a structural moiety represented by the following structural formula (x1) or (x2). ]

[In Formula (x1) or (x2), R ¹ and R ² are each 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; Is an integer from 0 to 3, and n is an integer from 0 to 4. When l or n is an integer of 2 or more, a plurality of R ¹ or R ² may be the same or different from each other. k is an integer of 1 to 3, m is an integer of 1 to 2, and * 1 represents a bonding point with an O atom in the general formula (I). Furthermore, Ar is a structural site represented by the following structural formula (Ar1) or (Ar2). When k or m is an integer of 2 or more, the plurality of Ars may be the same or different. ]

[In Formula (Ar1) or (Ar2), Z is the active ester-forming structure site (z1) or hydrogen atom (z2), and p and r are 1 to 2, respectively. When p and r are 2, two Z in the formula may be the same or different. R ³ and R ⁴ are each 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, and R ⁴ and OZ in formula (Ar2) May be bonded to either of the two aromatic nuclei. q is an integer of 0 to 4, s is an integer of 0 to 6, and when q or s is an integer of 2 or more, a plurality of R ³ or R ⁴ may be the same or different from each other. good. * 2 represents the point of attachment to the aromatic nucleus in the structural formula (x1) or (x2). ]   An active ester resin containing the active ester compound according to claim 1.   The active ester resin according to claim 2, wherein 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 in the range of 60 to 300 g / eq.   The active ester resin according to claim 2, 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 active ester resin is 40% or more.   A phenol intermediate (a) is obtained 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, and then the obtained phenol intermediate (a) And a monocarboxylic acid compound or a halide (b) thereof, and a method for producing an active ester resin.   A curable composition comprising the active ester compound according to claim 1 or the active ester resin according to any one of claims 2 to 4 and an epoxy resin.   Hardened | cured material formed by carrying out hardening reaction of the curable composition of Claim 6.   A buildup film, wherein the curable composition according to claim 6 diluted in an organic solvent is applied onto a substrate film and dried.   The semiconductor sealing material which contains the curable composition of Claim 6, and an inorganic filler, and content of an inorganic filler is the range of 70-95 mass%.   A prepreg obtained by impregnating a reinforced composition obtained by diluting the curable composition according to claim 6 with an organic solvent into a reinforcing base material and semi-curing the resulting impregnated base material.   The circuit board obtained by obtaining the varnish which diluted the curable composition of Claim 6 in the organic solvent, and shape | molding this in plate shape and copper foil.

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