JP6403003B2 - Cyanate ester compound, cyanate ester resin, curable composition, cured product thereof, build-up film, semiconductor sealing material, prepreg, circuit board, and method for producing cyanate ester resin - Google Patents

Description

  The present invention provides a cured product obtained by a cyanate ester compound, a cyanate ester resin, a curable composition, and a cured product thereof having a low dielectric constant, dielectric loss tangent, and excellent heat resistance, heat decomposition resistance, and flame retardancy. And a buildup film, a semiconductor sealing material, a prepreg, a circuit board, and a cyanate ester resin manufacturing method using the same.

  In recent years, frequencies used in fields such as the electronics industry, communications, and computers are becoming high frequency regions such as the gigahertz band. A material having a low dielectric constant and a low dielectric loss tangent is required for an insulating layer such as an electrical laminate used in such a high frequency region. For this reason, various low dielectric constant and low dielectric loss tangent resins have been developed.

  Among them, cyanate ester compounds are known to have excellent dielectric constant and dielectric loss tangent in cured products. Patent Document 1 describes a bisphenol A-type cyanate ester compound which is a 2,2-bis (4-hydroxyphenyl) propane (bisphenol A) derivative as a representative cyanate ester compound. However, the conventional cyanate ester resin composition containing the compound is generally used as an epoxy resin composition, a polyester resin composition, a phenol resin composition, or a polyimide resin composition, which is generally used as a matrix resin for an electronic circuit board. Although it has excellent dielectric properties in the high-frequency region, particularly in the gigahertz band, compared to other materials, there is a problem that the dielectric properties cannot meet the demands of the market.

  In addition, in recent years, high melting point solder that does not use lead has become mainstream due to environmental regulations and the like, and this lead-free solder has a use temperature of about 20 to 40 ° C. higher than conventional eutectic solder. In addition, because it is required to show high flame retardancy without using a halogen-based flame retardant for environmental reasons and disaster prevention reasons, when using a cyanate ester resin composition as an electronic material, The cyanate ester resin composition is required to have higher heat resistance, heat decomposition resistance, and flame retardancy than ever before.

JP 2002-69156 A

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

  As a result of intensive studies to solve the above problems, the present inventors have found that a cyanate ester compound represented by the following structural formula (I) has a rigid molecular structure in which aromatic nuclei are directly bonded, As compared with typical resins, it has a low molecular weight and a high cyanate group concentration, so 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. The present invention has been completed.

  That is, this invention relates to the cyanate ester compound characterized by having the molecular structure represented by the following general formula (I).

  In formula (1), X is a structural site 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, plural or R ² may be the same or different from each other. Ar is a structural moiety represented by the following structural formula (Ar1) or (Ar2), k is an integer of 1 to 3, and m is an integer of 1 to 2. When k or m is an integer of 2 or more, the plurality of Ars may be the same or different. In addition, * 1 shows the coupling | bonding point with O atom in the said general formula (I).

In the formula (Ar1) or (Ar2), 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 each an integer of 1 to 2. R ⁴ and the cyanato group in the formula (Ar2) may be bonded to any one of the two aromatic nuclei. In addition, * 2 shows the coupling | bonding point with the carbon atom on an aromatic nucleus in the said structural formula (x1) or (x2).

  The present invention further relates to a cyanate ester resin containing a cyanate 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 a cyanate ester resin, wherein the intermediate (a) is cyanated.

  The present invention further relates to a curable composition comprising the cyanate ester compound or the cyanate ester resin and a curing agent as essential components.

  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, in the obtained cured product, a cyanate ester compound, a cyanate ester resin, which have a low dielectric constant, a dielectric loss tangent, excellent heat resistance, heat decomposition resistance, and flame retardancy, and a curable composition containing these Product, its cured product, build-up film, semiconductor encapsulating material, prepreg, circuit board, and cyanate ester resin production method.

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 cyanate ester compound of the present invention is a compound having a molecular structure represented by the following general formula (I).

  In the formula (I), 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, the plurality of R ¹ or R ² may be the same or different from each other. Ar is a structural moiety represented by the following structural formula (Ar1) or (Ar2), k is an integer of 1 to 3, and m is an integer of 1 to 2. When k or m is an integer of 2 or more, the plurality of Ars may be the same or different. In addition, * 1 shows the coupling | bonding point with O atom in the said general formula (I).

In the formula (Ar1) or (Ar2), 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 each an integer of 1 to 2. R ⁴ and the cyanato group in the formula (Ar2) may be bonded to any one of the two aromatic nuclei. In addition, * 2 shows the coupling | bonding point with the carbon atom on an aromatic nucleus in the said structural formula (x1) or (x2).

  In the cyanate ester compound of the present invention, as described above, a cyanate group is introduced into a structure in which aromatic nuclei are bonded without using a methylene chain (structure represented by structural formulas (x1) and (x2)). Consists of configuration. In this way, a compound having a rigid molecular structure in which aromatic nuclei are bonded to each other without a methylene chain suppresses molecular motion and has a high aromatic ring concentration compared to a long-chain resin such as a novolak resin. Therefore, the obtained cured product has the characteristics that the dielectric constant and the dielectric loss tangent are low and the thermal decomposition temperature is high.

  Furthermore, a compound in which a cyanate group is introduced into 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) is a general resin. Compared with the above, since the cyanate group concentration is high and the cured product has a high cross-linking density, the obtained cured product is characterized by high heat resistance.

  In general, a compound having a high cyanate group concentration tends to be inferior in flame retardancy of a cured product because a flammable cyanate group is present in close proximity. However, the cyanate ester compound of the present invention has the above-described properties. In this way, in the structural formula (x1) or (x2), the two cyanate groups introduced at the para position of the aromatic nucleus have excellent reactivity. Since it has, it has the characteristic of having the outstanding flame retardance in hardened | cured material.

  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

  The cyanate ester compound represented by the general formula (I) includes, for example, a non-catalyzed compound (Q) having a quinone structure in the molecular structure and a compound (P) having a phenolic hydroxyl group in the molecular structure. Alternatively, it is produced by a method in which a phenol intermediate (a) is obtained by reaction in a temperature range of 40 to 180 ° C. under acid catalyst conditions, and then the obtained phenol intermediate (a) is reacted with cyanogen halide. Things. When the cyanate ester compound of the present invention is produced by such a method, an arbitrary component is selectively produced depending on the reaction conditions, or it is produced as a cyanate ester resin that is a mixture of plural kinds of cyanate ester compounds. I can do it. Moreover, you may isolate and use only arbitrary components from the cyanate ester resin which is a mixture.

  Examples of the compound (Q) having a quinone structure in the molecular 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, the plurality of R ¹ or R ² may be the same or different from each other.

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

  Examples of the compound (P) having a phenolic hydroxyl group in the molecular structure 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, and 2,4-dimethyl. Phenol, 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- Methoxyphenol, 2-ethoxyphenol, 3-ethoxyphenol, 4-ethoxyphenol, 2-phenylphenol, 3-phenylphenol, 4-phenylphenol, 4-benzylphenol, 1,2-dihydroxybenzene, 1,3-dihydroxy Benzene, 1,4-dihydroxybenzene, 1-naphthol, 2-naphthol, 1,4-dihydroxynaphthalene, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, 2,7-dihydroxy And naphthalene. These may be used alone or in combination of two or more.

  The reaction between the compound (Q) having a quinone structure in the molecular structure and the compound (P) having a phenolic hydroxyl group in the molecular structure proceeds under non-catalytic conditions because of its high reactivity. You may carry out using a 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, they should be used in an amount of 5.0% by mass or less based on the total mass of the compound (Q) having the quinone structure and the compound (P) having a phenolic hydroxyl group in the molecular structure. Is preferred.

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

  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 cyanogen halide, whereby the cyanate compound binuclear compound (Α1) is generated. Similarly, by reacting with the following cyanogen halide, the phenol intermediate corresponding to the case where the value of k or m is 2 produces the trinuclear compound (α2), and the value of k is 3. To form 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 dinuclear compound (α1) in the cyanate ester compound, and the value of k or m is The compound in the case of 2 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). When a cyanate ester resin described below is synthesized from the phenol intermediate (a), a binuclear compound (α1), a trinuclear compound (α2), and a tetranuclear compound (α3) in the cyanate ester resin are used. ) Depends on the proportion of the precursor contained in the phenol intermediate (a), and is maintained and does not change even after reaction with cyanogen halide.

  Next, examples of the cyanogen halide to be reacted with the obtained phenol intermediate (a) include cyanogen chloride and cyanogen bromide. The reaction in step 2 is preferable because the reaction is promoted under basic catalyst conditions. The basic catalyst used here is, for example, a tertiary amine such as triethylamine or trimethylamine, sodium hydroxide or hydroxide. Examples thereof include alkali metal hydroxides such as potassium.

  The reaction of the phenol intermediate (a) with cyanogen halide is preferably performed by dissolving each raw material component in an organic solvent. Examples of the organic solvent used here include benzene, toluene, xylene and the like. Aromatic compound solvents and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone are listed.

  After completion of the reaction, an appropriate amount of water is added to the reaction solution to dissolve the produced salt, and washing with water is repeated to remove the produced salt in the system. Subsequently, further purification is performed by dehydration or filtration, and the organic solvent is removed by distillation, whereby a target cyanate ester resin can be obtained.

  The cyanate ester compound of the present invention has a low dielectric constant and dielectric loss tangent in the cured product obtained in any case as long as it has the structure represented by the general formula (I). , Heat resistance, heat decomposability, and flame retardancy. Hereinafter, the more preferable thing of the cyanate ester compound which has a structure represented by the said general formula (I) is explained in full detail.

  Representative examples of the cyanate ester compound represented by the general formula (I) include compounds having a molecular structure represented by any one of the following structural formulas (I-1) to (I-3). .

  In formulas (I-1) to (I-3), k is an integer of 1 to 3, m is an integer of 1 to 2, and when k or m is an integer of 2 or more, a plurality of Ars are the same. It may be different or different. Ar is a structural portion represented by either the following structural formula (Ar1) or (Ar2).

In the formula (Ar1) or (Ar2), 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 each an integer of 1 to 2. R ⁴ and the cyanato group in the formula (Ar2) may be bonded to any one of the two aromatic nuclei. In addition, * 2 shows the coupling | bonding point with the carbon atom on an aromatic nucleus in the said structural formula (x1) or (x2).

  More specifically, examples of the cyanate ester compound represented by the structural formula (I-1) include compounds having a molecular structure represented by any one of the following structural formulas (1) to (7).

In formulas (1) to (7), k is an integer of 1 to 3, and u is an integer of 1 to 4. 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. When u is an integer of 2 or more, a plurality of R ⁵ are the same. There may be different or different.

  Hereinafter, a cyanate ester resin including a cyanate ester compound having a molecular structure of the structural formulas (1) to (7) and a cyanate ester compound having a molecular structure of the structural formulas (1) to (7). This will be described in detail.

  Among the cyanate ester compounds of the present invention, the cyanate ester compound represented by the following structural formula (1) has a particularly low melt viscosity, and has heat resistance, heat decomposition resistance, flame retardancy, and It has a feature that it is particularly excellent in balance with dielectric properties.

  In formula (1), k is an integer of 1-3.

  The cyanate ester resin containing the cyanate ester compound represented by the structural formula (1) has the same characteristics as the cyanate ester compound represented by the structural formula (1), but the heat resistance in the cured product, Since the thermal decomposition resistance and flame retardancy are further improved, a binuclear compound (α1) having a k value of 1 and a trinuclear compound (α2) having a k value of 2 in the structural formula (1). And a cyanate ester resin containing Among the resins, the content of the binuclear compound (α1) in the cyanate ester resin is in the range of 10 to 50% as an area ratio in GPC measurement, and the content of the trinuclear compound (α2) Is more preferably a cyanate ester resin having an area ratio of 10 to 50% in GPC measurement.

  In particular, in addition to the binuclear compound (α1) and the trinuclear compound (α2), the k value is 3 because the obtained cured product has more excellent heat resistance, thermal decomposition resistance, and flame retardancy. A cyanate ester resin containing a certain tetranuclear compound (α3) or a tetranuclear compound (α3 ′) represented by the following structural formula (1 ′) is preferable. At this time, the 4 in the cyanate ester resin is preferable. The total content of the nucleus compound (α3) and the tetranuclear compound (α3 ′) is preferably in the range of 2 to 20% in terms of area ratio in GPC measurement.

In the present invention, the dinuclear compound (α1), the trinuclear compound (α2), the tetranuclear compound (α3), and the tetranuclear compound (α3 ′) are contained in the cyanate ester resin. The rate is the ratio of the peak area of each component to the total peak area of the cyanate 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”.
(Polystyrene used)
“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 cyanate ester compound represented by the structural formula (1) includes, for example, parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure, and a compound (P) having a phenolic hydroxyl group in the molecular structure. Can be produced by the above-mentioned method using phenol. At this time, the reaction ratio of parabenzoquinone and phenol is adjusted so that the content of the binuclear compound (α1) and the trinuclear compound (α2) in the obtained cyanate ester resin is within the preferable range described above. Therefore, it is preferable that phenol is in a range of 0.1 to 10.0 moles with respect to 1 mole of parabenzoquinone.

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

  The cyanate ester compound represented by the following structural formula (2) has a particularly low melt viscosity among the cyanate ester compounds represented by the general formula (I), and has a dielectric property, heat resistance, and thermal decomposition in a cured product. It has the characteristic that it is excellent in property and a flame retardance.

  In formula (2), k is an integer of 1 to 3.

  The cyanate ester resin containing the cyanate ester compound represented by the structural formula (2) has the same characteristics as the cyanate ester compound represented by the structural formula (2), but the heat resistance in the cured product, Since the thermal decomposition resistance and flame retardancy are further improved, the binuclear compound (α1) having a k value of 1 in the structural formula (2) and the k value of 2 in the structural formula (2) A cyanate ester resin containing a trinuclear compound (α2) is preferred. Among the resins, the content of the binuclear compound (α1) in the cyanate ester resin is in the range of 2 to 50% as an area ratio in GPC measurement, and the content of the trinuclear compound (α2) Is more preferably a cyanate ester resin in the range of 10 to 90% in area ratio in GPC measurement, the content of the binuclear compound (α1) is in the range of 2 to 25% in area ratio in GPC measurement, And the cyanate ester resin whose content rate of the said trinuclear compound ((alpha) 2) is the range of 25 to 90% by the area ratio in GPC measurement is still more preferable.

  In particular, the value of k in the structural formula (2) is 3 in addition to the dinuclear compound (α1) and the trinuclear compound (α2) in that a cured product having further excellent heat resistance is obtained. A cyanate ester resin containing a tetranuclear compound (α3) or a tetranuclear compound (α3 ′) represented by the following structural formula (2 ′) is preferable. At this time, the four nuclei in the cyanate ester resin are preferred. The total content of the body compound (α3) and the tetranuclear compound (α3 ′) is more preferably in the range of 2 to 20% in terms of area ratio in GPC measurement.

  The cyanate ester compound represented by the structural formula (2) is, for example, a compound (P) having parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure and a phenolic hydroxyl group in the molecular structure. Can be produced by the above-described method using cresol. At this time, the reaction ratio of parabenzoquinone and cresol is adjusted so that the content of the binuclear compound (α1) and the trinuclear compound (α2) in the obtained cyanate ester resin is within the preferred range described above. Therefore, it is preferable that cresol is in a range of 0.1 to 10.0 moles per 1 mole of parabenzoquinone.

  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 a cyanate 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 a cyanate ester compound represented by any of the following structural formulas (2-1) to (2-31).

  The cyanate ester compound represented by the following structural formula (3) has a particularly low melt viscosity among the cyanate ester compounds represented by the general formula (I), and has a dielectric property, heat resistance, and thermal decomposition in a cured product. It has the characteristic that it is excellent in property and a flame retardance.

  In formula (3), k is an integer of 1-3.

  The cyanate ester resin containing the cyanate ester compound represented by the structural formula (3) has the same characteristics as the cyanate ester compound represented by the structural formula (3), but has a low melt viscosity and is cured. The binuclear compound (α1) having a k value of 1 in the structural formula (3) and k in the structural formula (3) are more excellent in heat resistance, thermal decomposition resistance, and flame retardancy in the product. A cyanate ester resin containing a trinuclear compound (α2) having a value of 2 is preferable. Among the resins, the content of the binuclear compound (α1) in the cyanate ester resin is in the range of 2 to 50% as an area ratio in GPC measurement, and the content of the trinuclear compound (α2) Is more preferably in the range of 10 to 95% in terms of area ratio in GPC measurement. Furthermore, the content of the dinuclear compound (α1) in the cyanate ester resin is in the range of 2 to 25% in terms of area ratio in GPC measurement, and the content of the trinuclear compound (α2) is GPC. The area ratio in the measurement is particularly preferably in the range of 50 to 95%.

  In particular, in terms of obtaining a cured product having further excellent heat resistance, the value of k in the structural formula (3) is 3 in addition to the dinuclear compound (α1) and the trinuclear compound (α2). A cyanate ester resin containing a tetranuclear compound (α3) or a tetranuclear compound (α3 ′) represented by the following structural formula (3 ′) is preferable. At this time, the four nuclei in the cyanate ester resin are preferred. The total content of the body compound (α3) and the tetranuclear compound (α3 ′) is more preferably in the range of 0.5 to 10% in terms of area ratio in GPC measurement.

  The cyanate ester compound represented by the structural formula (3) is, for example, a compound (P) having parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure and a phenolic hydroxyl group in the molecular structure. As dimethylphenol, it can be produced by the method described above. At this time, the reaction ratio of parabenzoquinone and dimethylphenol is adjusted so that the content of the binuclear compound (α1) and the trinuclear compound (α2) in the obtained cyanate ester resin is within the preferred range described above. Since it becomes easy, it is preferable that it is a ratio from which a dimethylphenol becomes the range of 0.1-10.0 mol with respect to 1 mol of para benzoquinone.

  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 a cyanate 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 compounds represented by any one of the following structural formulas (3-1) to (3-3).

  The cyanate ester compound represented by the following structural formula (4) is, for example, a compound (P) having parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure and a phenolic hydroxyl group in the molecular structure. Can be produced by the above-mentioned method using dihydroxybenzene as At this time, the reaction ratio of parabenzoquinone and dihydroxybenzene is low in melt viscosity, and a cyanate ester resin having further excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. On the other hand, it is preferable that the ratio is such that dihydroxybenzene is in the range of 0.1 to 10.0 mol.

  In formula (4), k is an integer of 1-3.

  The dihydroxybenzene used above may be any positional isomer such as 1,2-dihydroxybenzene, 1,3-dihydroxybenzene, 1,4-dihydroxybenzene. Among these, 1,3-dihydroxybenzene is preferable because a cyanate 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 cyanate ester compound represented by the structural formula (4) include compounds represented by any of the following structural formulas (4-1) to (4-3).

  The cyanate ester resin containing the cyanate ester compound represented by the structural formula (4) may further contain other cyanate ester compounds. Examples of the other cyanate ester compounds include compounds represented by any one of the following structural formulas (4′-1) to (4′-8).

  In formulas (4′-1) to (4′-8), u and v are each an integer of 1 to 2.

  When the cyanate ester resin contains the other cyanate ester compound in addition to the compound represented by the structural formula (4), the content ratio of each component in the cyanate ester resin is low in the melt viscosity and cured. Therefore, the dinuclear compound (α1) having a k value of 1 in the structural formula (4) and the structural formula (4) are obtained. A trinuclear compound in which the total content with the compound represented by 4′-1) is in the range of 5 to 40% in terms of area ratio in GPC measurement, and the value of k is 2 in the structural formula (4) The total content of the compound represented by (α2) or the structural formula (4′-2) and the compound represented by the structural formula (4′-4) or (4′-5) is 10 to 60. % Is preferable.

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

  In formula (5), k is an integer of 1-3.

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

  The cyanate ester resin containing the cyanate ester compound represented by the structural formula (5) is particularly excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product. A cyanate ester resin containing a binuclear compound (α1) having a k value of 1 and a trinuclear compound (α2) having a k value of 2 in the structural formula (5) is preferable. Among the resins, the content of the binuclear compound (α1) in the cyanate ester resin is in the range of 5 to 60% as an area ratio in GPC measurement, and the content of the trinuclear compound (α2). Is particularly preferably a cyanate ester resin having an area ratio of 5 to 50% in GPC measurement.

  As the cyanate ester compound represented by the following structural formula (6), among the cyanate ester compounds represented by the general formula (I), particularly in the heat resistance, heat decomposition resistance, and flame retardancy in the cured product. It has the feature of being excellent.

  In formula (6), k is an integer of 1-3.

  The cyanate ester resin containing the cyanate ester compound represented by the structural formula (6) has the same characteristics as the cyanate ester compound represented by the structural formula (6). The binuclear compound (α1) having a value of k of 1 in the structural formula (6) and the structural formula (6) are low and more excellent in heat resistance, thermal decomposition resistance, and flame retardancy in the cured product. ), A cyanate ester resin containing a trinuclear compound (α2) having a k value of 2 is preferable, and the content ratio of the dinuclear compound (α1) in the cyanate ester resin is an area ratio in GPC measurement. More preferably, the content of the trinuclear compound (α2) is in the range of 5 to 50% in terms of area ratio in GPC measurement.

  The cyanate ester compound represented by any one of the structural formula (6) is, for example, a compound having parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure and a phenolic hydroxyl group in the molecular structure. (P) can be produced by the above-described method using dihydroxynaphthalene. At this time, since the reaction ratio of parabenzoquinone and dihydroxynaphthalene is a cyanate ester resin having a low melt viscosity and further excellent heat resistance, heat decomposability and flame retardancy in the cured product, The ratio of dihydroxynaphthalene is preferably 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 preferable because a cyanate 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 cyanate ester compound represented by the structural formula (6) include compounds represented by any of the following structural formulas (6-1) to (6-30).

The cyanate ester compound represented by the following structural formula (7) is, for example, a compound (P) having parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure and a phenolic hydroxyl group in the molecular structure. Can be produced by the above-described method using phenylphenol. At this time, the reaction ratio of parabenzoquinone and phenylphenol is a cyanate ester resin having a low melt viscosity and further excellent heat resistance, heat decomposition resistance and flame retardancy in the cured product. The ratio of phenylphenol is preferably in the range of 0.1 to 10.0 mol.

In formula (7), 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 k is an integer of 1 to 3. .

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

  More specifically, examples of the cyanate ester compound represented by the structural formula (I-2) include compounds represented by any of the following structural formulas (8) to (11). Hereinafter, each will be described in detail.

In formulas (8) to (11), 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, and an aralkyl group, and q is 0 to 4 An integer, r is an integer of 1 to 2, 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 cyanate ester compound represented by the following structural formula (8) includes, for example, 2,4,6-trimethyl-parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure, and phenol in the molecular structure. It can be produced by the above-described method using phenol, cresol, dimethylphenol or the like as the compound (P) having a functional hydroxyl group. At this time, the reaction rate of 2,4,6-trimethyl-parabenzoquinone and the compound (P) having a phenolic hydroxyl group in the molecular structure has a low melt viscosity, and the heat resistance, heat decomposition resistance, and Since a cyanate ester resin having further excellent flame retardancy can be obtained, the compound (P) having a phenolic hydroxyl group in the molecular structure is 0.1 to 1 mol of 2,4,6-trimethyl-parabenzoquinone. The ratio is preferably in the range of 10.0 mol.

  In formula (8), q is an integer of 0-4.

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

  The cyanate ester compound represented by the following structural formula (9) includes, for example, 2,4,6-trimethyl-parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure, and phenol in the molecular structure. It can be produced by the above-mentioned method using dihydroxybenzene as the compound (P) having a functional hydroxyl group. At this time, the reaction rate of 2,4,6-trimethyl-parabenzoquinone and dihydroxybenzene has a low melt viscosity, and a cyanate ester resin having further excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product is 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.

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

  The cyanate ester compound represented by the following structural formula (10) includes, for example, 2,4,6-trimethyl-parabenzoquinone as the compound (Q) having a quinone structure in the molecular structure, and phenol in the molecular structure. It can be produced by the above-described method using dihydroxynaphthalene or naphthol as the compound (P) having a functional hydroxyl group. At this time, the reaction ratio between 2,4,6-trimethyl-parabenzoquinone and the compound (P) having a phenolic hydroxyl group in the molecular structure has a low melt viscosity, and the heat resistance, heat decomposition resistance, and difficulty in the cured product are low. Since a cyanate ester resin having further excellent flammability can be obtained, the compound (P) having a phenolic hydroxyl group in the molecular structure is used in an amount of 0.1 to 10. with respect to 1 mol of 2,4,6-trimethyl-parabenzoquinone. The ratio is preferably in the range of 0 mole.

  In formula (10), r is an integer of 1-2.

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

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

In formula (11), 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 a cyanate ester compound represented by any one of the following structural formulas (11-1) to (11-3).

  More specifically, examples of the cyanate ester compound represented by the structural formula (I-3) include cyanate ester compounds represented by any of the following structural formulas (12) to (16). Each will be described in detail below.

  In formulas (12) to (16), R5 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, and an aralkyl group. q is an integer of 0-4, m is an integer of 1-2, u is an integer of 1-4. When u is an integer of 2 or more, the plurality of R5s may be the same or different.

  The cyanate ester compound represented by the following structural formula (12) includes, for example, naphthoquinone as the compound (Q) having a quinone structure in the molecular structure and phenol as a compound (P) having a phenolic hydroxyl group in the molecular structure. , Cresol, dimethylphenol and the like can be produced by the method described above. At this time, the reaction ratio between naphthoquinone and the compound (P) having a phenolic hydroxyl group in the molecular structure is low in melt viscosity, and is more excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product. Since the resin is obtained, it is preferable that the compound (P) having a phenolic hydroxyl group in the molecular structure is in a range of 0.1 to 10.0 mol with respect to 1 mol of naphthoquinone.

  In formula (12), 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 cyanate ester compounds represented by any of the following structural formulas (12-1) to (12-9).

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

  In formula (13), m is an integer of 1-2.

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

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

  In formula (14), m is an integer of 1-2.

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

  Among the cyanate ester compounds represented by the following structural formula (15), the cyanate ester compound represented by the general formula (I) is particularly excellent in heat resistance, heat decomposition resistance, and flame retardancy in a cured product. It has the feature of being excellent.

  In formula (15), m is an integer of 1-2.

  The cyanate ester compound represented by the structural formula (15) includes, for example, naphthoquinone as the compound (Q) having a quinone structure in the molecular structure, and the compound (P) having a phenolic hydroxyl group in the molecular structure. Using dihydroxynaphthalene, it can be produced by the method described above. At this time, since the reaction rate of naphthoquinone and dihydroxynaphthalene is low in melt viscosity, a cyanate ester resin having a further excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product can be obtained. It is preferable that the dihydroxynaphthalene has a ratio 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 preferable because a cyanate 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 cyanate ester compounds represented by any of the following structural formulas (15-1) to (15-8).

  The cyanate ester resin containing the cyanate ester compound represented by the structural formula (15) may further contain other cyanate ester compounds. Especially, since it is excellent in the flame retardance in hardened | cured material, it is preferable to contain the dinaphthofuran type compound represented by following structural formula (15 ').

  In this case, the content ratio of each component in the cyanate 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). % And the content of the dinaphthofuran compound is preferably in the range of 1 to 60%.

  The cyanate ester compound represented by the following structural formula (16) includes, for example, naphthoquinone as the compound (Q) having a quinone structure in the molecular structure and phenyl as a compound (P) having a phenolic hydroxyl group in the molecular structure. It can be produced by the above-described method using a phenol compound. At this time, the reaction ratio between naphthoquinone and the phenylphenol compound is low in melt viscosity, and since a cyanate ester resin having more excellent heat resistance, heat decomposition resistance, and flame retardancy in a cured product is obtained, 1 mol of naphthoquinone is obtained. The proportion of the phenylphenol compound is preferably in the range of 0.1 to 10.0 mol.

In Formula (16), 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 a cyanate ester compound represented by any one of the following structural formulas (16-1) to (16-7).

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

  Next, the curable composition of this invention is demonstrated. The curable composition of the present invention comprises the cyanate ester compound or cyanate ester resin detailed above and a curing accelerator as essential components.

  Specific examples of the curing accelerator used here include phenol compounds, amine compounds, Lewis acids, tertiary sulfonium salts, quaternary ammonium salts, quaternary phosphonium salts, and epoxy group-containing compounds. Among these, nonylphenol, 2,4,6-tris (dimethylaminomethyl) phenol, benzyldimethylamine, copper, lead, tin are highly compatible with cyanate ester resins and the reaction proceeds smoothly. , Manganese, Nickel, Iron, Zinc, Cobalt and other carboxylates, Titanium tetra-n-butoxide and its polymer, Copper, Nickel, Cobalt and other pentadionate salts, Tetrabutylammonium bromide, Tetrabutylphosphonium chloride, Octyl Zinc acid is preferred. Moreover, an epoxy group-containing compound is particularly preferable because the reaction rate is further increased.

  The amount of the curing accelerator used is preferably in the range of 0.001 to 1 part by mass with respect to 100 parts by mass of the cyanate ester resin, for example, since the ability to accelerate curing is sufficiently exhibited.

  Moreover, the curable composition of this invention is preferable from the further that the solubility to an organic solvent and a moldability become better by containing an epoxy resin in addition to the said hardening accelerator.

  Examples of the epoxy resin used here include bisphenol type epoxy resins such as bisphenol A type epoxy resins and bisphenol F type epoxy resins; biphenyl type epoxy resins such as biphenyl type epoxy resins and tetramethylbiphenyl type epoxy resins; and phenol novolac type epoxy resins. , Cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, epoxidized product of condensation product of phenol compound and aromatic aldehyde having phenolic hydroxyl group, novolac type epoxy resin such as biphenyl 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 novola Type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, diglycidyloxynaphthalene, 1,1-bis (2,7-diglycidyloxy- An epoxy resin having a naphthalene skeleton in a molecular structure such as 1-naphthyl) alkane; a phosphorus atom-containing epoxy resin, and the like.

  Among these, since a cured product having higher heat resistance can be obtained, a phenol aralkyl type epoxy resin, a biphenyl novolac type epoxy resin, a naphthol novolak type epoxy resin containing a naphthalene skeleton, a naphthol aralkyl type epoxy resin, a naphthol-phenol Co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, crystalline biphenyl type epoxy resin, tetramethylbiphenyl type epoxy resin, xanthene type epoxy resin, alkoxy group-containing aromatic ring-modified novolak type epoxy resin ( A compound in which a glycidyl group-containing aromatic ring and an alkoxy group-containing aromatic ring are linked with formaldehyde is preferable.

  When using the said epoxy resin, it is preferable that the usage-amount is the range of 10-50 mass% in the curable composition of this invention.

  When using the said epoxy resin, you may use together the hardening | curing agent for epoxy resins. The epoxy resin curing agent used here is, for example, an amine compound such as diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF3-amine complex, guanidine derivative, etc .; dicyandiamide Amide compounds such as polyamide resin synthesized from dimer of linolenic acid and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, Acid anhydrides such as methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; modified phenol novolac resin, cresol novolac resin, aromatic hydrocarbon formaldehyde resin Enol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (Xylok resin), naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol-cresol co Condensed novolac resin, biphenyl-modified phenol 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 phenol resin ( Polyphenolic compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.) and alkoxy group-containing aromatic ring-modified novolak resins (formaldehyde with phenol) Nuclear and alkoxy groups polyhydric phenol compound-containing aromatic ring are connected) polyhydric phenol compound of the like. These may be used alone or in combination of two or more.

  Moreover, when using together the said epoxy resin, you may use together suitably the hardening accelerator for epoxy resins 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.

  The curable composition of the present invention may further contain a bismaleimide compound in addition to the cyanate ester resin of the present invention and the curing accelerator. The bismaleimide compound used here is not particularly limited as long as it is a compound having two or more maleimide groups in one molecule. Specifically, N-cyclohexylmaleimide, N-methylmaleimide, Nn -N-aliphatic maleimides such as butylmaleimide, N-hexylmaleimide, N-tert-butylmaleimide; N-aromatic maleimides such as N-phenylmaleimide, N- (P-methylphenyl) maleimide, N-benzylmaleimide; 4,4′-diphenylmethane bismaleimide, 4,4′-diphenylsulfone bismaleimide, m-phenylene bismaleimide, bis (3-methyl-4-maleimidophenyl) methane, bis (3-ethyl-4-maleimidophenyl) methane Bis (3,5-dimethyl-4-maleimidophenyl) meta , Bis (3-ethyl-5-methyl-4-maleimide phenyl) methane, bis (3,5-diethyl-4-maleimide phenyl) bismaleimide compounds such methane and the like.

  Among these, since the heat resistance of the cured product is particularly good, 4,4′-diphenylmethane bismaleimide, bis (3,5-dimethyl-4-maleimidophenyl) methane, bis (3-ethyl-5 -Methyl-4-maleimidophenyl) methane and bis (3,5-diethyl-4-maleimidophenyl) methane are preferred.

  When the curable composition of the present invention described above in detail is used as a varnish for a printed wiring board, it is preferable to add an organic solvent in addition to the above components. Examples of the organic solvent used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like. The type and appropriate amount of organic solvent can be appropriately selected depending on the application, but 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, It is preferable to use it in the ratio which becomes 40-80 mass% of non volatile matters. On the other hand, in build-up adhesive film applications, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, cellosolve, butyl carbitol, etc. Carbitol solvent, aromatic hydrocarbon solvent such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone and the like are preferably used, and the nonvolatile content is preferably 30 to 60% by mass.

  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 -Dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide and other cyclic organic phosphorus compounds, and derivatives obtained by reacting them with compounds such as epoxy resins and phenol resins.

  The blending amount thereof is appropriately selected according to the type of the phosphorus-based flame retardant, the other components of the curable composition, and the desired degree of flame retardant. For example, epoxy resin, curing agent, non-halogen In 100 parts by mass of the curable composition containing all of the flame retardant and other fillers and additives, when using red phosphorus as a non-halogen flame retardant, in the range of 0.1 to 2.0 parts by mass It is preferable to mix, and when using an organophosphorus compound, it is also preferable to mix 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. Is preferred.

  In addition, when using the phosphorus flame retardant, the phosphorus 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 paulownia 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, epoxy resin, curing It is preferable to mix in the range of 0.05 to 10 parts by mass, especially in 0.1 to 10 parts by mass, in 100 parts by mass of the curable composition containing all of the agent, non-halogen flame retardant and other fillers and additives. 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 flame retardant is appropriately selected depending on the type of the silicone 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 0.05 to 20 parts by mass in 100 parts by mass of the curable composition containing all of the agent, 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, Shipley (Bokusui Brown), hydrated glass SiO2-MgO-H2O, PbO-B2O3 series, ZnO-P2O5-MgO series, P2O5-B2O3-PbO-MgO series Examples thereof include glassy compounds such as P—Sn—O—F, PbO—V 2 O 5 —TeO 2, Al 2 O 3 —H 2 O, and lead borosilicate.

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, other components of the curable composition, and the desired degree of flame retardancy. For example, epoxy resin, curing 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 the agent, non-halogen flame retardant and other fillers and additives, and particularly 0.5 to 20 parts by mass. 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 epoxy resin, curing agent, 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 containing the cyanate ester compound or cyanate ester resin of the present invention, a curing accelerator, and, if necessary, an epoxy resin, can be easily made into a cured product by a method similar to a conventionally known method. Can do. As said hardened | cured material, shaping | molding hardened | cured materials, such as a laminated body, a casting, an adhesive layer, a coating film, a film, are mentioned.

  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 and semiconductor sealing materials, 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 a 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 shaped into a plate shape and laminated with a copper foil, followed by heat and pressure molding. The method of doing is mentioned.

  Among circuit boards, a method for obtaining a hard printed wiring board from the curable composition of the present invention is to reinforce a varnish-like curable composition containing an organic solvent and further varnished using an organic solvent. A method of impregnating a base material and semi-curing to obtain a prepreg, and then laminating a copper foil on the prepreg and heat-pressing the prepreg may be mentioned. Examples of the reinforcing substrate that can be used here include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. 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, The intended hard printed wiring board can be obtained.

  Among circuit boards, a method for obtaining a flexible wiring board from the curable composition of the present invention includes a reverse roll coater, a comma coater and the like in which a cyanate ester resin, a curing accelerator, an epoxy resin, and an organic solvent are blended. Using an applicator, it is applied to an electrically insulating film, then heated using a heater at 60-170 ° C. for 1-15 minutes, the solvent is evaporated, and the adhesive composition is B-staged, then And a method of thermocompression bonding a metal foil to the adhesive using a heating roll or the like. 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.

  Among circuit boards, a method for obtaining a build-up board from the curable composition of the present invention is to apply a curable composition onto a circuit board on which a circuit is formed using a spray coating method, a curtain coating method, or the like. After curing, the process of forming irregularities on the surface of the surface coated with the curable composition using a roughening agent and plating a metal such as copper is repeated sequentially as desired, and the resin insulation layer and the conductor One way is to build up the layers alternately. 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, a compounding agent such as a cyanate ester resin, a curing accelerator, an epoxy resin, and an inorganic filler, if necessary, an extruder, a kneader, A method of sufficiently melt-mixing until uniform using a roll or the like can be mentioned. 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.

  Examples of the method for obtaining the build-up adhesive film from the curable composition of the present invention include a method of applying the curable composition on a support film. When the adhesive film manufactured by the above method is used, the adhesive film is softened under the temperature condition of the laminate in the vacuum laminating method (usually 70 ° C. to 140 ° C.), and is present on the circuit board simultaneously with the lamination of the circuit board. It is important to show fluidity (resin flow) capable of filling the resin in the via hole or the through hole, and it is preferable to blend each of the 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 curable 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.

  The lamination conditions are such that the pressure bonding temperature (laminating temperature) is preferably 70 to 140 ° C., the pressure bonding pressure is preferably 9.8 × 10 4 to 107.9 × 104 N / m 2, and the lamination is performed under a reduced pressure of 26.7 hPa or less. It is preferable to do.

  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.

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”.
(Polystyrene used)
“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.

<IR measurement conditions>
The following apparatus was used as an IR measurement apparatus.
Equipment: “FT / IR-550” manufactured by JASCO Corporation

Example 1 Production of Cyanate Ester Resin (A-1) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer was charged with 282 g (3.0 mol) of phenol 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, 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, 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%.

Subsequently, 44 g (0.5 mol) of the phenol intermediate (A) obtained above and an odor were obtained while flowing nitrogen gas through a four-necked flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer. After 106 g (1.0 mol) of cyanide was charged and dissolved in 1000 g of acetone, it was cooled to −3 ° C. Next, 111 g (1.1 mol) of triethylamine was charged into the dropping funnel, and dropped at a rate such that the temperature inside the flask did not exceed 10 ° C. while stirring. After completion of the dropwise addition, the mixture was stirred at a temperature of 10 ° C. or lower for 2 hours. This was extracted with methylene chloride and washed with water to obtain 55 g of cyanate ester resin (A-1). The cyanate group equivalent of the obtained cyanate ester resin (A-1) was 113 g / eq. Moreover, since the IR spectrum of cyanate ester resin (A-1) showed absorption of 2264 cm ⁻¹ (cyanato group) and no hydroxyl group absorption, the target cyanate ester resin (A-1) It was confirmed that it was obtained.

Example 2 Production of Cyanate Ester Resin (B-1) In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, 649 g of orthocresol (6.0 mol) and 162 g of parabenzoquinone (1. 5 mol) and 8 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 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%.

Next, 50 g of cyanate ester resin (B-1) was obtained in the same manner as in Example 1, except that the phenol intermediate (B) was changed to 41 g (hydroxyl group: 0.5 eq). The functional group equivalent of this cyanate ester resin (B-1) was 106 g / eq from the charged ratio. Moreover, since the IR spectrum of cyanate ester resin (B-1) showed absorption of 2264 cm ⁻¹ (cyanato group) and no hydroxyl group absorption, the target cyanate ester resin (B-1) It was confirmed that it was obtained.

Example 3 Production of Cyanate Ester Resin (C-1) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer was charged with 649 g of orthocresol (6.0 mol) and 3 g of paratoluenesulfonic acid. The temperature was raised from room temperature to 80 ° C. while charging and 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 for reaction. 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%.

Next, 60 g of cyanate ester resin (C-1) was obtained in the same manner as in Example 1 except that the phenol intermediate (C) was changed to 49 g (hydroxyl group: 0.5 eq). The functional group equivalent of this cyanate ester resin (C-1) was 122 g / eq from the charged ratio. Moreover, since the IR spectrum of cyanate ester resin (C-1) showed absorption of 2264 cm ⁻¹ (cyanato group) and no hydroxyl group, the target cyanate ester resin (C-1) was It was confirmed that it was obtained.

Example 4 Production of cyanate ester resin (D-1) Into a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer, 733 g (6.0 mol) of 2,6-dimethylphenol, parabenzoquinone 216 g (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.

Next, 55 g of cyanate ester resin (D-1) was obtained in the same manner as in Example 1 except that the phenol intermediate (D) was changed to 44 g (hydroxyl group: 0.5 eq). The functional group equivalent of this cyanate ester resin (D-1) was 113 g / eq from the charged ratio. Moreover, since the IR spectrum of cyanate ester resin (D-1) showed absorption of 2264 cm ⁻¹ (cyanato group) and no hydroxyl group, the target cyanate ester resin (D-1) It was confirmed that it was obtained.

Example 5 Production of Cyanate Ester Resin (E-1) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 165 g (1.5 mol) of resorcin, 162 g (1.5 mol) of parabenzoquinone 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 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 CNMR 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%.

Next, 40 g of cyanate ester resin (E-1) was obtained in the same manner as in Example 1 except that the phenol intermediate (E) was changed to 30 g (hydroxyl group: 0.5 eq). The functional group equivalent of this cyanate ester resin (E-1) was 85 g / eq from the charged ratio. Moreover, since the IR spectrum of cyanate ester resin (E-1) showed absorption of 2264 cm ⁻¹ (cyanato group) and no hydroxyl group absorption, the target cyanate ester resin (E-1) was It was confirmed that it was obtained.

Example 6 Production of Cyanate Ester Resin (F-1) 240 g (1.5 mol) of 2,7-dihydroxynaphthalene and parabenzoquinone were placed in a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer. 162 g (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%.

Next, 45 g of cyanate ester resin (F-1) was obtained in the same manner as in Example 1, except that the phenol intermediate (F) was changed to 34 g (hydroxyl group: 0.5 eq). The functional group equivalent of this cyanate ester resin (F-1) was 93 g / eq from the charged ratio. Moreover, since the IR spectrum of cyanate ester resin (F-1) showed absorption of 2264 cm ⁻¹ (cyanato group) and no hydroxyl group absorption, the target cyanate ester resin (F-1) It was confirmed that it was obtained.

Example 7 Production of Cyanate Ester Resin (G-1) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 160 g (1.0 mol) of 2,7-dihydroxynaphthalene and 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%.

Next, 61 g of cyanate ester resin (G-1) was obtained in the same manner as in Example 1 except that the phenol intermediate (G) was changed to 51 g (hydroxyl group: 0.5 eq). The functional group equivalent of this cyanate ester resin (G-1) was 126 g / eq based on the charge ratio. Moreover, since the IR spectrum of cyanate ester resin (G-1) showed absorption of 2264 cm ⁻¹ (cyanato group) and no hydroxyl group, the target cyanate ester resin (G-1) It was confirmed that it was obtained.

Examples 8-14, Comparative Example 1
Cyanate ester resins (A-1), (B-1), (C-1), (D-1), (E-1), (F-1), (G) obtained in Examples 1 to 7 -1) or a comparative cyanate ester compound ("BA-200" manufactured by LONZA: bisphenol A type cyanate ester resin) 100g, zinc octylate 0.01Phr as a curing accelerator is blended, and a curable composition is prepared. It was adjusted. The obtained curable composition was molded with a press for 10 minutes under a temperature condition of 200 ° C., and then cured for 5 hours under a temperature condition of 200 ° C. to prepare a test piece. The obtained test pieces were evaluated for dielectric properties, heat resistance, heat decomposition resistance, and flame retardancy by the following methods. The results are shown in Table 1.

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

<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 weight was evaluated.

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

Claims (9)

A cyanate ester compound having a molecular structure represented by the following general formula (I):

[In formula (I), X is a structural site 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. Ar is a structural moiety represented by the following structural formula (Ar1) or (Ar2), k is an integer of 1 to 3, and m is an integer of 1 to 2. When k or m is an integer of 2 or more, the plurality of Ars may be the same or different. In addition, * 1 shows the coupling | bonding point with O atom in the said general formula (I). ]

[In the formula (Ar1) or (Ar2), 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 an integer from 0 to 4, and s is an integer from 0 to 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 each an integer of 1 to 2. R ⁴ and the cyanato group in the formula (Ar2) may be bonded to any one of the two aromatic nuclei. In addition, * 2 shows the coupling | bonding point with the carbon atom on an aromatic nucleus in the said structural formula (x1) or (x2). ]   A cyanate ester resin comprising the cyanate ester compound according to claim 1. 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) A process for producing a cyanate ester resin, characterized in that cyanate is converted into cyanate.   A curable composition comprising the cyanate ester compound according to claim 1 or the cyanate ester resin according to any one of claim 2 and a curing accelerator as essential components.   Hardened | cured material formed by carrying out hardening reaction of the curable composition of Claim 4.   A buildup film, wherein the curable composition according to claim 4 diluted with an organic solvent is applied onto a base film and dried.   The semiconductor sealing material which contains the curable composition and inorganic filler of Claim 4, and whose 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 4 with an organic solvent into a reinforcing base material and semi-curing the resulting impregnated base material.   A circuit board obtained by obtaining a varnish obtained by diluting the curable composition according to claim 4 in an organic solvent, and subjecting the varnish to a plate shape and a copper foil by heating and pressing.

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