JP5924523B2 - Active ester resin, curable resin composition, cured product thereof, semiconductor sealing material, prepreg, circuit board, and build-up film - Google Patents

Description

  The present invention provides a curable resin composition that exhibits excellent heat resistance and low dielectric loss tangent in the cured product, the cured product, and an active ester resin used therefor, and the curable resin composition semiconductor sealing material, The present invention relates to a prepreg, a circuit board, and a buildup film.

A curable resin composition containing an epoxy resin and a curing agent as an essential component exhibits excellent heat resistance and insulation in the cured product, and is therefore widely used in electronic component applications such as semiconductors and multilayer printed boards. Yes.
Among these electronic component applications, in the technical field of multilayer printed circuit board insulating materials, in recent years, signal speed and frequency have been increasing in various electronic devices. However, with the increase in signal speed and frequency, it is becoming difficult to obtain a low dielectric loss tangent while maintaining a sufficiently low dielectric constant.
Therefore, it is desired to provide a curable resin composition capable of obtaining a cured product that exhibits a sufficiently low dielectric loss tangent while maintaining a sufficiently low dielectric constant even with respect to high-speed and high-frequency signals. It is rare. As a material capable of realizing these low dielectric constants and low dielectric loss tangents, a technique using an active ester compound obtained by esterifying a phenolic hydroxyl group in a phenol novolac resin as a curing agent for an epoxy resin is known (see below, Patent Document 1).

  However, because of the trend toward higher frequency and smaller size in electronic components, multilayer printed circuit board insulating materials are required to have extremely high heat resistance, and active esters obtained by esterifying phenolic hydroxyl groups in the above-described phenol novolac resins. The compound had a reduced cross-linking density of the cured product due to the introduction of the ester structure, and the heat resistance of the cured product was insufficient. Thus, it was difficult to achieve both heat resistance and low dielectric constant / low dielectric loss tangent.

JP 7-82348 A

  Therefore, the problem to be solved by the present invention is that the cured product has a low dielectric constant and a low dielectric loss tangent, and can have excellent heat resistance, the cured product, and these cured products. An object of the present invention is to provide an active ester resin exhibiting performance, a semiconductor sealing material obtained from the composition, a prepreg, a circuit board, and a buildup film.

  As a result of intensive studies to solve the above problems, the present inventors have obtained an active ester resin obtained by arylating or acylating a calixarene type naphthol compound obtained by reacting naphthol and formaldehyde under predetermined conditions. The cured product has been found to have a low dielectric constant, a low dielectric loss tangent, and excellent heat resistance, and has completed the present invention.

  That is, the present invention provides the following structural formula (1)

（式中、Ｘは、ベンゾイル基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたベンゾイル基、ナフトイル基、及び炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフトイル基、炭素原子数２〜６のアシル基から成る群から選択されたエステル形成構造部位（ｘ１）、又は、水素原子（ｘ２）であり、Ｒ^１はそれぞれ独立的に、水素原子、アルキル基、アルコキシ基を表し、ｎは２〜１０の整数である。但し、Ｘの少なくとも一つは前記エステル形成構造部位（ｘ１）である。）で表わされる樹脂構造を有することを特徴とする活性エステル樹脂に関する。

(In the formula, X represents benzoyl group, benzoyl group substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, naphthoyl group, and 1 to 3 alkyl groups with 1 to 4 carbon atoms. A naphthoyl group substituted with a nucleus, an ester-forming structural site (x1) selected from the group consisting of an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (x2), and each R ¹ is independently It represents a hydrogen atom, an alkyl group, or an alkoxy group, and n is an integer of 2 to 10, provided that at least one of X is the ester forming structure site (x1)). It relates to a featured active ester resin.

  The present invention further comprises a curable resin composition comprising an active ester resin (A) and an epoxy resin (B) as essential components, wherein the active ester resin (A) is the active ester. The present invention relates to a curable resin composition characterized by using a resin.

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

  In the present invention, in addition to the active ester resin (A) and the epoxy resin (B) in the curable resin composition, the inorganic filler (C) is further added in a proportion of 70 to 95% by mass in the composition. The present invention relates to a semiconductor sealing material comprising a curable resin composition to be contained.

  The present invention further relates to a prepreg obtained by impregnating a reinforcing substrate with a solution obtained by diluting the curable resin 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 resin composition in an organic solvent, and heating and press-molding a varnish shaped into a plate shape and a copper foil.
The present invention further relates to a build-up film obtained by applying a material obtained by diluting the curable resin composition in an organic solvent onto a base film and drying it.

  According to the present invention, the cured product has an active ester resin, a curable resin composition, a cured product thereof, and a combination thereof, which can have excellent heat resistance while having a low dielectric constant and a low dielectric loss tangent. A semiconductor sealing material, a prepreg, a circuit board, and a buildup film can be provided.

FIG. 1 is a GPC chart of the active ester resin (A-2) obtained in Example 1.

  Hereinafter, the present invention will be described in detail.

  As described above, the active ester resin of the present invention has the following structural formula (1).

（式中、Ｘは、ベンゾイル基、炭素原子数１〜４のアルキル基の１〜３つで核置換されたベンゾイル基、ナフトイル基、及び炭素原子数１〜４のアルキル基の１〜３つで核置換されたナフトイル基、炭素原子数２〜６のアシル基から成る群から選択されたエステル形成構造部位（ｘ１）、又は、水素原子（ｘ２）であり、Ｒ^１はそれぞれ独立的に、水素原子、アルキル基、アルコキシ基を表し、ｎは２〜１０の整数である。但し、Ｘの少なくとも一つは前記エステル形成構造部位（ｘ１）である。）で表わされる樹脂構造を有するものである。

(In the formula, X represents benzoyl group, benzoyl group substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, naphthoyl group, and 1 to 3 alkyl groups with 1 to 4 carbon atoms. A naphthoyl group substituted with a nucleus, an ester-forming structural site (x1) selected from the group consisting of an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (x2), and each R ¹ is independently Represents a hydrogen atom, an alkyl group, or an alkoxy group, and n is an integer of 2 to 10, provided that at least one of X is a resin structure represented by the ester-forming structure moiety (x1). is there.

As described above, the active ester resin has a so-called calixarene-type cyclic structure, and as a result, molecular motion in the cured product of the active ester resin is suppressed, so that excellent heat resistance is expressed. Furthermore, in addition to the molecular motion suppression effect by the calixarene skeleton, the cured product obtained is more excellent in the dielectric loss tangent because the molecular motion is further suppressed due to the intermolecular interaction between acyl groups and the rigidity is increased. In addition, in the structural formula 1, it is easy to produce the active ester resin that the bonding position of the methylene group on the naphthalene ring has two bonding sites on the same ring. It is preferable from the point, and it is particularly preferable that a methylene group is bonded at the 2,4-position of the naphthalene ring because a regular molecular structure is formed and the cured product is excellent in heat resistance.
In addition, n in the structural formula 1 is an integer of 2 to 10, and is preferably 2, 4, 6, or 8 from the viewpoint that the chemical structure is excellent and the effect of improving the heat resistance is remarkably exhibited. In particular, 4 is most preferable.

  Such an active ester resin can be identified by confirming the molecular weight of the theoretical structure in the MS spectrum.

  X in the structural formula 1, as described above, is a benzoyl group, a benzoyl group substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms, a naphthoyl group, and an alkyl having 1 to 4 carbon atoms. A naphthoyl group nucleus-substituted with 1 to 3 of the groups, an ester-forming structural site (x1) selected from the group consisting of an acyl group having 2 to 6 carbon atoms, or a hydrogen atom (x2). Here, at least one of X is the ester forming structure site (x1), specifically, the ester forming structure with respect to the sum of the ester forming structure site (x1) and the hydrogen atom (x2). It is preferable from the point which is excellent in the dielectric property of hardened | cured material that a site | part (x1) is a ratio used as 40% or more.

  Thus, all of X in the structural formula 1 may be the ester-forming structural site (x1), but a part of X is a hydrogen atom (x2), that is, a phenolic hydroxyl group. When it has a part, sclerosis | hardenability will become favorable and a heat resistant improvement effect will become remarkable. In this case, the proportion of the ester-forming structural site (x1) and the hydrogen atom (x2) is specifically such that the ester-forming structural site (x1) is 40 to 95% of the total of both. Preferably there is.

Here, the benzoyl group nucleus-substituted with 1 to 3 alkyl groups having 1 to 4 carbon atoms is 2,4-dimethylbenzoyl group, 2,6-dimethylbenzoyl group, 2,4,6-trimethyl. Benzoyl group, 2-ethylbenzoyl group, 4-ethylbenzoyl group 2-t-butyl-4-ethylbenzoyl group, 4-i-propylbenzoyl group, 4-t-butylbenzoyl group, 2,6-di-t- A butylbenzoyl group is mentioned.

  In addition, a naphthoyl group that is nucleus-substituted with one or two alkyl groups having 1 to 4 carbon atoms includes a 2-methyl-1-naphthol group, a 4-methyl-1-naphthoyl group, and 2-ethyl-1- Naphthoyl group, 3-methyl-4-ethyl-2-naphthoyl group, 2-propyl-1-naphthoyl group, 2-propyl-4-ethyl-1-naphthoyl group, 6-propyl-2-naphthoyl group, 2-t -Butyl-1-naphthyl group, 3-t-butyl-1-naphthyl group, 4-t-butyl-1-naphthyl group and the like can be mentioned. Examples of the acyl group having 2 to 6 carbon atoms include acetyl group, propionyl group, butyryl group, isobutyryl group, pentanoyl group, and caproyl group.

  Among the structures described above, the ester-forming structure site (x1) is an acetyl group because it is particularly excellent in dielectric properties at the time of curing, and particularly has good reactivity with the epoxy resin (A) described later. , A benzoyl group or a naphthoyl group is preferable, and a benzoyl group is particularly preferable.

Further, R ¹ in the structural formula 1, as described above, a hydrogen atom, an alkyl group, or an alkoxy group. Here, examples of the alkyl group include alkyl groups having 1 to 4 carbon atoms such as a methyl group, an ethyl group, an i-propyl group, and a t-butyl group, and examples of the alkoxy group include a methoxy group, an ethoxy group, i- C1-C4 alkoxy groups, such as a propyloxy group and t-butyloxy group, are mentioned. In the present invention, R ¹ is particularly preferably a hydrogen atom, a methyl group, an ethyl group, or a methoxy group, and particularly preferably a hydrogen atom from the viewpoint of excellent heat resistance of the cured product.

Further, the bonding position of the ester bond in the structural formula 1 (carbonyl group) is preferable from the viewpoint of excellent heat resistance in the cured product of the active ester resin that is the 1-position of the naphthalene skeleton is finally obtained.

The above-mentioned active ester resin of the present invention can be produced by the following method.
That is, a naphthol compound and formaldehyde are reacted in the presence of a basic catalyst at a molar ratio (naphthol compound / formaldehyde) of 1.0 / 1.0 to 1.0 / 2.0 to calix. An arene-type naphthol compound (a) is obtained (step 1), and then the obtained calixarene-type naphthol compound (a) is combined with a phenyl group, a naphthyl group, and an alkyl group having 1 to 4 carbon atoms. Aromatic monocarboxylic acid having a hydrocarbon structure selected from the group consisting of a phenyl group, naphthyl group, and naphthyl group, which is substituted with 1 to 3 of alkyl groups having 1 to 4 carbon atoms, Or its halide (b-1) (hereinafter abbreviated as “aromatic monocarboxylic acid or its halide (b-1)”), or a saturated fatty acid having 2 to 5 carbon atoms, or Halide (b-2) (hereinafter, abbreviated to "saturated fatty acid or a halide (b-2)".) And include a method of reacting a.

  Here, the reaction of the step 1 can be specifically performed under a temperature condition of 20 to 100 ° C.

Also, naphthol compound used in step 1, specifically, alpha-naphthol, Or, methyl these aromatic nucleus, ethyl, i- propyl group, number of carbon atoms a t- butyl group and the like 1 Examples include compounds substituted with an alkyl group of ˜4, and compounds substituted with an alkoxy group of 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, an i-propyloxy group, and a t-butyloxy group. Specifically, α-naphthol, 1-hydroxy-3-methylnaphthalene, 1-hydroxy-5-methylnaphthalene, 1-hydroxy-6-methylnaphthalene, 1-hydroxy-5-ethylnaphthalene, 1-hydroxy-6 -Ethylnaphthalene, 1-hydroxy-5-butylnaphthalene, 1-hydroxy-6-butylnaphthalene, 1-hydroxy-5-propylnaphthalene, 1-hydroxy-6-propylnaphthalene, 1-hydroxy-5-methoxynaphthalene, 1 -Hydroxy-6-methoxynaphthalene, 1-hydroxy-5-ethoxynaphthalene, 1-hydroxy-6-ethoxynaphthalene, 1-hydroxy-5-propyloxynaphthalene, 1-hydroxy-6-propyloxynaphthalene, 1-hydroxy- 5-Butyloxynaphthale , 1-hydroxy-6-butyl-α- naphthol compound oxy naphthalene, but from the viewpoint of heat resistance in the cured product finally obtained the active ester resin (A) is α- naphthol compound In particular, α-naphthol is preferred.

In the present invention, the α-naphthol compound and the β-naphthol compound may be used in combination, and in such a case, the β-naphthol compound is 1.2 mol or less with respect to 1 mol of the α-naphthol compound. It is preferable from the viewpoint of heat resistance described above.
On the other hand, the formaldehyde source used in step 1 includes, for example, formalin, paraformaldehyde, trioxane and the like. Here, it is preferable that formalin is 30-60 mass% formalin from the point of water dilutability and workability | operativity at the time of manufacture.

  Specific examples of the basic catalyst used in Step 1 include alkaline earth metal hydroxides, alkali metal carbonates, and alkali metal hydroxides. In particular, alkali metal hydroxides such as sodium hydroxide and potassium hydroxide are preferred from the viewpoint of excellent catalytic activity. In use, these basic catalysts may be used in the form of an aqueous solution of about 10 to 55% by mass, or in the form of a solid.

  Moreover, it is preferable from the point that formation of a calixarene structure is easy for the usage-amount of the basic catalyst in the process 1 to be the ratio used as 0.02 mol or more with respect to 1 mol of said naphthol compounds. Furthermore, the molar ratio (naphthol compound / formaldehyde) is preferably 1.0 or less from the viewpoint that the selectivity of the naphthol-type calix (4) arene compound which is the most preferable molecular structure can be enhanced. Here, the naphthol-type calix (4) arene compound is a compound in which four molecules of a naphthol compound are bonded via a methylene bond to form a cyclic structure.

  Next, as step 2, calixarene-type naphthol compound (a) obtained in step 1 is mixed with aromatic monocarboxylic acid or its halide (b-1), or saturated fatty acid or its halide (b-2). By making it react, the target active ester resin can be obtained.

  The aromatic monocarboxylic acid or its halide (b-1) used here is specifically benzoic acid, methylbenzoic acid, 2,4-dimethylbenzoic acid, 2,6-dimethylbenzoic acid, 2, Alkyl such as 4,6-trimethylbenzoic acid, 2-ethylbenzoic acid, 4-ethylbenzoic acid, 2-t-butyl-4-ethylbenzoic acid, 4-i-propylbenzoic acid, 4-t-butylbenzoic acid Benzoic acid, 1-naphthoic acid, 2-naphthoic acid, 2-methyl-1-naphthoic acid, 4-methyl-1-naphthoic acid, 2-ethyl-1-naphthoic acid, 3-methyl-4-ethyl-2- Naphthoic acid, 2-propyl-1-naphthoic acid, 2-propyl-4-ethyl-1-naphthoic acid, 6-propyl-2-naphthoic acid, 2-t-butyl-1-naphthoic acid, 3-t-butyl -1-naphthoic acid, 4-t Butyl-1-naphthoic acid, as well as their acid fluorides, acid chlorides, acid bromides, acid halides such as acid iodide and the like.

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

  Among these, acid chlorides of benzoic acid and ethanoic acid are particularly preferable from the viewpoint of excellent dielectric properties.

  The reaction between the calixarene-type naphthol compound (a) in Step 2 and the aromatic monocarboxylic acid or its halide (b-1) or the saturated fatty acid or its halide (b-2) is specifically, Examples thereof include a method in which a calixarene type naphthol compound (a) is reacted with the above (b-1) or (b-2) in the presence of a basic catalyst.

  Here, the reaction ratio between the calixarene-type naphthol compound (a) and the aromatic monocarboxylic acid or its halide (b-1), or the saturated fatty acid or its halide (b-2) is as shown in (a) The equivalent ratio of the phenolic hydroxyl group of (b-1) or the carboxyl group (or halide) in (b-2) [OH / carboxyl group (or halide) in (a)] is 1.0 / 0. A ratio of 40 to 1.0 / 0.95 is preferable from the viewpoint of good solvent solubility of the obtained active ester resin.

  Examples of the alkali catalyst that can be used in the reaction of Step 2 include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. Of these, sodium hydroxide and potassium hydroxide are particularly preferred because they can be used in the form of an aqueous solution and the productivity is good.

  In the reaction of Step 2, each raw material component is preferably dissolved in an organic solvent and used for the reaction. Examples of the organic solvent used here include toluene and dichloromethane.

  After carrying out the reaction under the above conditions, an appropriate amount of water is added to the reaction solution to dissolve the produced salt. Thereafter, washing with water is repeated to remove the generated salt in the system, and further purification is performed by dehydration or filtration, and the organic solvent is removed by distillation to obtain the desired active ester resin.

  The active ester resin thus obtained has a carbonyloxy group equivalent in the resin of 198 to 400 g / eq. Those in the range are preferable from the viewpoint of good dielectric properties such as low dielectric constant and low dielectric loss tangent of the cured product.

The curable resin composition of the present invention comprises the above-mentioned active ester resin (hereinafter referred to as “active ester resin (A)”) and an epoxy resin (B) as essential components. Is.
Here, in addition to the active ester resin (A) and the epoxy resin (B), the curable resin composition further includes another naphthalene skeleton-containing active ester resin (A ′) of the active ester resin (A). Is preferable from the viewpoint of improving the solvent solubility of the composition and facilitating adjustment of the composition for a printed wiring board.

  Specifically, the naphthalene skeleton-containing active ester resin (A ′) used here is 2,7-dihydroxynaphthalene, α-naphthol novolak resin, β-naphthol novolak resin, α-naphthol / β-naphthol co-condensed novolak. Resin, naphthol aralkyl resin, naphthol resin such as 1,1-bis (2,7-hydroxy-1-naphthyl) alkane, aromatic monocarboxylic acid or its halide (b-1), or saturated fatty acid Or the active ester resin obtained by making it react with the halide (b-2) is mentioned.

  Among these, in terms of excellent compatibility with the active ester resin (A), 2,7-dicyanatonaphthalene, α-naphthol novolak cyanate ester resin, β-naphthol novolak cyanate ester resin, or An active ester resin obtained by reacting an α-naphthol / β-naphthol co-condensation type novolak with the above (b-1) or (b-2) is preferable.

  In particular, in the present invention, when the calixarene naphthol resin (a) which is the precursor of the active ester resin (A) is produced, β-naphthol is used together with α-naphthol, and the calixarene naphthol compound and α -A mixture of naphthol / β-naphthol co-condensation type novolak was obtained, and then this was esterified with (b-1) or (b-2), whereby the active ester resin (A) and α- A naphthol / β-naphthol co-condensation type novolak mixture prepared with an active ester resin is preferred because of its excellent solvent solubility.

  Here, the abundance ratio of the active ester resin (A) and the naphthalene skeleton-containing active ester resin (A ′) is determined by measuring the naphthol resin of both precursor mixtures by GPC (Naphthalene skeleton-containing active ester resin ( It is preferable from the point which is excellent in the heat resistance and solvent solubility of hardened | cured material that the content rate of the area ratio reference | standard of the precursor naphthol resin of A ') will be 3-50%.

  When the active ester resin (A) and the naphthalene skeleton-containing active ester resin (A ′) are used as a mixture, the mixture has a carbonyloxy group equivalent of 198 to 400 / eq. It is preferable from the point which is excellent in heat resistance.

  The content ratio of the active ester resin (A ′) and the active ester resin (A ′) based on the area ratio standard of the active ester resin (A ′) when the mixture of both is measured by GPC From the viewpoint of heat resistance and solvent solubility, it is preferable that the ratio is 3 to 50%.

Here, the GPC measurement conditions specifically include 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 refraction diameter)
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).

  Furthermore, when the active ester resin (A) is applied to circuit board applications, it is preferable to further reduce the functional group concentration in the epoxy resin to improve the dielectric properties and moisture resistance after curing. On the other hand, when the molecular weight in the active ester resin (A) is small, the active ester resin (A) is inferior in solubility in an organic solvent and difficult to apply to a circuit board varnish. A) is a functional group equivalent of 400 to 600 g / eq. Based on the total number of functional groups of the arylcarbonyloxy group and phenolic hydroxyl group in the resin structure. It is preferable that it is the range of these.

Next, the epoxy resin (B) used in the curable resin composition of the present invention is, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a biphenyl type epoxy resin, a tetramethylbiphenyl type epoxy resin, or a phenol novolac type epoxy. Resin, cresol novolac type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin , Naphthol-phenol co-condensed novolak type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenolic resin type epoxy resin Resins, biphenyl-modified novolak type epoxy resins. Among these epoxy resins, tetramethylbiphenol type epoxy resin, biphenyl aralkyl type epoxy resin, in particular, since a cured product having excellent flame retardancy can be obtained.
It is preferable to use a novolac type epoxy resin.

  The compounding amount of the active ester resin (A) and the epoxy resin (B) in the curable resin composition of the present invention is such that the active ester resin (A) has good curability and various physical properties of the cured product. It is preferable that the epoxy group in the epoxy resin (B) is in a ratio of 0.8 to 1.2 equivalents with respect to 1 equivalent of the carbonyloxy group constituting the ester in FIG. When the naphthalene skeleton-containing active ester resin (A ′) is used as the curing agent for the epoxy resin (B), the active ester resin (A) and the naphthalene skeleton-containing active ester resin (A ′) are used. It is preferable to mix each component in such a ratio that the epoxy group in the epoxy resin (B) is 0.8 to 1.2 equivalents per 1 equivalent of the total carbonyloxy group.

In addition to the active ester resin (A) and the epoxy resin (B) described above, the curable resin composition of the present invention includes another epoxy resin curing agent (hereinafter referred to as “epoxy resin”). Abbreviated as “curing agent”). As the curing agent for epoxy resin that can be used here, for example, curing agents such as amine compounds, amide compounds, acid anhydride compounds, phenol compounds, and the like can be used. Specifically, examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, and guanidine derivative. Examples of the amide compound include dicyandiamide. And polyamide resins synthesized from dimer of linolenic acid and ethylenediamine. Examples of acid anhydride compounds include phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, and tetrahydrophthalic anhydride. Acid, methyltetrahydrophthalic anhydride, methyl nadic anhydride, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, etc., and phenolic compounds include phenol novolac resin, cresol novolac resin Aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin, naphthol aralkyl resin, trimethylol methane resin, tetraphenylol ethane resin, naphthol novolak resin, naphthol-phenol co-condensed novolak resin, naphthol -Cresol-condensed novolak resin, biphenyl-modified phenolic resin (polyhydric phenol compound in which phenol nucleus is linked by bismethylene group), biphenyl-modified naphthol resin (polyvalent naphthol compound in which phenol nucleus is linked by bismethylene group), aminotriazine modified Examples thereof include polyhydric phenol compounds such as phenol resins (polyhydric phenol compounds in which phenol nuclei are linked with melamine or benzoguanamine).

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

  When the above curing agent for epoxy resin is used in combination, the amount used is preferably in the range of 10 to 50% by mass from the viewpoint of dielectric properties.

  Moreover, a hardening accelerator can also be suitably used together with the curable resin composition of this invention as needed. Various curing accelerators can be used, and examples thereof include phosphorus compounds, tertiary amines, imidazoles, organic acid metal salts, Lewis acids, and amine complex salts. In particular, when used as a build-up material application or a circuit board application, dimethylaminopyridine and imidazole are preferable from the viewpoint of excellent heat resistance, dielectric characteristics, solder resistance, and the like. 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.

  As described above, the curable resin composition of the present invention described in detail above is characterized by exhibiting excellent solvent solubility. Therefore, the curable resin composition preferably contains an organic solvent (C) in addition to the above components. Examples of the organic solvent (C) that can be used here include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. The proper amount used can be appropriately selected depending on the application, but for example, in a printed wiring board application, it is preferable to use a polar solvent having a boiling point of 160 ° C. or lower, such as methyl ethyl ketone, acetone, 1-methoxy-2-propanol, etc. The non-volatile content is preferably 40 to 80% by mass. On the other hand, in the adhesive film use for build-up, as the organic solvent (C), for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, acetic acid such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, etc. Esters, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, etc. are preferably used, and non-volatile content is 30 to 60 mass. It is preferable to use it at a ratio of%.

  Moreover, another curable resin can also be suitably used together with the curable resin composition of this invention as needed. Examples of other curable resins that can be used here include cyanate ester compounds, vinyl benzyl compounds, acrylic compounds, maleimide compounds, and the like. When the other curable resins described above are used in combination, the amount used is not particularly limited as long as the effects of the present invention are not impaired, but 1 to 80 masses based on the total mass of the curable resin composition of the present invention. % Is preferable.

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

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

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

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

  Examples of the organic phosphorus compound include, for example, general-purpose organic phosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphorane compounds, organic nitrogen-containing phosphorus compounds, and 9,10- Dihydro-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene = 10-oxide, 10- (2,7 -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 depending on the type of the phosphorus-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, the active ester resin (A), In 100 parts by mass of curable resin composition containing all of epoxy resin (B), if necessary, naphthalene skeleton-containing active ester resin (A ′), non-halogen flame retardant and other fillers and additives, red phosphorus When used as a non-halogen flame retardant, it is preferably blended in the range of 0.1 to 2.0 parts by mass, and when using an organophosphorus compound, similarly in the range of 0.1 to 10.0 parts by mass. It is preferable to mix | blend, and it is preferable to mix | blend especially in the range of 0.5-6.0 mass parts.

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

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

  Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylene dimelamine, melamine polyphosphate, triguanamine, and the like, for example, guanylmelamine sulfate, melem sulfate, melam sulfate, etc. Examples thereof include an aminotriazine sulfate compound, aminotriazine-modified phenol resin, and aminotriazine-modified phenol resin further modified with tung oil, isomerized linseed oil, and the like.

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

  The amount of the nitrogen-based flame retardant is appropriately selected depending on the type of the nitrogen-based flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, the active ester resin (A), epoxy resin (B), non-halogen flame retardant and other fillers and additives are blended in a range of 0.05 to 10 parts by mass in 100 parts by mass of curable resin composition. It is particularly preferable to blend in the range of 0.1 to 5 parts by mass.

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

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

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

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

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

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

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

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

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

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

  The blending amount of the inorganic flame retardant is appropriately selected according to the type of the inorganic flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. For example, the active ester resin (A), epoxy resin (B), non-halogen flame retardant, and other fillers and additives are blended in a range of 0.05 to 20 parts by mass in 100 parts by mass of curable resin composition. It is particularly preferable to blend in the range of 0.5 to 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 flame retardant is appropriately selected depending on the type of the organic metal salt flame retardant, the other components of the curable resin composition, and the desired degree of flame retardancy. , 0.005 to 10 parts by mass in 100 parts by mass of the curable resin composition containing all of the active ester resin (A), epoxy resin (B), non-halogen flame retardant and other fillers and additives. It is preferable to mix in a range.

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

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

  The curable resin composition of the present invention can be obtained by uniformly mixing the above-described components. The curable resin composition of the present invention in which the active ester resin (A), the epoxy resin (B) of the present invention and, if necessary, a curing accelerator is blended can be easily cured by a method similar to a conventionally known method. It can be. Examples of the cured product include molded cured products such as laminates, cast products, adhesive layers, coating films, and films.

  Examples of uses in which the curable resin composition of the present invention is used include hard printed wiring board materials, flexible wiring board resin compositions, insulating materials for circuit boards such as build-up board interlayer insulating materials, semiconductor sealing materials, Examples include conductive pastes, build-up adhesive films, resin casting materials, and adhesives. Among these various applications, in hard printed wiring board materials, insulating materials for electronic circuit boards, and adhesive film for build-up, passive parts such as capacitors and active parts such as IC chips are embedded in so-called electronic parts. It can be used as an insulating material for a substrate. Among these, circuit boards such as hard printed wiring board materials, resin compositions for flexible wiring boards, and interlayer insulation materials for build-up boards because of their high flame resistance, high heat resistance, low thermal expansibility, and solvent solubility. It is preferable to use it for a material and a semiconductor sealing material.

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

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

  As a method for obtaining an interlayer insulating material for build-up substrates from the curable resin composition of the present invention, for example, the curable resin composition appropriately blended with rubber, filler, etc., is spray-coated on a wiring board on which a circuit is formed. After applying using a curtain coating method or the like, it is cured. Then, after drilling a predetermined through-hole part etc. as needed, it treats with a roughening agent, forms the unevenness | corrugation by washing the surface with hot water, and metal-treats, such as copper. As the plating method, electroless plating or electrolytic plating treatment is preferable, and examples of the roughening agent include an oxidizing agent, an alkali, and an organic solvent. Such operations are sequentially repeated as desired, and a build-up base can be obtained by alternately building up and forming the resin insulating layer and the conductor layer having a predetermined circuit pattern. However, the through-hole portion is formed after the outermost resin insulating layer is formed. In addition, a resin-coated copper foil obtained by semi-curing the resin composition on the copper foil is thermocompression-bonded at 170 to 250 ° C. on a circuit board on which a circuit is formed, thereby forming a roughened surface and plating treatment. It is also possible to produce a build-up substrate by omitting the process.

  Next, in order to produce a semiconductor sealing material from the curable resin composition of the present invention, an active ester resin (A), an epoxy resin (B), and a compounding agent such as an inorganic filler are extruded as necessary. , Kneading, rolling, etc., and sufficient melt mixing until uniform. At that time, silica is usually used as the inorganic filler. In that case, by blending the inorganic filler in the curable resin composition in a proportion of 70 to 95% by mass, the semiconductor encapsulation of the present invention is performed. Become a material. For semiconductor package molding, the composition is molded by casting, using a transfer molding machine, an injection molding machine or the like, and further heated at 50 to 200 ° C. for 2 to 10 hours to form a semiconductor device which is a molded product. The method of obtaining is mentioned.

  The method for producing an adhesive film for buildup from the curable resin composition of the present invention is, for example, a multilayer printed wiring board in which the curable resin composition of the present invention is applied on a support film to form a resin composition layer. And an adhesive film for use.

  When the curable resin composition of the present invention is used for a build-up adhesive film, the adhesive film is softened under the temperature condition of the laminate in the vacuum laminating method (usually 70 ° C. to 140 ° C.), and simultaneously with the lamination of the circuit board, It is important to show fluidity (resin flow) that allows resin filling in via holes or through holes present in a circuit board, and it is preferable to blend the above-described components so as to exhibit such characteristics.

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

  Specifically, the method for producing the adhesive film described above is, after preparing the varnish-like curable resin composition of the present invention, coating the varnish-like composition on the surface of the support film, further heating, Or it can manufacture by drying an organic solvent by hot air spraying etc. and forming the layer ((alpha)) of a curable resin composition.

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

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

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

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

  The above support film is peeled off after being laminated on a circuit board or after forming an insulating layer 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.

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

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

  When the curable resin composition of the present invention is used as a conductive paste, for example, a method of dispersing fine conductive particles in the curable resin composition to obtain a composition for anisotropic conductive film, liquid at room temperature And a paste resin composition for circuit connection and an anisotropic conductive adhesive.

  Further, the curable resin composition of the present invention can be further used as a resist ink. In this case, the curable resin composition is blended with a vinyl monomer having an ethylenically unsaturated double bond, and a cationic polymerization catalyst as a curing agent, and further added with a pigment, talc, and filler to form a resist ink composition. After making it into a product, after applying on a printed board by a screen printing method, a method of forming a resist ink cured product can be mentioned.

  As a method for obtaining the cured product of the present invention, for example, the composition obtained by the above method may be heated in a temperature range of about 20 to 250 ° C.

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

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

1) GPC:
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 refraction diameter)
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).
2) FD-MS: Measured with a double convergence mass spectrometer “AX505H (FD505H)” manufactured by JEOL Ltd.

Example 1
In a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer, 216 parts by mass of α-naphthol (1.50 mol), 146 parts by mass of a 37% by weight aqueous formaldehyde solution (1.80 mol), isopropyl 121 parts by mass of alcohol and 46 parts by mass (0.56 mol) of a 49% aqueous sodium hydroxide solution were added and stirred at room temperature while blowing nitrogen. Then, it heated up at 80 degreeC and stirred for 1 hour. After completion of the reaction, 40 parts by mass of first sodium phosphate was added for neutralization, and then cooled and the crystalline substance was filtered off. Then, after repeating washing | cleaning 3 times with 200 mass parts of water, it dried under heating and pressure reduction, and obtained 224 mass parts of naphthol compounds (A-1). The hydroxyl group equivalent of the obtained naphthol compound (A-1) was 156 g / equivalent. The naphthol compound (A-1) has the following structural formula from the MS spectrum.

ｎ＝４を示す６２４のピークが検出された。

624 peaks showing n = 4 were detected.

Subsequently, 156 g of phenol resin (A-1) and methyl isobutyl ketone (hereinafter abbreviated as “MIBK”) were charged in a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer. The inside of the system was purged with nitrogen under reduced pressure, and then 126.5 g (0.90 mol) of benzoyl chloride was charged. 181.8 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours while controlling the temperature below 0 ° C. Stirring was continued for 1.0 hour under these conditions. Further, water was added to the MIBK phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the aqueous layer was removed by leveling and removing until the pH of the water tank reached 7. Thereafter, the water was removed by decanter dehydration, and then MIBK was removed by dehydration under reduced pressure to obtain 220 parts of an active ester resin (A-2). The group equivalent was 244 g / equivalent from the charging ratio, and the esterification rate with respect to the phenolic hydroxyl group was 90%, and the GPC chart of the obtained active ester resin is shown in Fig. 1. From the MS spectrum, the following structural formula is shown.

においてｎ＝４を示す１０４０のピークが検出された。

1040 peaks showing n = 4 were detected.

Example 2
Except that 216 parts by mass (1.50 mol) of α-naphthol was changed to 144 parts by mass (1.00 mol) of α-naphthol and 72 parts by mass (0.50 mol) of β-naphthol, A naphthol resin (A-3) was obtained. The hydroxyl group equivalent of the obtained naphthol resin (A-3) was 158 g / equivalent.
Subsequently, 158 parts by mass of phenol resin (A-3) and methyl isobutyl ketone (hereinafter abbreviated as “MIBK”) are placed in a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer. Then, 98.4 parts by mass (0.70 mol) of benzoyl chloride was charged, 0.55 g of tetrabutylammonium bromide was dissolved, and a nitrogen gas purge was performed. However, the inside of the system was controlled to 60 ° C. or lower, and 181.8 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours, and the stirring was continued for 1.0 hour under these conditions. Water was added to the MIBK phase in which the reactants were dissolved, and the mixture was stirred and mixed for about 15 minutes, and the water layer was removed by ground leveling. Thereafter, the water was removed by decanter dehydration, and then MIBK was removed by vacuum dehydration to obtain 180 parts by mass of an active ester resin (A-4). The functional group equivalent of 4) was 219 grams / equivalent from the charging ratio, and the esterification rate with respect to the phenolic hydroxyl group was 70%.

におけるｎ＝４体の含有率は２３．９％であった。従って、前記シアン酸エステル樹脂（Ａ−４）は、前記構造式においてｎ＝４の活性エステル樹脂とα−ナフトール／β−ナフトール共縮合型ノボラックの活性エステル樹脂との混合物であることが判明した。

The content of n = 4 compounds in was 23.9%. Therefore, it was found that the cyanate ester resin (A-4) was a mixture of an active ester resin of n = 4 in the structural formula and an active ester resin of α-naphthol / β-naphthol co-condensation type novolak. .

Comparative Example 1
The reaction was conducted in the same manner as in Example 1 except that the naphthol compound (A-1) was changed to 105 parts by mass of a phenol novolac resin (“TD-2090” manufactured by DIC) to obtain 188 parts by mass of an active ester resin (A-5). It was. The functional group equivalent of this active ester resin (A-5) was 199 grams / equivalent from the charge ratio.

Examples 3 and 4 and Comparative Example 2 (Adjustment of curable resin composition and evaluation of physical properties)
In accordance with the composition shown in Table 1 below, 850-S (bisphenol A type epoxy resin, epoxy equivalent: 187 g / eq) made by DIC is blended as an epoxy resin, and (A-2) and (A-3) are blended as curing agents. Furthermore, 0.5 phr of dimethylaminopyridine was added as a curing catalyst, and methyl ethyl ketone was blended and adjusted so that the nonvolatile content (NV) of each composition was finally 58% by mass. This was transferred to an aluminum petri dish and dried at 120 ° C. to remove methyl ethyl ketone to obtain a semi-cured product. Next, the semi-cured product is put into a 15 cm × 15 cm × 2 mm mold and vacuum press-molded (temperature conditions: 200 ° C., pressure: 40 kg / cm ² , molding time: 1.5 hours) to obtain a plate-shaped cured product. Obtained. Using this as a test piece, the following various evaluations were performed. The results are shown in Table 1.

[Heat resistance test]
Glass transition temperature: The test piece was measured by the DMA method. Temperature rising speed 3 ° C / min [Measurement of dielectric constant and dielectric loss tangent]
In accordance with JIS-C-6481, the dielectric material at 1 GHz of the test piece after being stored in an indoor room at 23 ° C. and 50% humidity for 24 hours after absolutely dry using an impedance material analyzer “HP4291B” manufactured by Agilent Technologies, Inc. Measured rate and dielectric loss tangent

表１の脚注：
Ａ−２：実施例１で得られた活性エステル樹脂（Ａ−２）
Ａ−４：実施例２で得られた活性エステル樹脂（Ａ−４）
Ａ−５：比較例１で得られた活性エステル樹脂（Ａ−５）

Footnotes in Table 1:
A-2: Active ester resin (A-2) obtained in Example 1
A-4: Active ester resin (A-4) obtained in Example 2
A-5: Active ester resin (A-5) obtained in Comparative Example 1

Claims (11)

The following structural formula (1)

(Wherein, X is a benzoyl group, one to three in the nucleus substituted selected from benzoyl or we group consisting ester formed structural site of an alkyl group having 1 to 4 carbon atoms (x1), or hydrogen An atom (x2), each R ¹ independently represents a hydrogen atom, an alkyl group, or an alkoxy group, and n is an integer of 2 to 10. However, in X in the resin, an ester-forming structural site The existing ratio of (x1) and hydrogen atom (x2) is such that the ester-forming structural site (x1) is 40% or more with respect to the total of both, and the ester bond (carbonyloxy) in the structural formula (1) bonding position of groups), curing, characterized in that a 1-position of the naphthalene skeleton.) having a resin structure that active ester resin represented by (a), and the epoxy resin (B) as essential components Resin composition. In X in the active ester resin (A), the proportion of the ester-forming structural site (x1) and the hydrogen atom (x2) is 40 to 95% of the ester-forming structural site (x1) relative to the total of both. The curable resin composition according to claim 1, wherein In addition to the active ester resin (A) and the epoxy resin (B),
2,7-dihydroxynaphthalene, α-naphthol novolak resin, β-naphthol novolak resin, α-naphthol / β-naphthol co-condensed novolak resin, naphthol aralkyl resin or 1,1-bis (2,7-hydroxy-1- Naphthyl) alkane and aromatic monocarboxylic acid or its halide (b-1), or other naphthalene skeleton-containing active ester resin (A ′) which is a reaction product of saturated fatty acid or its halide (b-2) The curable resin composition of Claim 1 or 2 to be used. The content ratio of the active ester resin (A ') and the active ester resin (A') is 3 based on the area ratio of the active ester resin (A ') when the mixture of both is measured by GPC. The curable resin composition according to claim 3, which has a ratio of ˜50%. The active ester resin (A) and the active ester resin (A ′) are used as a mixture of both, and the carbonyloxy group equivalent in the mixture is 198 to 400 g / eq. The curable resin composition according to claim 3 , which falls within the range of The active ester resin (A) uses the active ester resin (A) and the active ester resin (A ′) as a mixture of both, and the total functionality of the carbonyloxy group and the phenolic hydroxyl group in the mixture The functional group equivalent based on the number of groups is 170 to 300 g / eq. The curable resin composition according to claim 3 , which falls within the range. A cured product obtained by curing the curable resin composition according to any one of claims 1 to 6 . In addition to the active ester resin (A) and the epoxy resin (B) in the curable resin composition according to any one of claims 1 to 6, an inorganic filler (C) is further added to the composition in an amount of 70 to 95. A semiconductor encapsulating material comprising a curable resin composition contained at a ratio of mass%. A prepreg obtained by impregnating a reinforcing substrate with the curable resin composition according to any one of claims 1 to 6 diluted in an organic solvent, and semi-curing the resulting impregnated substrate. A varnish obtained by diluting the curable resin composition according to any one of claims 1 to 6 in an organic solvent is obtained, and obtained by heating and press-molding a varnish shaped into a plate shape and a copper foil. Circuit board. A build-up film obtained by applying a solution obtained by diluting the curable resin composition according to any one of claims 1 to 6 to an organic solvent and drying the substrate.

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