TW201833165A - Active ester resin and cured product thereof - Google Patents

Abstract

Provided are: an active ester resin having low cure shrinkage, having excellent dielectric properties, etc., in a cured product, and also having high solvent solubility; a curable resin composition containing same; a cured product thereof; a printed wiring board; and a semiconductor sealing material. The active ester resin is characterized by having, as essential reactive raw materials thereof: (A) a novolac resin having a naphthol compound (a) as a reactive raw material thereof and containing a component having at least three nuclear bodies as essential components thereof; (B) a compound having one phenolic hydroxyl group in the molecules thereof; and (C) an aromatic polycarboxylic acid or an acid halide thereof.

Description

 Active ester resin and cured product thereof  

The present invention relates to an active ester resin having a high curing shrinkage ratio, a dielectric property of a cured product, and a high solvent solubility, a curable resin composition containing the same, a cured product thereof, a printed wiring substrate, and a semiconductor sealing material. .

In the technical field of insulating materials used for semiconductors, multilayer printed boards, and the like, as various electronic components are thinned, signals are speeded up, and frequency is increased, new resin materials that are compatible with these market trends are being developed. For example, as the thickness of the electronic component is reduced, the "warpage" of the member due to heat is marked, and in order to suppress it, a resin material having a low curing shrinkage ratio and high dimensional stability is being developed. In addition, in order to reduce the energy loss due to heat generation, etc., in order to reduce the speed of the signal and to increase the frequency, a resin material having a low dielectric constant and a dielectric loss tangent of the cured product is being developed. In addition, as an industrial use value, workability such as excellent solubility in various general-purpose solvents is also an important performance.

As a resin material having a relatively low dielectric constant and dielectric loss tangent of a cured product, there is known a technique of esterifying a dicyclopentadiene phenol resin with α-naphthol using o-phthalic acid chloride. The obtained active ester resin is used as a curing agent for an epoxy resin (see Patent Document 1 below). The active ester resin described in Patent Document 1 has a characteristic that the dielectric constant or dielectric loss tangent of the cured product is low as compared with the case of using a prior type hardener such as a phenol novolak type resin. It has not met the recent market demand level, especially for the value of the dielectric loss tangent to seek further reduction. Further, the hardening shrinkage ratio is further reduced.

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2004-169021

Therefore, an object of the present invention is to provide an active ester resin having a high curing shrinkage ratio, a dielectric property of a cured product, and a high solvent solubility, a curable resin composition containing the same, a cured product thereof, and a cured product thereof. Printed wiring board and semiconductor sealing material.

In order to solve the above problems, the inventors of the present invention have found that an active ester resin having a "novolak-type resin containing a naphthol compound as a reaction raw material and containing a component having a core number of 3 or more" as a reaction raw material is found. The present invention has been completed in that the curing shrinkage rate is low, the dielectric properties of the cured product are excellent, and the solvent solubility is also high.

That is, the present invention relates to an active ester resin characterized by the following (A), (B), and (C) as essential reaction materials: a novolac type resin (A) which is a naphthol compound (a) The reaction raw material contains a component having a nucleus number of 3 or more as an essential component; a compound (B) having a phenolic hydroxyl group in the molecule; and an aromatic polycarboxylic acid or an acid halide (C) thereof.

The present invention further relates to a hard resin composition containing the above-mentioned active ester resin and a curing agent.

The present invention further relates to a cured product of the above curable resin composition.

The present invention further relates to a printed wiring board using the above-described curable resin composition.

The present invention further relates to a semiconductor sealing material using the above-described curable resin composition.

According to the present invention, it is possible to provide an active ester resin having a high curing shrinkage ratio, a dielectric property of a cured product, and a high solvent solubility, a curable resin composition containing the cured resin composition, a cured product thereof, a printed wiring board, and a semiconductor. Sealing material.

Fig. 1 is a GPC line diagram of the active ester resin (1) obtained in Example 1.

Fig. 2 is a 13C-NMR chart of the active ester resin (1) obtained in Example 1.

Figure 3 is an MS spectrum of the active ester resin (1) obtained in Example 1.

Fig. 4 is a GPC line diagram of the active ester resin (2) obtained in Example 2.

Fig. 5 is a GPC line diagram of the active ester resin (3) obtained in Example 3.

Hereinafter, the present invention will be described in detail.

The active ester resin of the present invention is characterized by the following (A), (B), and (C) as essential reaction materials: a novolac type resin (A) having a naphthol compound (a) as a reaction material. Further, a component having a nucleus number of 3 or more is contained as an essential component; a compound (B) having a phenolic hydroxyl group in the molecule; and an aromatic polycarboxylic acid or an acid halide (C) thereof.

In the above-mentioned novolak-type resin (A), the naphthol compound (a) may be any compound as long as it has a hydroxyl group on the naphthalene ring, and its specific structure or presence or absence of other substituents is not particularly limited. In the present invention, the naphthol compound (a) may be used alone or in combination of two or more. Specific examples of the naphthol compound (a) include 1-naphthol and 2-naphthol, and compounds having one or more substituents on the aromatic nucleus. Examples of the substituent on the aromatic nucleus include methyl group, ethyl group, vinyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, decyl group, undecyl group, and the like. An aliphatic hydrocarbon group such as a dodecyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a phenyl group, a naphthyl group or a fluorenyl group; An aryl group; an aralkyl group such as a phenylmethyl group, a phenylethyl group, a naphthylmethyl group or a naphthylethyl group. Among these, it is preferably 1-naphthol or 2-naphthol in terms of an active ester resin having a low curing shrinkage ratio and excellent dielectric properties of a cured product.

In the above-mentioned novolak-type resin (A), the naphthol compound (a) is used as a raw material of the reaction, and other phenol-containing hydroxy compound (a') may be used in combination with the desired resin properties and the like. Examples of the other phenolic hydroxy compound (a') include phenol, indophenol, and compounds having one or more substituents on the aromatic nucleus. Examples of the substituent on the aromatic nucleus include methyl group, ethyl group, vinyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, decyl group, decyl group, undecyl group, and the like. An aliphatic hydrocarbon group such as a dodecyl group; an alkoxy group such as a methoxy group, an ethoxy group, a propoxy group or a butoxy group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a phenyl group, a naphthyl group or a fluorenyl group; An aryl group; an aralkyl group such as a phenylmethyl group, a phenylethyl group, a naphthylmethyl group or a naphthylethyl group.

When the above-mentioned other phenol-containing hydroxy compound (a') is used in combination with the above naphthol compound (a), the curing shrinkage ratio is sufficiently low, the dielectric properties of the cured product are excellent, and the solvent solubility is also high. In view of the effects of the invention, the ratio of the naphthol compound (a) is preferably 50% by mole or more, more preferably 80% by mole or more, and particularly preferably 90% by mole based on the total of the two. the above.

The novolac type resin (A) contains a component having a number of cores of 3 or more as an essential component. The number of the above-mentioned nuclei refers to the number of structural sites derived from the naphthol compound (a) or the other phenolic hydroxy compound (a') contained in one molecule. For example, the component of the number of nuclei 3 can be as follows. The formula (1) shows that the component of the number of cores 4 can be represented by the following formula (2-1) or (2-2).

Ar-CH ₂ -Ar-CH ₂ -Ar (1)

[In the formula, Ar is a structural moiety derived from the above naphthol compound (a) or the above other phenolic hydroxy compound (a')]

Ar-CH ₂ -Ar-CH ₂ -Ar-CH ₂ -Ar (2-1)

[In the formula, Ar is a structural moiety derived from the above naphthol compound (a) or the above other phenolic hydroxy compound (a')]

In the case where the number of cores is 3 or 4, Ar in the above formulas (1), (2-1), and (2-2) is a structural moiety derived from the above naphthol compound (a) or from the other phenols mentioned above. The structural part of the hydroxy compound (a') may be the same as the above formula (1), (2-) in terms of the effect that the hardening shrinkage ratio is low and the dielectric properties of the cured product are more excellent. All of Ar in 1) and (2-2) is a structural moiety derived from the above naphthol compound (a).

In the above-mentioned novolak-type resin (A), it is preferable that the number of nuclei is 3 in the range of 1 to 50% in terms of the effect that the curing shrinkage ratio is low and the dielectric properties of the cured product are excellent. Or a component of 4, more preferably contained in the range of 5 to 30%. Further, the content of the component having a nuclear number of 3 is preferably in the range of 1 to 30%, more preferably in the range of 5 to 20%. The content of the component having a core number of 4 is preferably in the range of 1 to 15%, more preferably in the range of 1 to 10%.

Further, the novolac type resin (A) can further reduce the curing shrinkage ratio of the obtained active ester resin, and more preferably contains a component having a number of cores of 2. The content of the component having the number of nuclei of 2 is preferably a ratio of the content (N2) of the component having the number of nuclei of 2 to the content (N3) of the component having the number of nuclei of 3 ((N3)/(N2)]. The ratio is in the range of 0.10 to 2.00, and more preferably in the range of 0.20 to 1.00.

In the present invention, the content of each component in the novolac type resin (A) is a value calculated from the area ratio of the GPC chart measured by the following conditions.

Measuring device: "HLC-8320 GPC" manufactured by Tosoh Co., Ltd.,

Pipe column: Protection column "HXL-L" manufactured by Tosoh Co., Ltd.

"TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

"TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

"TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

"TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

Data Processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40 ° C

Developing solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: The following monodisperse polystyrene having a known molecular weight is used in accordance with the above-mentioned "GPC-8320" measurement manual.

(using polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

Sample: 1.0% by mass of tetrahydrofuran solution in terms of resin solid content conversion was filtered using a microfilter to obtain (50 μl)

The method for producing the novolak-type resin (A) is not particularly limited, and examples thereof include the above-described naphthol compound (a) and the above-mentioned other phenol-containing properties as needed, similarly to the usual phenol novolak type resin. The hydroxy compound (a') and formaldehyde are reacted at a temperature of 40 to 200 ° C in the absence of a catalyst, an acid catalyst or a base catalyst. After completion of the reaction, an excess of the above compound (a) or compound (a') may be distilled off as needed. Further, the unreacted compound (a) or the compound (a') which is unreacted in the reaction mixture may be used as the compound (B) having a phenolic hydroxyl group in the molecule to be described later.

The above formaldehyde can be used as a formalin solution or as a polyoxymethylene. The amount of formaldehyde added is preferably in a range of from 0.01 to 0.9 mol per mol of the total of the compound (a) and the compound (a') in terms of the ease of controlling the reaction.

Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid; organic acids such as methanesulfonic acid, p-toluenesulfonic acid, and oxalic acid; and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. These may be used alone or in combination of two or more. The amount of the acid catalyst used is preferably in the range of 0.1 to 5% by mass based on the total mass of the reaction raw material.

Examples of the base catalyst include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These may be used alone or in combination of two or more. Further, it can be used in an aqueous solution of about 3.0 to 50%. Among them, sodium hydroxide or potassium hydroxide having a high catalytic energy is preferred. The amount of the alkali catalyst used is preferably in the range of 0.1 to 20% by mass based on the total mass of the reaction raw material.

The synthesis reaction of the above novolac type resin (A) can be carried out in an organic solvent as needed. The organic solvent to be used herein is not particularly limited as long as it is an organic solvent which can be used under the above temperature conditions, and specific examples thereof include methyl acesulfame, ethyl ceramide, toluene, xylene, and methyl group. Isobutyl ketone and the like. In the case of using these organic solvents, it is preferably used in the range of 10 to 500% by mass based on the total mass of the reaction raw materials.

In the synthesis reaction of the novolac type resin (A), various antioxidants or reducing agents may be used in order to suppress the coloration of the obtained novolac type resin (A). Examples of the antioxidant include a hindered phenol compound such as a 2,6-dialkylphenol derivative, a divalent sulfur compound, and a phosphite compound containing a trivalent phosphorus atom. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrogensulfite, salts thereof, zinc, and the like.

After the completion of the reaction, the reaction mixture may be subjected to a neutralization treatment or a water washing, and thereafter, the unreacted reaction raw material or by-products may be distilled off or the like to obtain a target novolac type resin (A).

The hydroxyl equivalent of the novolak-type resin (A) is preferably in the range of 110 to 250 g/eq. in terms of high solvent solubility and easy to be used in various active ester resins. Further, the softening point of the novolac type resin (A) is preferably in the range of 40 to 130 °C.

The compound (B) having one phenolic hydroxyl group in the above molecule may be any compound as long as it is an aromatic compound having one hydroxyl group in the aromatic ring, and other specific structures are not particularly limited. In the present invention, the compound (B) having one phenolic hydroxyl group in the molecular structure may be used alone or in combination of two or more. With respect to the compound (B) having a phenolic hydroxyl group in the above molecular structure, specifically, a phenol compound having one or more substituents on the aromatic nucleus of phenol or phenol, a naphthol or a naphthol having an aromatic nucleus may be mentioned. A naphthol compound having one or more substituents on the aromatic core of one to a plurality of substituents, an anthracene phenol or an anthracene phenol. Examples of the substituent on the aromatic nucleus include an aliphatic hydrocarbon group such as a methyl group, an ethyl group, a vinyl group, a propyl group, a butyl group, a pentyl group, a hexyl group, a cyclohexyl group, a heptyl group, an octyl group or a decyl group; An alkoxy group such as an ethoxy group, a propoxy group or a butoxy group; a halogen atom such as a fluorine atom, a chlorine atom or a bromine atom; a phenyl group, a naphthyl group, an anthracenyl group, and the like, and the above aromatic hydrocarbon group or An aryl group substituted with an alkoxy group, a halogen atom or the like; a phenylmethyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and the above aromatic hydrocarbon group or alkoxy group, halogen An aralkyl group substituted with an atom or the like.

Among these, it is preferably 1-naphthol or 2-naphthol in terms of an active ester resin having a low curing shrinkage ratio and excellent dielectric properties of a cured product.

The aromatic polycarboxylic acid or the acid halide (C) thereof can form an ester by reacting with the phenolic hydroxyl group of the novolak-type resin (A) and the compound (B) having one phenolic hydroxyl group in the molecule. The specific structure of the aromatic compound of the bond is not particularly limited and may be any compound. Specific examples thereof include benzenedicarboxylic acid such as isophthalic acid and terephthalic acid; benzenetricarboxylic acid such as 1,2,4-benzenetricarboxylic acid; and naphthalene-1,4-dicarboxylic acid and naphthalene- Naphthalene dicarboxylic acid such as 2,3-dicarboxylic acid, naphthalene-2,6-dicarboxylic acid, naphthalene-2,7-dicarboxylic acid; such acid halides, and the above-mentioned fats on the aromatic nucleus A compound substituted with a hydrocarbon group or an alkoxy group, a halogen atom or the like. Examples of the acid halide include ruthenium chloride, ruthenium bromide, ruthenium fluoride, ruthenium iodide, and the like. These may be used alone or in combination of two or more. Among them, in terms of an active ester resin having high reactivity and excellent curability, a benzene dicarboxylic acid such as isophthalic acid or terephthalic acid or an acid halide thereof is preferred.

The reaction of the novolac type resin (A), the compound (B) having one phenolic hydroxyl group in the molecule, and the aromatic polycarboxylic acid or the acid halide (C) thereof can be carried out, for example, by the following method: In the presence of a catalyst, heating and stirring are carried out at a temperature of about 40 to 65 °C. The reaction can also be carried out in an organic solvent as needed. Further, after the completion of the reaction, the reaction product may be purified by water washing or reprecipitation or the like as needed.

Examples of the base catalyst include sodium hydroxide, potassium hydroxide, triethylamine, and pyridine. These may be used alone or in combination of two or more. Further, it can be used as an aqueous solution of about 3.0 to 30%. Among them, sodium hydroxide or potassium hydroxide having a high catalytic energy is preferred.

Examples of the organic solvent include a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone; ethyl acetate, butyl acetate, ceramide acetate, propylene glycol monomethyl ether acetate, carbitol acetate, and the like. Acetate solvent; carbitol solvent such as celecoxime, butyl carbitol, aromatic hydrocarbon solvent such as toluene or xylene; dimethylformamide, dimethylacetamide, N-methylpyrrolidine Ketones, etc. These may be used alone or in combination of two or more.

The reaction ratio of the above-mentioned novolac type resin (A), the compound (B) having one phenolic hydroxyl group in the above molecule, and the above aromatic polycarboxylic acid or its acid halide (C) can be appropriately selected according to the desired molecular design. change. Among them, in terms of an ester resin having high solvent solubility and being easily used in various applications, it is preferred that the hydroxyl group (A _OH ) of the hydroxyl group of the novolak type resin (A) is the same as the above molecule. The ratio (A _OH ) / (B _OH ) of the hydroxyl group (B _OH ) of the hydroxyl group (B) having a phenolic hydroxyl group is 10/90 to 75/25, more preferably Become a ratio of 20/80~50/50. Further, it is preferably 1 mol of the carboxyl group or the oxime halide group of the aromatic polycarboxylic acid or the acid halide (C), and the number of moles of the hydroxyl group of the novolac type resin (A) The total number of moles of the hydroxyl group of the compound (B) having one phenolic hydroxyl group in the above molecule is 0.9 to 1.1 moles.

The active ester resin of the present invention may further contain the compound (B) having a phenolic hydroxyl group in the above molecule and the ester compound (BC) of the above aromatic polycarboxylic acid or its acid halide (C). The ester compound (BC) is reacted, for example, by the above-mentioned novolac type resin (A), the compound (B) having one phenolic hydroxyl group in the above molecule, and the above aromatic polycarboxylic acid or its acid halide (C). The ratio is adjusted to be produced in the form of one of the active ester resins.

An example of a specific structure of the above-mentioned ester compound (BC) is, for example, a structure of the following formula (3), that is, a naphthol compound is used as the compound (B) having one phenolic hydroxyl group, Further, benzenedicarboxylic acid or an acid halide thereof is used as the above aromatic polycarboxylic acid or an acid halide (C) thereof. Further, the following structural formula (3) is merely an example of a specific structure of the above ester compound (BC), and a diester compound having another molecular structure is not excluded.

Wherein R ^{1 is} independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group or an aralkyl group, and may be bonded to any carbon atom forming a naphthalene ring; p is 0 or 1 An integer of ~3)

In the case where the active ester resin contains the above ester compound (BC), the content thereof is preferably less than 40%, more preferably from 0.5 to 35%, of the active ester resin.

The content of the above ester compound (BC) in the active ester resin is a value calculated from the area ratio of the GPC chart, and the GPC chart is measured under the same conditions as the component analysis of the novolac type resin (A). Winner.

The functional group equivalent of the active ester resin of the present invention is preferably in the range of 150 to 350 g/eq. from the viewpoint of an active ester resin having a low curing shrinkage ratio and excellent curability. In the present invention, the functional group in the active ester resin means an ester bond site and a phenolic hydroxyl group in the active ester resin. Further, the functional group equivalent of the active ester resin is a value calculated based on the amount of the reaction raw material added.

The softening point of the active ester resin of the present invention is based on the value measured by JIS K7234 and is preferably in the range of 85 to 160 ° C, more preferably in the range of 100 to 150 ° C.

The weight average molecular weight (Mw) of the active ester resin of the present invention is preferably in the range of 600 to 5,000, particularly preferably in the range of 800 to 3,000, in terms of the active ester resin having a low curing shrinkage ratio. Further, the weight average molecular weight (Mw) of the active ester resin is a value calculated based on the area ratio of the GPC chart, and the GPC chart is measured under the same conditions as the component analysis of the novolac type resin (A). Winner.

The curable resin composition of the present invention contains the above-mentioned active ester resin and a curing agent. The curing agent may be any compound that can react with the active ester resin of the present invention, and various compounds can be used without particular limitation. An example of the curing agent is an epoxy resin.

Examples of the epoxy resin include a phenol novolac type epoxy resin, a cresol novolak type epoxy resin, a naphthol novolac type epoxy resin, a bisphenol novolac type epoxy resin, and a biphenol novolac type epoxy resin. Resin, bisphenol type epoxy resin, biphenyl type epoxy resin, trisphenol methane type epoxy resin, tetraphenol ethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aryl An alkyl type epoxy resin, a naphthol aralkyl type epoxy resin, or the like.

When an epoxy resin is used as the above-mentioned curing agent, other hardeners for epoxy resins may be used in addition to the active ester resin of the present invention. Other hardeners for epoxy resins used herein include, for example, diaminodiphenylmethane, diethylidenetriamine, tris-ethyltetramine, diaminodiphenylphosphonium, isophorone II. An amine compound such as an amine, an imidazole, a BF ₃ -amine complex or an anthracene derivative; a decylamine compound; a guanamine compound such as a polyamine resin synthesized from a dimer of linoleic acid and ethylenediamine; Phthalic anhydride, 1,2,4-benzenetricarboxylic anhydride, pyrogalic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylic acid anhydride ( An acid anhydride such as methyl nadic anhydride, hexahydrophthalic anhydride or methylhexahydrophthalic anhydride; a phenol novolak type resin, a cresol novolak resin, a naphthol novolak resin, a bisphenol novolac type resin, Bisphenol novolak resin, dicyclopentadiene-phenol addition resin, phenol aralkyl resin, naphthol aralkyl resin, trisphenol methane resin, tetraphenol ethane resin, amine tris A phenol resin such as a phenol resin is modified.

The blending ratio of the active ester resin, the epoxy resin, and the other hardener composition for an epoxy resin of the present invention is preferably a ratio of 1 mol to the total of the epoxy groups in the epoxy resin, and the above active ester The total of the functional groups in the resin and other epoxy resin hardeners is 0.7 to 1.5 moles.

Further, the curable resin composition of the present invention may further contain a cyanate resin, a bismaleimide resin, benzo Resin, styrene-maleic anhydride resin, allyl-containing resin, polyphosphate or phosphate-carbonate copolymer represented by diallyl bisphenol or triallyl isocyanurate Wait. These may be used alone or in combination of two or more.

The curable resin composition of the present invention may optionally contain various additives such as a curing accelerator, a flame retardant, an inorganic filler, a decane coupling agent, a release agent, a pigment, and an emulsifier.

Examples of the hardening accelerator include a phosphorus compound, a tertiary amine, an imidazole compound, a pyridine compound, an organic acid metal salt, a Lewis acid, and an amine complex salt. Among them, among the phosphorus compounds, triphenylphosphine is preferred in terms of excellent properties such as hardenability, heat resistance, electrical properties, moisture resistance reliability, etc., among the tertiary amines, preferred is 1,8-diazabicyclo ring. -[5.4.0]-undecene (DBU), preferably 2-ethyl-4-methylimidazole in the imidazole compound, and 4-dimethylaminopyridine in the pyridine compound.

Examples of the flame retardant include inorganic phosphorus compounds such as ammonium phosphate and ammonium phosphate such as red phosphorus, ammonium phosphate, diammonium phosphate, triammonium phosphate, and ammonium polyphosphate; phosphate compounds, phosphonic acid compounds, and phosphinic acid. Acid) compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide (9,10-dihydro- 9-oxa-10-phospha phenanthrene-10-oxide), 10-(2,5-dihydroxyphenyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10-(2,7 a cyclic organophosphorus compound such as -dihydroxynaphthyl)-10H-9-oxa-10-phosphaphenanthrene-10-oxide, and a derivative obtained by reacting a compound such as an epoxy resin or a phenol resin Phosphorus compound; three Compound, cyanuric acid compound, isomeric cyanuric acid compound, thiophene Nitrogen-based flame retardants; polyfluorene-based flame retardants such as polyoxygenated oils, polyoxyxene rubbers, polyfluorene oxide resins; metal hydroxides, metal oxides, metal carbonate compounds, metal powders, boron compounds, Inorganic flame retardants such as low-melting glass. In the case of using such a flame retardant, it is preferably in the range of 0.1 to 20% by mass in the curable resin composition.

The inorganic filler is blended, for example, when the curable resin composition of the present invention is used for a semiconductor sealing material. Examples of the inorganic filler include molten cerium oxide, crystalline cerium oxide, aluminum oxide, cerium nitride, and aluminum hydroxide. Among them, in view of the fact that the inorganic filler is more blended, the above-mentioned molten cerium oxide is preferred. The molten cerium oxide can be used in any form of a crushed shape or a spherical shape. In order to increase the amount of molten cerium oxide to be added and to suppress an increase in the melt viscosity of the curable composition, it is preferred to use a spherical shape. Further, in order to increase the blending amount of the spherical cerium oxide, it is preferred to appropriately adjust the particle size distribution of the spherical cerium oxide. The filling rate is preferably in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

In the case where the curable resin composition of the present invention is used for a conductive paste or the like, a conductive filler such as silver powder or copper powder can be used.

As described in detail above, the active ester resin of the present invention is characterized in that the cured product has high heat resistance and moisture absorption resistance and is excellent in dielectric properties. In addition, it is high in the solubility required in a common organic solvent or the usual required performance of a resin material such as an epoxy resin, in addition to a printed wiring substrate, a semiconductor sealing material, a resist material, or the like. In addition to the use of electronic materials, it can also be widely used in applications such as coatings, adhesives, and molded articles.

When the curable resin composition of the present invention is used for a printed wiring board application or a build-up film application, it is generally preferred to use an organic solvent to be diluted and used. The above organic solvent may, for example, be methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cyproterone or ethyl diethylene glycol. Acetate, propylene glycol monomethyl ether acetate, and the like. The type or blending amount of the organic solvent can be appropriately adjusted depending on the use environment of the curable resin composition. For example, in the use of a printed wiring board, it is preferably a boiling point of 160 such as methyl ethyl ketone, acetone or dimethylformamide. The polar solvent of ° C or less is preferably used in a proportion of 40 to 80% by mass of nonvolatile matter. In the use of the build-up film, it is preferred to use a ketone solvent such as acetone, methyl ethyl ketone or cyclohexanone; ethyl acetate, butyl acetate, ceramide acetate, propylene glycol monomethyl ether acetate, carbitol. Acetate solvent such as acetate; carbitol solvent such as celecoxime and butyl carbitol; aromatic hydrocarbon solvent such as toluene or xylene; dimethylformamide, dimethylacetamide, N- Methylpyrrolidone or the like; preferably used in a proportion of 30 to 60% by mass of nonvolatile matter.

In addition, a method of producing a printed wiring board using the curable resin composition of the present invention is, for example, a method in which a reinforcing substrate is impregnated with a curable composition and cured to obtain a prepreg, which is superposed on the copper foil. Heat crimping. Examples of the reinforcing substrate include paper, glass cloth, glass non-woven fabric, polyarsenamide paper, polyarsenide cloth, glass mat, glass roving cloth, and the like. The impregnation amount of the curable resin composition is not particularly limited, but it is usually preferably prepared so that the resin component in the prepreg is 20 to 60% by mass.

When the curable resin composition of the present invention is used for the use of a semiconductor sealing material, it is generally preferred to blend an inorganic filler. The semiconductor sealing material containing the active ester resin of the present invention, a curing agent, an inorganic filler, and other optional components can be prepared, for example, by mixing the blend using an extruder, a kneader, a roll, or the like. The method of molding a semiconductor package using the obtained semiconductor sealing material is, for example, molding the semiconductor sealing material by a casting molding, a transfer molding machine, an injection molding machine, or the like, and further heating at a temperature of 50 to 200 ° C for 2 to 10 hours. By this method, a semiconductor device which is a molded article can be obtained.

 [Examples]  

Next, the present invention will be specifically described by way of examples and comparative examples. The description of "parts" and "%" in the examples is a quality standard unless otherwise specified. In addition, the measurement conditions of GPC, 13C-NMR, and MALDI-TOF-MS in this Example are as follows.

GPC measurement conditions

Measuring device: "HLC-8320 GPC" manufactured by Tosoh Co., Ltd.,

Pipe column: Protection column "HXL-L" manufactured by Tosoh Co., Ltd.

"TSK-GEL G4000HXL" manufactured by Tosoh Co., Ltd.

"TSK-GEL G3000HXL" manufactured by Tosoh Co., Ltd.

"TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

"TSK-GEL G2000HXL" manufactured by Tosoh Co., Ltd.

Detector: RI (differential refractometer)

Data Processing: "GPC Workstation EcoSEC-WorkStation" manufactured by Tosoh Co., Ltd.

Measurement conditions: column temperature 40 ° C

Developing solvent tetrahydrofuran

Flow rate 1.0ml/min

Standard: The following monodisperse polystyrene having a known molecular weight is used in accordance with the above-mentioned "GPC-8320" measurement manual.

(using polystyrene)

"A-500" manufactured by Tosoh Co., Ltd.

"A-1000" manufactured by Tosoh Co., Ltd.

"A-2500" manufactured by Tosoh Co., Ltd.

"A-5000" manufactured by Tosoh Co., Ltd.

"F-1" manufactured by Tosoh Co., Ltd.

"F-2" manufactured by Tosoh Co., Ltd.

"F-4" manufactured by Tosoh Co., Ltd.

"F-10" manufactured by Tosoh Co., Ltd.

"F-20" manufactured by Tosoh Co., Ltd.

"F-40" manufactured by Tosoh Co., Ltd.

"F-80" manufactured by Tosoh Co., Ltd.

"F-128" manufactured by Tosoh Co., Ltd.

Sample: 1.0% by mass of tetrahydrofuran solution in terms of resin solid content conversion was filtered by a microfilter to obtain (50 μl)

13C-NMR measurement conditions

Device: Japan Electronics Co., Ltd. manufactures ECA-500

Measurement mode: SINGLE-PULSE-DEC (1E complete decoupling method for NOE elimination)

Solvent: deuterated chloroform

Pulse angle: 30° pulse

Sample concentration: 30wt%

Cumulative number: 4000 times

MALDI-TOF-MS measurement conditions

Device: AXIMA-TOE2 manufactured by Shimadzu / KRSTOS

Ionization method: matrix-assisted laser desorption free method

Example 1 Production of Active Ester Resin (1)

288 parts by mass of 1-naphthol, 288 parts by mass of 2-naphthol, 576 parts by mass of toluene, and 81% by weight of 37% fumarin aqueous solution were added to the flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer. A portion, a 49% aqueous sodium hydroxide solution, 10 parts by mass. The mixture was heated to 75 ° C while stirring the contents of the flask, and stirred at 75 ° C for 1 hour to carry out a reaction. After completion of the reaction, 13 parts by mass of 35% hydrochloric acid was added for neutralization, and then washed three times with 200 parts by mass of water. Toluene or the like was distilled off under heating and reduced pressure to obtain 568 parts by mass of a mixture (1) containing unreacted naphthol and a novolac type resin (A-1). The obtained hydroxyl group equivalent of the mixture (1) was 147 g/eq. The content of the component of the mixture (1) calculated according to the area ratio of the GPC line diagram is 32.6%, the content of the component having the number of cores of 3 is 12.2%, and the content of the component having the number of cores of 4 is The ratio of the content of the component (N2) having a core number of 2 (N2) to the content of the component having a number of nuclei (N3) [(N3)/(N2)] was 0.37.

141 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were added to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer, and nitrogen gas was decompressed in the system. Displace one side to dissolve it. Then, 206 parts by mass of the previously obtained mixture (1) was added, and it was dissolved while being subjected to a reduced pressure nitrogen substitution in the system. 0.4 g of tetrabutylammonium bromide was added, and while the nitrogen purge was performed, the inside of the reaction system was controlled to 60 ° C or lower, and 280 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour to carry out the reaction. After the reaction was completed, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the residual organic layer and stirred for about 15 minutes, after which the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and thereafter, toluene or the like was distilled off under heating and reduced pressure to obtain 285 parts by mass of the active ester resin (1). The functional group equivalent of the active ester resin (1) was 212 g/eq., and the softening point measured based on JIS K7234 was 124 °C. The GPC chart of the obtained active ester resin (1) is shown in Fig. 1, 13C-NMR is shown in Fig. 2, and MS is shown in Fig. 3. The content of the ester compound (BC) in the active ester resin (1) calculated according to the area ratio of the GPC line chart was 28.7%, and the weight average molecular weight (Mw) was 1219.

Example 2 Production of Active Ester Resin (2)

432 parts by mass of 1-naphthol, 144 parts by mass of 2-naphthol, 576 parts by mass of toluene, and 81% by weight of 37% fumarin aqueous solution were added to the flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer. A portion, a 49% aqueous sodium hydroxide solution, 10 parts by mass. The mixture was heated to 75 ° C while stirring the contents of the flask, and stirred at 75 ° C for 1 hour to carry out a reaction. After completion of the reaction, 13 parts by mass of 35% hydrochloric acid was added for neutralization, and then washed three times with 200 parts by mass of water. Toluene or the like was distilled off under heating and reduced pressure to obtain 565 parts by mass of a mixture (2) containing unreacted naphthol and a novolac type resin (A-2). The obtained hydroxyl group equivalent of the mixture (2) was 147 g/eq. The content of the component of the mixture (2) calculated according to the area ratio of the GPC line diagram is 19.7%, the content of the component having the number of cores of 3 is 14.1%, and the content of the component having the number of cores of 4 is 6.5%, the ratio of the content of the component having a number of nuclei of 2 (N2) to the content of the component having a number of nuclei of 3 (N3) [(N3)/(N2)] was 0.72.

141 parts by mass of m-xylylene chloride and 1000 parts by mass of toluene were added to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer, and the pressure was replaced with nitrogen under a reduced pressure in the system. Dissolved. Then, 206 parts by mass of the previously obtained mixture (2) was added, and it was dissolved while being subjected to a reduced pressure nitrogen substitution in the system. 0.4 g of tetrabutylammonium bromide was added, and while the nitrogen purge was performed, the inside of the reaction system was controlled to 60 ° C or lower, and 280 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour to carry out the reaction. After the reaction was completed, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the residual organic layer and stirred for about 15 minutes, after which the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and then toluene or the like was distilled off under heating and reduced pressure to obtain 287 parts by mass of the active ester resin (2). The functional group equivalent of the active ester resin (2) was 212 g/eq., and the softening point measured based on JIS K7234 was 131 °C. The GPC chart of the obtained active ester resin (2) is shown in Fig. 4 . The content of the ester compound (BC) in the active ester resin (2) calculated based on the area ratio of the GPC chart was 32.7%, and the weight average molecular weight (Mw) was 1621.

Example 3 Production of Active Ester Resin (3)

576 parts by mass of 1-naphthol, 81 parts by mass of water, and 81 parts by mass of a 37% formalin aqueous solution were placed in a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer. The mixture was heated to 95 ° C while stirring the contents of the flask, and stirred at 95 ° C for 2 hours to carry out a reaction. After completion of the reaction, water or the like was distilled off under heating and reduced pressure to obtain 570 parts by mass of a mixture (3) containing unreacted naphthol and a novolac type resin (A-3). The obtained hydroxyl group equivalent of the mixture (3) was 147 g/eq. The content of the component of the mixture (3) calculated according to the area ratio of the GPC diagram is 23.4%, the content of the component having the number of cores of 3 is 11.1%, and the content of the component having the number of cores of 4 is 3.6%, the ratio of the content of the component having a number of nuclei of 2 (N2) to the content of the component having a number of nuclei of 3 (N3) [(N3)/(N2)] was 0.33.

141 parts by mass of m-xylylene chloride and 1000 parts by mass of toluene were added to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer, and the pressure was replaced with nitrogen under a reduced pressure in the system. Dissolved. Then, 206 parts by mass of the previously obtained mixture (3) was added, and it was dissolved while being subjected to a reduced pressure nitrogen substitution in the system. 0.4 g of tetrabutylammonium bromide was added, and while the nitrogen purge was performed, the inside of the reaction system was controlled to 60 ° C or lower, and 280 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour to carry out the reaction. After the reaction was completed, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the residual organic layer and stirred for about 15 minutes, after which the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and then toluene or the like was distilled off under heating and reduced pressure to obtain 282 parts by mass of the active ester resin (3). The functional group equivalent of the active ester resin (3) was 212 g/eq, and the softening point measured based on JIS K7234 was 131 °C. The GPC chart of the obtained active ester resin (3) is shown in Fig. 5. The content of the ester compound (BC) in the active ester resin (3) calculated according to the area ratio of the GPC chart was 27.5%, and the weight average molecular weight (Mw) was 1,285.

Comparative Production Example 1 Production of Active Ester Resin (1')

Adding 165 parts by mass of an addition reaction product (hydroxyl group equivalent: 165 g/eq, softening point 85 ° C) of dicyclopentadiene and phenol to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer, 72 parts by mass of 1-naphthol and 630 parts by mass of toluene were dissolved while being subjected to a reduced pressure nitrogen substitution in the system. Then, 152 parts by mass of m-xylylene chloride was added, and it was dissolved while being subjected to a reduced pressure nitrogen substitution in the system. While performing nitrogen purge, the inside of the system was controlled to 60 ° C or lower, and 210 g of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour to carry out the reaction. After the reaction was completed, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the residual organic layer and stirred for about 15 minutes, after which the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and thereafter, toluene or the like was distilled off under heating and reduced pressure to obtain an active ester resin (1'). The functional group equivalent of the active ester resin (1') was 223 g/eq., and the softening point measured based on JIS K7234 was 150 °C.

Comparative Production Example 2 Production of Active Ester Resin (2')

576 parts by mass of 2-naphthol, 576 parts by mass of toluene, 81 parts by mass of a 37% formalin aqueous solution, and 49% aqueous sodium hydroxide solution were added to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer. 10 parts by mass. The mixture was heated to 75 ° C while stirring the contents of the flask, and stirred at 75 ° C for 1 hour to carry out a reaction. After completion of the reaction, 13 parts by mass of 35% hydrochloric acid was added for neutralization, and then washed three times with 200 parts by mass of water. Toluene or the like was distilled off under heating and reduced pressure to obtain 520 parts by mass of a mixture (1') containing unreacted naphthol and a novolac type resin (A'-1). The hydroxyl equivalent of the mixture (1') was 147 g/eq. The content of the component of the mixture (1') based on the area ratio of the GPC diagram is 2:40. The content of the component having the number of core bodies of 3 is 0%, and the content of the number of cores is 4%. The ratio [(N3)/(N2)] of the content (N2) of the component (N2) having a content of 2% of the nuclei and the content of the component having a number of nuclei of 3 (N3) was 0.00.

141 parts by mass of m-xylylene chloride and 1000 parts by mass of toluene were added to a flask equipped with a thermometer, a dropping funnel, a condenser, a shunt tube, and a stirrer, and the pressure was replaced with nitrogen under a reduced pressure in the system. Dissolved. Then, 206 parts by mass of the previously obtained mixture (1') was added, and it was dissolved while being subjected to a reduced pressure nitrogen substitution in the system. 0.4 g of tetrabutylammonium bromide was added, and while the nitrogen purge was performed, the inside of the reaction system was controlled to 60 ° C or lower, and 280 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After the completion of the dropwise addition, stirring was continued for 1 hour to carry out the reaction. After the reaction was completed, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. Water was added to the residual organic layer and stirred for about 15 minutes, after which the mixture was allowed to stand for liquid separation, and the aqueous layer was removed. This operation is repeated until the pH of the aqueous layer becomes 7, and thereafter, toluene or the like is distilled off under heating and reduced pressure to obtain an active ester resin (2'). The functional group equivalent of the active ester resin (2') was 212 g/eq. according to the addition ratio.

Evaluation of solvent solubility

10 parts by mass of the active ester resin obtained in Examples 1 to 3 and Comparative Production Examples 1 and 2, and 6.7 parts by mass of toluene were placed in a sample bottle and sealed, and the mixture was heated to 80 ° C to be dissolved. Thereafter, the mixture was cooled to 25 ° C to evaluate whether or not crystals were precipitated. The case where the crystal was not precipitated was judged as A, and the case where the crystal was precipitated was judged as B. The results are shown in Table 1.

Examples 4 to 6 and Comparative Examples 1, 2

Each component was blended in a ratio shown in the following Table 2 to obtain a curable resin composition (1). The hardening shrinkage ratio of the curable resin composition (1) obtained was measured according to the following points. The results are shown in Table 2. Further, in Comparative Example 2 using the above-mentioned active ester resin (2'), the test piece could not be produced because of high crystallinity, and the evaluation test could not be performed.

Determination of hardening shrinkage

Using a transfer molding machine ("KTS-15-1.5C" manufactured by Kohtaki Precision Machine Co., Ltd.), the curable resin composition (1) was obtained under the conditions of a mold temperature of 154 ° C, a molding pressure of 9.8 MPa, and a curing time of 600 seconds. Injection molding was carried out to obtain a molded article having a length of 110 mm, a width of 12.7 mm, and a thickness of 1.6 mm. Then, the obtained molded product was cured at 175 ° C for 5 hours, and then left at room temperature (25 ° C) for 24 hours or more, and this was used as a test piece. The dimensions of the test piece in the longitudinal direction at room temperature and the dimension in the longitudinal direction of the mold at 154 ° C were measured, and the curing shrinkage ratio was calculated by the following formula.

Hardening shrinkage ratio (%) = {(mold dimension in the longitudinal direction at 154 ° C) - (dimension in the longitudinal direction of the test piece at room temperature)} / (size in the longitudinal direction of the mold at 154 ° C) × 100 ( %)

Epoxy resin (*): bisphenol A epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation, epoxy equivalent 188g / equivalent)

Examples 7 to 9 and Comparative Examples 3 and 4

Each component was blended in a ratio shown in the following Table 3 to obtain a curable resin composition (2). With respect to the obtained curable resin composition (2), the dielectric loss tangent of the cured product was measured in accordance with the following points. The results are shown in Table 3. Further, in Comparative Example 2 using the above-mentioned active ester resin (2'), the test piece could not be produced because of high crystallinity, and the evaluation test could not be performed.

Determination of dielectric loss tangent

The curable resin composition (2) was poured into a mold frame using a press machine, and molded at a temperature of 175 ° C for 10 minutes. The molded product was taken out from the mold frame and allowed to harden at a temperature of 175 ° C for 5 hours. The molded product after hardening was cut out to a size of 1 mm × 100 mm × 1.6 mm, and this was used as a test piece. Using a network analyzer "E8362C" manufactured by Agilent Technology Co., Ltd., the dielectric loss tangent at 1 GHz of a test piece which was stored in a chamber at 23 ° C and a humidity of 50% after heating and vacuum drying for 24 hours was measured by a cavity resonance method. .

Epoxy resin (*): bisphenol A type epoxy resin ("EPICLON 850-S" manufactured by DIC Corporation, epoxy equivalent: 188 g/eq.).

Claims (7)

 An active ester resin having the following (A), (B), and (C) as essential reaction materials: a novolac type resin (A) having a naphthol compound (a) as a reaction raw material and containing a number of nuclei A component of 3 or more is an essential component; a compound (B) having a phenolic hydroxyl group in the molecule; and an aromatic polycarboxylic acid or an acid halide (C) thereof.    The active ester resin according to the first aspect of the invention, wherein the novolak-type resin (A) contains a component having a number of nuclei of 3 or 4 in a range of from 1 to 50%.    The active ester resin according to the first aspect of the invention, wherein the naphthol compound (a) is the same compound as the compound (B) having one phenolic hydroxyl group in the molecule.    A curable resin composition comprising the active ester resin according to any one of claims 1 to 3, and a curing agent.    A cured product which is a cured product of the curable resin composition of claim 4 of the patent application.    A printed wiring board obtained by using the curable resin composition of the fourth application of the patent application.    A semiconductor sealing material obtained by using a curable resin composition of the fourth application of the patent application.