JP2018009129A - Active ester resin and cured product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an active ester resin which has a low curing shrinkage rate and gives a cured product excellent in dielectric characteristics, a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor sealing material.SOLUTION: The active ester resin uses as essential reaction raw materials: a compound (A) having one phenolic hydroxyl group in the molecular structure; a phenolic hydroxyl group-containing resin (B) using as essential reaction raw materials a phenolic hydroxyl group-containing compound (b1) and a divinyl compound (b2); and an aromatic polycarboxylic acid or an acid halide thereof (C). The curable resin composition containing the active ester resin, the cured product thereof, the printed wiring board, and the semiconductor sealing material are also provided.SELECTED DRAWING: None

Description

  The present invention relates to an active ester resin having a low cure shrinkage and excellent dielectric properties in a cured product, a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor sealing material.

  In the technical field of insulating materials used for semiconductors and multilayer printed circuit boards, development of new resin materials that meet these market trends is required as various electronic components become thinner and signals become faster and higher in frequency. ing. For example, as the electronic member becomes thinner, the “warping” of the member due to heat becomes more prominent. In order to suppress this, development of a resin material having a low curing shrinkage rate and high dimensional stability is underway. In addition, in order to reduce the energy loss due to heat generation or the like for increasing the signal speed and frequency, development of a resin material having both low values of dielectric constant and dielectric loss tangent in the cured product is underway.

  Technology that uses an active ester resin obtained by esterifying dicyclopentadiene-modified phenolic resin and α-naphthol with phthalic acid chloride as a curing agent for epoxy resin, as a resin material having a relatively low dielectric constant and dielectric loss tangent in the cured product Is known (see Patent Document 1 below). The active ester resin described in Patent Document 1 has a low dielectric constant and dielectric loss tangent in a cured product as compared with the case where a conventional curing agent such as a phenol novolac resin is used. However, the value of the dielectric loss tangent has been required to be further reduced. Further, there has been a demand for further reduction in curing shrinkage.

JP 2004-169021 A

  Accordingly, the problem to be solved by the present invention is an active ester resin having a low cure shrinkage and excellent dielectric properties in a cured product, a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor It is to provide a sealing material.

  As a result of intensive studies to solve the above problems, the present inventors have found that an active ester resin obtained using a phenolic hydroxyl group-containing resin having a phenolic hydroxyl group-containing compound and a divinyl compound as essential reaction raw materials has a cure shrinkage rate. Was found to be low and the dielectric constant and dielectric loss tangent of the cured product were both extremely low, leading to the completion of the present invention.

  That is, the present invention relates to a phenolic hydroxyl group-containing resin comprising a compound (A) having one phenolic hydroxyl group in the molecular structure, a phenolic hydroxyl group-containing compound (b1) and a divinyl compound (b2) as essential reaction materials ( The present invention relates to an active ester resin characterized by using B) and an aromatic polycarboxylic acid or an acid halide (C) thereof as an essential reaction raw material.

  The present invention further relates to a curable resin composition containing the active ester resin and a curing agent.

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

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

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

  According to the present invention, there are provided an active ester resin having a low cure shrinkage and excellent dielectric properties in a cured product, a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor sealing material. be able to.

1 is a GPC chart of the active ester resin (1) obtained in Example 1. FIG. FIG. 2 is a GPC chart of the active ester resin (2) obtained in Example 2. FIG. 3 is a GPC chart of the active ester resin (3) obtained in Example 3. FIG. 4 is a GPC chart of the active ester resin (4) obtained in Example 4. FIG. 5 is a GPC chart of the active ester resin (5) obtained in Example 5. FIG. 6 is a GPC chart of the active ester resin (6) obtained in Example 6. FIG. 7 is a 13 C-NMR chart of the active ester resin (6) obtained in Example 6. FIG. 8 is an MS chart of the active ester resin (6) obtained in Example 6.

Hereinafter, the present invention will be described in detail.
The active ester resin of the present invention contains a phenolic hydroxyl group containing a compound (A) having one phenolic hydroxyl group in the molecular structure, a phenolic hydroxyl group-containing compound (b1) and a divinyl compound (b2) as essential reaction materials. Resin (B) and aromatic polycarboxylic acid or its acid halide (C) are used as essential reaction raw materials.

  The compound (A) having one phenolic hydroxyl group in the molecular structure may be any compound as long as it is an aromatic compound having one hydroxyl group on the aromatic ring, and other specific structures are not particularly limited. In the present invention, the compound (A) having one phenolic hydroxyl group in the molecular structure may be used alone or in combination of two or more. The compound (A) having one phenolic hydroxyl group in the molecular structure is specifically a phenol compound having one or more substituents on the aromatic nucleus of phenol or phenol, naphthol or naphthol aromatic nucleus. And naphthol compounds having one or more substituents, anthracenol, or naphthol compounds having one or more substituents on the aromatic nucleus of anthracenol. Substituents on the aromatic nucleus include, for example, aliphatic carbonization such as methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, and nonyl groups. Hydrogen group; alkoxy group such as methoxy group, ethoxy group, propyloxy group, butoxy group; halogen atom such as fluorine atom, chlorine atom, bromine atom; phenyl group, naphthyl group, anthryl group, and the aromatic nucleus An aryl group substituted by an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, etc .; a phenylmethyl group, a phenylethyl group, a naphthylmethyl group, a naphthylethyl group, and the aliphatic hydrocarbon group or alkoxy group on the aromatic nucleus thereof; And an aralkyl group substituted with a halogen atom or the like.

  Among these, a naphthol compound is preferable because it has a low cure shrinkage and is excellent in dielectric properties in a cured product, and 1-naphthol or 2-naphthol is particularly preferable.

  Regarding the phenolic hydroxyl group-containing resin (B), the phenolic hydroxyl group-containing compound (b1) may be any compound as long as it is an aromatic compound having a hydroxyl group on the aromatic ring, and the other specific structure is not particularly limited. Specific examples include the same compounds as the various compounds exemplified as the compound (A) having one phenolic hydroxyl group in the molecular structure. Moreover, a phenolic hydroxyl group containing compound (b1) may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, a naphthol compound is preferable because it has a low cure shrinkage and is excellent in dielectric properties in a cured product, and 1-naphthol or 2-naphthol is particularly preferable.

  The divinyl compound (b2) may be any compound as long as it can react with the phenolic hydroxyl group-containing compound (b1) and knot the phenolic hydroxyl group-containing compound (b1), and the other specific structures are as follows. There is no particular limitation. Moreover, a divinyl compound (b2) may be used individually by 1 type, and may be used in combination of 2 or more types. Among them, a compound having an aromatic ring or a cyclo ring in the molecular structure is preferable because it becomes an active ester resin having a low cure shrinkage and excellent dielectric properties in a cured product. As a more preferable specific structure of the divinyl compound (b2), for example, the following structural formulas (1-1) to (1-4)

（式中Ｒ^１はそれぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかであり、ｉは０又は１〜４の整数である。Ｙは炭素原子数１〜４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは１〜４の整数である。）
の何れかで表される化合物等が挙げられる。

(In the formula, each R ¹ is independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and i is an integer of 0 or 1 to 4. Y is the number of carbon atoms. Any one of an alkylene group of 1-4, an oxygen atom, a sulfur atom, and a carbonyl group, j is an integer of 1-4.)
Or a compound represented by any of the above.

R ¹ in the structural formulas (1-1) to (1-4) is each independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group. Specifically, , Aliphatic hydrocarbon groups such as methyl group, ethyl group, vinyl group, propyl group, butyl group, pentyl group, hexyl group, cyclohexyl group, heptyl group, octyl group, nonyl group; methoxy group, ethoxy group, An alkoxy group such as a propyloxy group and a butoxy group; a halogen atom such as a fluorine atom, a chlorine atom and a bromine atom; a phenyl group, a naphthyl group, an anthryl group, and the aliphatic hydrocarbon group and alkoxy group on the aromatic nucleus; Aryl groups substituted by halogen atoms, etc .; phenylmethyl group, phenylethyl group, naphthylmethyl group, naphthylethyl group, and aliphatic hydrocarbons on these aromatic nuclei And an aralkyl group substituted with a group, an alkoxy group, a halogen atom, or the like.

  Among the compounds represented by any of the structural formulas (1-1) to (1-4), an active ester resin having a low curing shrinkage rate and excellent dielectric properties in a cured product is used. It is preferable that it is a compound represented by (1-1).

  When the compound represented by any of the structural formulas (1-1) to (1-4) is used as the divinyl compound (b2), the phenolic hydroxyl group-containing resin (B) is a phenolic hydroxyl group-containing compound. (B1) is the following structural formula (2)

［式中Ｘは下記構造式（Ｘ−１）〜（Ｘ−４）の何れかで表される構造部位である。

[Wherein X is a structural moiety represented by any of the following structural formulas (X-1) to (X-4).

（式中Ｒ^１はそれぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかであり、ｉは０又は１〜４の整数である。Ｙは炭素原子数１〜４のアルキレン基、酸素原子、硫黄原子、カルボニル基の何れかである。ｊは１〜４の整数である。）］
で表される構造部位（α）で結節された分子構造を有するものとなる。

(In the formula, each R ¹ is independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and i is an integer of 0 or 1 to 4. Y is the number of carbon atoms. Any one of an alkylene group of 1-4, an oxygen atom, a sulfur atom, and a carbonyl group, j is an integer of 1-4)
It has a molecular structure knotted at the structural site (α) represented by

  In addition to the phenolic hydroxyl group-containing compound (b1) and the divinyl compound (b2), the phenolic hydroxyl group-containing resin (B) may contain other compounds as reaction raw materials. The other compound is, for example, a compound (b2 ′) that is a compound other than the divinyl compound (b2) such as various aldehyde compounds and can knot the naphthol compound (b), or a phenolic hydroxyl group-containing resin (B). Examples of the substituent on the aromatic ring include a substituent introducing agent (b3) for introducing an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, and an aralkyl group.

  When the compound (b2 ′) is used, the divinyl compound (b2) and the compound are sufficiently exhibited because the effect of the present invention is sufficiently exhibited that the cure shrinkage ratio is low and the dielectric loss tangent in the cured product is low. It is preferable that the said divinyl compound (b2) will be 50 mass% or more with respect to the sum total with (b2 '), and it is preferable that it will be 80 mass% or more.

  Examples of the substituent introduction agent (b3) include aralkyl group introduction agents such as a phenylmethanol compound, a phenylmethyl halide compound, a naphthylmethanol compound, a naphthylmethyl halide compound, and a styrene compound.

  The method for producing the phenolic hydroxyl group-containing resin (B) is not particularly limited, but it is preferable to adjust the ratio of reaction raw materials so that the number of phenolic hydroxyl groups per molecule is 2 or more. For example, the phenolic hydroxyl group-containing compound (b1) is used in a range of 2 to 10 moles with respect to 1 mole of the divinyl compound (b2), and heated and stirred under acid catalyst conditions and at a temperature of about 80 to 180 ° C. It can be manufactured by a method. You may perform reaction in an organic solvent as needed. After completion of the reaction, an excessive amount of the phenolic hydroxyl group-containing compound (b1) may be distilled off as desired. Further, the unreacted phenolic hydroxyl group-containing compound (b1) in the reaction product may be used as it is as the compound (A) having one phenolic hydroxyl group in the molecular structure.

  Examples of the acid catalyst include p-toluenesulfonic acid, dimethyl sulfate, diethyl sulfate, sulfuric acid, hydrochloric acid, and oxalic acid. These may be used alone or in combination of two or more. The addition amount of the acid catalyst is preferably in the range of 0.01 to 10% by mass with respect to the phenolic hydroxyl group-containing compound (b1).

  Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; and carbitols such as cellosolve and butyl carbitol. Examples include solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. These may be used alone or as a mixed solvent of two or more.

  As an example of a specific structure of the phenolic hydroxyl group-containing resin (B), for example, a structure example in the case of using naphthol as the phenolic hydroxyl group-containing compound (b1) and divinylbenzene as the divinyl compound (b2) is shown below. Shown in Structural Formula (B-1) The following structural formula (B-1) is merely an example of the specific structure of the phenolic hydroxyl group-containing resin (B), and does not exclude other resin structures.

［式中ｎは１〜１０の整数である。Ｒはそれぞれ独立に水素原子又は下記構造式（Ｒ−１）で表される構造部位である。］

[Wherein n is an integer of 1 to 10. Each R is independently a hydrogen atom or a structural moiety represented by the following structural formula (R-1). ]

  Further, commercially available divinylbenzene may contain a part of ethylstyrene. In this case, a part of the structure represented by the following structural formula (R-2) may be introduced as R in the structural formula (B-1).

  The hydroxyl equivalent of the phenolic hydroxyl group-containing resin (B) is preferably in the range of 130 to 300 g / equivalent because it is highly soluble in a solvent and becomes an active ester resin that can be easily used for various applications.

  The aromatic polycarboxylic acid or its acid halide (C) reacts with the compound (A) having one phenolic hydroxyl group in the molecular structure and the phenolic hydroxyl group of the phenolic hydroxyl group-containing resin (B). The specific structure is not particularly limited as long as it is an aromatic compound capable of forming an ester bond, and any compound may be used. Specific examples include benzenedicarboxylic acids such as isophthalic acid and terephthalic acid, benzenetricarboxylic acids such as trimellitic acid, naphthalene-1,4-dicarboxylic acid, naphthalene-2,3-dicarboxylic acid, and naphthalene-2,6. -Naphthalene dicarboxylic acid such as dicarboxylic acid and naphthalene-2,7-dicarboxylic acid, acid halides thereof, and compounds in which the aliphatic hydrocarbon group, alkoxy group, halogen atom, etc. are substituted on the aromatic nucleus Can be mentioned. Examples of the acid halide include acid chloride, acid bromide, acid fluoride, and acid iodide. These may be used alone or in combination of two or more. Among these, benzenedicarboxylic acids such as isophthalic acid and terephthalic acid or acid halides thereof are preferable because they are active ester resins having high reaction activity and excellent curability.

  The active ester resin of the present invention includes, for example, a compound (A) having one phenolic hydroxyl group in the molecular structure, the phenolic hydroxyl group-containing resin (B), the aromatic polycarboxylic acid or an acid halide thereof ( A reaction raw material essentially comprising C) can be produced by a method of heating and stirring under a temperature condition of about 40 to 65 ° C. in the presence of an alkali catalyst. You may perform reaction in an organic solvent as needed. Further, after completion of the reaction, the reaction product may be purified by washing, reprecipitation or the like, if desired.

  Examples of the alkali catalyst include sodium hydroxide, potassium hydroxide, triethylamine, pyridine and the like. These may be used alone or in combination of two or more. Further, it may be used as an aqueous solution of about 3.0 to 30%. Among these, sodium hydroxide or potassium hydroxide having high catalytic ability is preferable.

  Examples of the organic solvent include ketone solvents such as acetone, methyl ethyl ketone, and cyclohexanone; acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate; and carbitols such as cellosolve and butyl carbitol. Examples include solvents, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. These may be used alone or as a mixed solvent of two or more.

The reaction ratio of the compound (A) having one phenolic hydroxyl group in the molecular structure, the phenolic hydroxyl group-containing resin (B), and the aromatic polycarboxylic acid or acid halide (C) thereof is determined as a desired molecule. It can be appropriately changed according to the design. Among them, since it becomes an active ester resin that has high solvent solubility and can be easily used for various applications, the number of moles of hydroxyl groups (A _OH ) of the compound (A) having one phenolic hydroxyl group in the molecular structure preferably the phenolic hydroxyl group-containing resin (B) is the number of moles of the hydroxyl groups the ratio of _{(B OH) [(a OH} ) / (B OH)] is the rate at which the 10 / 90-75 / 25, The ratio is more preferably 25/75 to 50/50. In addition, with respect to a total of 1 mol of the carboxyl group or acid halide group of the aromatic polycarboxylic acid or its acid halide (C), the hydroxyl group of the compound (A) having one phenolic hydroxyl group in the molecular structure It is preferable that the sum of the number of moles and the number of moles of hydroxyl groups of the phenolic hydroxyl group-containing resin (B) is 0.95 to 1.05 moles.

  The active ester resin of the present invention is a part of the ester compound (AC) of the compound (A) having one phenolic hydroxyl group in the molecular structure and the aromatic polycarboxylic acid or its acid halide (C). You may contain. The ester compound (AC) includes, for example, a compound (A) having one phenolic hydroxyl group in the molecular structure, the phenolic hydroxyl group-containing resin (B), the aromatic polycarboxylic acid or an acid halide thereof ( By adjusting the reaction ratio of C), it can be produced as one component of an active ester resin.

  As an example of the specific structure of the ester compound (AC), for example, a naphthol compound is used as the compound (A) having one phenolic hydroxyl group in the molecular structure, and the aromatic polycarboxylic acid or its acid halide (C A structural example in the case of using benzenedicarboxylic acid or an acid halide thereof as () is shown in the following structural formula (3). The following structural formula (3) is merely an example of the specific structure of the ester compound (AC), and does not exclude other diester compounds having a molecular structure.

（式中Ｒ^２はそれぞれ独立して脂肪族炭化水素基、アルコキシ基、ハロゲン原子、アリール基、アラルキル基の何れかであり、ナフタレン環を形成するどの炭素原子に結合していても良い。ｐは０又は１〜３の整数である。）

(In the formula, each R ² 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. Is an integer of 0 or 1-3.)

  When the active ester resin contains the ester compound (AC), the content is less than 40% of the active ester resin because the active ester resin has a low cure shrinkage and excellent curability. Is preferably 10% or more and less than 35%.

  The content of the ester compound (AC) in the active ester resin is a value calculated from the area ratio of the GPC chart measured under the following conditions.

Measuring device: “HLC-8320 GPC” manufactured by Tosoh Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G4000HXL”
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: “GPC workstation EcoSEC-WorkStation” 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-8320”.
(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, filtered through a microfilter (50 μl)

  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, from the viewpoint of becoming an active ester resin having a low cure shrinkage rate. . In addition, the weight average molecular weight (Mw) of active ester resin is a value measured by GPC of the same conditions as the time of calculating | requiring content of the said ester compound (AC).

  Further, the softening point of the active ester resin of the present invention is preferably a range of 80 to 180 ° C, more preferably a range of 85 to 160 ° C as a value measured based on JIS K7234.

  The functional group equivalent of the active ester resin of the present invention is preferably in the range of 200 to 350 g / equivalent, since it becomes an active ester resin having a low cure shrinkage and excellent curability. An equivalent range is particularly preferable. 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. The functional group equivalent of the active ester resin is a value calculated from the charged amount of the reaction raw material.

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

  Examples of the epoxy resin include phenol novolac type epoxy resin, cresol novolac type epoxy resin, naphthol novolac type epoxy resin, bisphenol novolac type epoxy resin, biphenol novolac type epoxy resin, bisphenol type epoxy resin, biphenyl type epoxy resin, and triphenolmethane. Type epoxy resin, tetraphenolethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol aralkyl type epoxy resin and the like.

When using an epoxy resin as the curing agent, in addition to the active ester resin of the present invention, other epoxy resin curing agents may be used in combination. Other epoxy resin curing agents used here are, for example, diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complexes, guanidine derivatives, and other amine compounds; dicyandiamide, linolene Amide compounds such as polyamide resin synthesized from acid dimer and ethylenediamine; phthalic anhydride, trimellitic anhydride, pyromellitic anhydride, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methyl anhydride Acid anhydrides such as nadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride; phenol novolak resin, cresol novolak resin, naphthol novolak resin, bisphenol novolak Fat, biphenyl novolac resins, dicyclopentadiene - phenol addition type resins, phenol aralkyl resins, naphthol aralkyl resins, triphenolmethane resins, tetraphenolethane type resins, phenolic resins such as aminotriazine-modified phenolic resin.

  The compounding ratio of the active ester resin, the epoxy resin, and the other epoxy resin curing agent of the present invention is in the active ester resin and the other epoxy resin curing agent with respect to a total of 1 mol of epoxy groups in the epoxy resin. It is preferable that it is a ratio from which the sum total of functional group becomes 0.7-1.5 mol.

  In addition, the curable resin composition of the present invention includes cyanate ester resin, bismaleimide resin, benzoxazine resin, styrene-maleic anhydride resin, allyl group-containing resin represented by diallyl bisphenol and triallyl isocyanurate, polyphosphorus An acid ester, a phosphate ester-carbonate copolymer, or the like may be contained. These may be used alone or in combination of two or more.

  The curable resin composition of this invention may contain various additives, such as a hardening accelerator, a flame retardant, an inorganic filler, a silane coupling agent, a mold release agent, a pigment, an emulsifier, as needed.

  Examples of the curing accelerator include phosphorus compounds, tertiary amines, imidazole compounds, pyridine compounds, organic acid metal salts, Lewis acids, amine complex salts, and the like. Among them, from the viewpoint of excellent curability, heat resistance, electrical properties, moisture resistance reliability, etc., triphenylphosphine for phosphorus compounds, 1,8-diazabicyclo- [5.4.0] -undecene (DBU for tertiary amines). ), 2-ethyl-4-methylimidazole is preferred for imidazole compounds, and 4-dimethylaminopyridine is preferred for pyridine compounds.

  The flame retardant is, for example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic phosphorus compounds such as phosphate amide; phosphate ester compound, phosphonic acid Compound, phosphinic acid compound, phosphine oxide compound, phosphorane compound, organic nitrogen-containing phosphorus compound, 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) ) Cyclic organic phosphorus such as -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,7-dihydrooxynaphthyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide Compound, and compound such as epoxy resin and phenol resin Organic phosphorus compounds such as reacted derivatives; nitrogen-based flame retardants such as triazine compounds, cyanuric acid compounds, isocyanuric acid compounds and phenothiazines; silicone-based flame retardants such as silicone oil, silicone rubber and silicone resin; metal hydroxides, metals Examples thereof include inorganic flame retardants such as oxides, metal carbonate compounds, metal powders, boron compounds, and low-melting glass. When using these flame retardants, it is preferable that it is the range of 0.1-20 mass% in curable resin composition.

  The said inorganic filler is mix | blended, for example when using the curable resin composition of this invention for a semiconductor sealing material use. Examples of the inorganic filler include fused silica, crystalline silica, alumina, silicon nitride, and aluminum hydroxide. Especially, since it becomes possible to mix | blend more inorganic fillers, the said fused silica is preferable. The fused silica can be used in either crushed or spherical shape, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the curable composition, a spherical one is mainly used. It is preferable. Furthermore, in order to 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 in the range of 0.5 to 95 parts by mass in 100 parts by mass of the curable resin composition.

  In addition, when using the curable resin composition of this invention for uses, such as an electrically conductive paste, electroconductive fillers, such as silver powder and copper powder, can be used.

  As described above in detail, the active ester resin of the present invention has excellent performance such as a low curing shrinkage and a low dielectric loss tangent in the cured product. In addition, the general required performance required for resin materials, such as solubility in general-purpose organic solvents and curability with epoxy resins, is sufficiently high, such as printed wiring boards, semiconductor encapsulation materials, resist materials, etc. In addition to the above electronic material applications, it can be widely used for applications such as paints, adhesives and molded products.

  When using the curable resin composition of this invention for a printed wiring board use or a buildup adhesive film use, generally it is preferable to mix | blend and use an organic solvent. Examples of the organic solvent include methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxypropanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate and the like. The type and blending amount of the organic solvent can be adjusted as appropriate according to the use environment of the curable resin composition. For example, for printed wiring board applications, methyl ethyl ketone, acetone, dimethylformamide and the like are polar solvents having a boiling point of 160 ° C. or lower. It is preferable to use it at a ratio that the nonvolatile content is 40 to 80% by mass. For build-up adhesive film applications, ketone solvents such as acetone, methyl ethyl ketone, cyclohexanone, etc., acetate solvents such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, carbitol acetate, carbitols such as cellosolve, butyl carbitol, etc. It is preferable to use a solvent, an aromatic hydrocarbon solvent such as toluene and xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like, and it is preferable to use the nonvolatile component in a proportion of 30 to 60% by mass.

  Moreover, the method of manufacturing a printed wiring board using the curable resin composition of the present invention includes, for example, impregnating a curable composition into a reinforcing base material and curing it to obtain a prepreg, and stacking this with a copper foil. The method of carrying out thermocompression bonding is mentioned. Examples of the reinforcing substrate include paper, glass cloth, glass nonwoven fabric, aramid paper, aramid cloth, glass mat, and glass roving cloth. The impregnation amount of the curable resin composition is not particularly limited, but it is usually preferable that the resin content in the prepreg is adjusted to 20 to 60% by mass.

  When using the curable resin composition of this invention for a semiconductor sealing material use, generally it is preferable to mix | blend an inorganic filler. The semiconductor sealing material can be prepared by mixing the compound using, for example, an extruder, a kneader, a roll, or the like. A method for molding a semiconductor package using the obtained semiconductor sealing material is, for example, molding the semiconductor sealing material using a casting or transfer molding machine, an injection molding machine, etc., and a temperature of 50 to 200 ° C. The method of heating for 2 to 10 hours under conditions is mentioned, By such a method, the semiconductor device which is a molding can be obtained.

  Next, the present invention will be specifically described with reference to examples and comparative examples. In the examples, “parts” and “%” are based on mass 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 Corporation
Column: Guard column “HXL-L” manufactured by Tosoh Corporation
+ Tosoh Corporation “TSK-GEL G4000HXL”
+ Tosoh Corporation “TSK-GEL G3000HXL”
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
+ "TSK-GEL G2000HXL" manufactured by Tosoh Corporation
Detector: RI (differential refractometer)
Data processing: “GPC workstation EcoSEC-WorkStation” 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-8320”.
(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, filtered through a microfilter (50 μl)

13C-NMR measurement condition apparatus: ECA-500 manufactured by JEOL Ltd.
Measurement mode: SINGLE-PULSE-DEC (1H complete decoupling method of NOE elimination)
Solvent: Deuterated chloroform pulse angle: 30 ° Pulse sample concentration: 30 wt%
Integration count: 4000 times

Measurement condition apparatus for MALDI-TOF-MS: Shimazu / AXIMA-TOF2 manufactured by KRSTOS
Ionization method: Matrix-assisted laser desorption ionization method

Example 1 Production of Active Ester Resin (1) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer was charged with 282 parts by mass of phenol, 200 parts by mass of toluene, and divinylbenzene (manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.). "DVB-810" divinylbenzene purity 81%, containing 19% ethylstyrene) 130 parts by weight and 1 part by weight of paratoluenesulfonic acid monohydrate were charged. While stirring the contents of the flask, the temperature was raised to 120 ° C., and the reaction was carried out by stirring at 120 ° C. for 1 hour. After the reaction was completed, 1 part by mass of a 49% aqueous sodium hydroxide solution was added for neutralization, 400 parts by mass of toluene was added, and the mixture was washed 3 times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 401 parts by mass of a mixture (1) containing unreacted phenol and a phenolic hydroxyl group-containing resin (B-1). The obtained mixture (1) had a hydroxyl group equivalent of 138 g / equivalent.

  A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 152 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene, and dissolved in the system while substituting with nitrogen under reduced pressure. Next, 206 parts by mass of the mixture (1) obtained above was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While adding 0.4 g of tetrabutylammonium bromide and performing a nitrogen gas purge, the inside of the reaction system was controlled to 60 ° C. or less, and 300 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and then toluene and the like were distilled off under heating and reduced pressure conditions to obtain 295 parts by mass of an active ester resin (1). The functional group equivalent of the active ester resin (1) was 202 g / equivalent, and the softening point measured based on JIS K7234 was 87 ° C. A GPC chart of the obtained active ester resin (1) is shown in FIG. The content of the ester compound (AC) in the active ester resin (1) calculated from the area ratio of the GPC chart was 19.2%, and the weight average molecular weight (Mw) was 1677.

Example 2 Production of Active Ester Resin (2) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 324 parts by mass of orthocresol, 200 parts by mass of toluene, and divinylbenzene (Nippon Steel & Sumikin Chemical Co., Ltd.). “DVB-810” manufactured by DVB-810 having a purity of 81% divinylbenzene and 19% ethyl styrene) was added in an amount of 130 parts by mass and 1 part by mass of paratoluenesulfonic acid monohydrate. While stirring the contents of the flask, the temperature was raised to 120 ° C., and the reaction was carried out by stirring at 120 ° C. for 1 hour. After the reaction was completed, 1 part by mass of a 49% aqueous sodium hydroxide solution was added for neutralization, 400 parts by mass of toluene was added, and the mixture was washed 3 times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 440 parts by mass of a mixture (2) containing unreacted orthocresol and a phenolic hydroxyl group-containing resin (B-2). The obtained mixture (2) had a hydroxyl group equivalent of 152 g / equivalent.

  A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 152 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene, and dissolved in the system while substituting with nitrogen under reduced pressure. Next, 227 parts by mass of the previously obtained mixture (2) was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While adding 0.4 g of tetrabutylammonium bromide and performing a nitrogen gas purge, the inside of the reaction system was controlled to 60 ° C. or less, and 300 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and then toluene and the like were distilled off under heating and reduced pressure to obtain 310 parts by mass of an active ester resin (2). The functional group equivalent of the active ester resin (2) was 216 g / equivalent, and the softening point measured based on JIS K7234 was 99 ° C. A GPC chart of the obtained active ester resin (2) is shown in FIG. The content of the ester compound (AC) in the active ester resin (2) calculated from the area ratio of the GPC chart was 17.4%, and the weight average molecular weight (Mw) was 1288.

Example 3 Production of Active Ester Resin (3) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 450 parts by mass of paratertiary butylphenol, 200 parts by mass of toluene, divinylbenzene (Nippon Steel & Sumitomo Metal) "DVB-810" divinylbenzene purity 81%, containing 19% ethyl styrene) 130 parts by mass and 1 part by mass of paratoluenesulfonic acid monohydrate were prepared. While stirring the contents of the flask, the temperature was raised to 120 ° C., and the reaction was carried out by stirring at 120 ° C. for 1 hour. After the reaction was completed, 1 part by mass of a 49% aqueous sodium hydroxide solution was added for neutralization, 400 parts by mass of toluene was added, and the mixture was washed 3 times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 565 parts by mass of a mixture (3) containing unreacted paratertiary butylphenol and a phenolic hydroxyl group-containing resin (B-3). The obtained mixture (3) had a hydroxyl group equivalent of 194 g / equivalent.

  A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 152 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene, and dissolved in the system while substituting with nitrogen under reduced pressure. Next, 290 parts by mass of the mixture (3) obtained above was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While adding 0.4 g of tetrabutylammonium bromide and performing a nitrogen gas purge, the inside of the reaction system was controlled to 60 ° C. or less, and 300 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and then toluene and the like were distilled off under heating and reduced pressure conditions to obtain 365 parts by mass of an active ester resin (3). The functional group equivalent of the active ester resin (3) was 258 g / equivalent, and the softening point measured based on JIS K7234 was 119 ° C. The GPC chart of the obtained active ester resin (3) is shown in FIG. The content of the ester compound (AC) in the active ester resin (3) calculated from the area ratio of the GPC chart was 20.0%, and the weight average molecular weight (Mw) was 1305.

Example 4 Production of Active Ester Resin (4) A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube and a stirrer was combined with 511 parts by mass of orthophenylphenol, 200 parts by mass of toluene, and divinylbenzene (Nippon Steel & Sumikin Chemical). "DVB-810" divinylbenzene purity 81%, containing 19% ethylstyrene) 130 parts by mass and 1 part by mass of paratoluenesulfonic acid monohydrate were charged. While stirring the contents of the flask, the temperature was raised to 120 ° C., and the reaction was carried out by stirring at 120 ° C. for 1 hour. After the reaction was completed, 1 part by mass of a 49% aqueous sodium hydroxide solution was added for neutralization, 400 parts by mass of toluene was added, and the mixture was washed 3 times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure to obtain 612 parts by mass of a mixture (4) containing unreacted orthophenylphenol and phenolic hydroxyl group-containing resin (B-4). The obtained mixture (4) had a hydroxyl group equivalent of 214 g / equivalent.

  A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 152 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene, and dissolved in the system while substituting with nitrogen under reduced pressure. Next, 320 parts by mass of the mixture (4) obtained above was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While adding 0.4 g of tetrabutylammonium bromide and performing a nitrogen gas purge, the inside of the reaction system was controlled to 60 ° C. or less, and 300 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and then toluene and the like were distilled off under heating and reduced pressure conditions to obtain 397 parts by mass of an active ester resin (4). The functional group equivalent of the active ester resin (4) was 278 g / equivalent, and the softening point measured based on JIS K7234 was 112 ° C. The GPC chart of the obtained active ester resin (4) is shown in FIG. The content of the ester compound (AC) in the active ester resin (4) calculated from the area ratio of the GPC chart was 18.2%, and the weight average molecular weight (Mw) was 1209.

Example 5 Production of Active Ester Resin (5) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 432 parts by mass of 2-naphthol, 200 parts by mass of toluene, and divinylbenzene (Nippon Steel & Sumikin Chemical). "DVB-810" divinylbenzene purity 81%, containing 19% ethylstyrene) 130 parts by mass and 1 part by mass of paratoluenesulfonic acid monohydrate were charged. While stirring the contents of the flask, the temperature was raised to 120 ° C., and the reaction was carried out by stirring at 120 ° C. for 1 hour. After the reaction was completed, 1 part by mass of a 49% aqueous sodium hydroxide solution was added for neutralization, 400 parts by mass of toluene was added, and the mixture was washed 3 times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 545 parts by mass of a mixture (5) containing unreacted 2-naphthol and a phenolic hydroxyl group-containing resin (B-5). The obtained mixture (5) had a hydroxyl equivalent of 187 g / equivalent.

  A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 152 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene, and dissolved in the system while substituting with nitrogen under reduced pressure. Next, 281 parts by mass of the previously obtained mixture (5) was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While adding 0.4 g of tetrabutylammonium bromide and performing a nitrogen gas purge, the inside of the reaction system was controlled to 60 ° C. or less, and 300 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and then toluene and the like were distilled off under heating and reduced pressure conditions to obtain 367 parts by mass of an active ester resin (5). The functional group equivalent of the active ester resin (5) was 252 g / equivalent, and the softening point measured based on JIS K7234 was 136 ° C. The GPC chart of the obtained active ester resin (5) is shown in FIG. The content of the ester compound (AC) in the active ester resin (5) calculated from the area ratio of the GPC chart was 20.9%, and the weight average molecular weight (Mw) was 1648.

Example 6 Production of Active Ester Resin (6) A flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer was charged with 404 parts by mass of 1-naphthol, 200 parts by mass of toluene, and divinylbenzene (Nippon Steel & Sumikin Chemical). "DVB-810" divinylbenzene purity 81%, containing 19% ethylstyrene) 91 parts by mass and 1 part by mass of paratoluenesulfonic acid monohydrate were charged. While stirring the contents of the flask, the temperature was raised to 120 ° C., and the reaction was carried out by stirring at 120 ° C. for 1 hour. After the reaction was completed, 1 part by mass of a 49% aqueous sodium hydroxide solution was added for neutralization, 400 parts by mass of toluene was added, and the mixture was washed 3 times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure to obtain 482 parts by mass of a mixture (6) containing unreacted 1-naphthol and a phenolic hydroxyl group-containing resin (B-6). The obtained mixture (6) had a hydroxyl equivalent of 177 g / equivalent.

  A flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer was charged with 141 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene, and dissolved in the system while substituting with nitrogen under reduced pressure. Next, 247 parts by mass of the mixture (6) obtained above was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While adding 0.4 g of tetrabutylammonium bromide and performing a nitrogen gas purge, 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 completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer reached 7, and then toluene and the like were distilled off under heating and reduced pressure conditions to obtain 320 parts by mass of an active ester resin (6). The functional group equivalent of the active ester resin (6) was 241 g / equivalent, and the softening point measured according to JIS K7234 was 130 ° C. The GPC chart of the obtained active ester resin (6) is shown in FIG. 6, the 13C-NMR is shown in FIG. 7, and the MS is shown in FIG. The content of the ester compound (AC) in the active ester resin (6) calculated from the area ratio in the GPC chart was 31.3%, and the weight average molecular weight (Mw) was 971.

Comparative Production Example 1 Production of Active Ester Resin (1 ′) Addition reaction product of dicyclopentadiene and phenol (hydroxyl equivalent 165 g / equivalent) to a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer , Softening point 85 ° C.) 165 parts by mass, 72 parts by mass of 1-naphthol, and 630 parts by mass of toluene were charged and dissolved in the system while substituting with nitrogen under reduced pressure. Next, 152 parts by mass of isophthalic acid chloride was charged, and the system was dissolved while substituting with nitrogen under reduced pressure. While performing nitrogen gas purging, the inside of the system was controlled to 60 ° C. or less, and 300 parts by mass of 20% aqueous sodium hydroxide solution was added dropwise over 3 hours. After completion of dropping, the reaction was continued for 1 hour with stirring. After completion of the reaction, the reaction mixture was allowed to stand for liquid separation, and the aqueous layer was removed. After adding water to the remaining organic layer and stirring and mixing for about 15 minutes, the mixture was allowed to stand and liquid-separated, and the aqueous layer was removed. This operation was repeated until the pH of the aqueous layer became 7, and then toluene and the like were distilled off under heating and reduced pressure conditions to obtain an active ester resin (1 ′). The functional group equivalent of the active ester resin (1 ′) was 223 g / equivalent, and the softening point measured based on JIS K7234 was 150 ° C.

Comparative Production Example 2 Production of Active Ester Resin (2 ′) Phenol novolac resin (“Phenolite TD-2131” manufactured by DIC, softening point) on a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer At 80 ° C., 104 parts by mass of hydroxyl equivalent 104) and 612 parts by mass of methyl isobutyl ketone were charged, and the system was purged with nitrogen under reduced pressure to dissolve. Next, 10.1 parts by mass of isophthalic acid chloride was charged, and the inside of the system was controlled to 60 ° C. or lower while performing nitrogen gas purge, and 21.0 parts by mass of a 20% aqueous sodium hydroxide solution was added dropwise over 1 hour. After further stirring for 1 hour, 133.5 parts by mass of benzoyl chloride was charged and the inside of the system was controlled to 60 ° C. or lower while carrying out a nitrogen gas purge, so that 189.0 parts by mass of 20% aqueous sodium hydroxide solution was reduced to 4%. It was added dropwise over time. After completion of the dropwise addition, stirring was continued for another hour. After completion of the reaction, the mixture was left to separate and the aqueous layer was removed. Water was added to the remaining organic layer, and the mixture was stirred and mixed for about 15 minutes. The mixture was allowed to stand and liquid layer was removed. This operation was repeated until the pH of the aqueous layer became 7. Thereafter, water was removed by decanter dehydration, and methyl isobutyl ketone was removed by vacuum dehydration to obtain an active ester resin (2 ′). The functional group equivalent of this active ester resin (2 ′) was 204 g / equivalent, and the softening point measured based on JIS K7234 was 92 ° C.

Examples 7 to 12 and Comparative Examples 1 and 2
Each component was mix | blended in the ratio shown in following Table 1, and curable resin composition was obtained. About the obtained curable resin composition, the cure shrinkage rate and the dielectric constant and dielectric loss tangent value in the cured product were measured in the following manner. The results are shown in Table 1.

Measurement of curing shrinkage Curing was performed using a transfer molding machine (“KTS-15-1.5C” manufactured by Kotaki Seiki Co., Ltd.) under conditions of a mold temperature of 154 ° C., a molding pressure of 9.8 MPa, and a curing time of 600 seconds. The resin composition was injection molded to obtain a molded product having a length of 110 mm, a width of 12.7 mm, and a thickness of 1.6 mm. Next, the obtained molded product was cured at 175 ° C. for 5 hours, and then allowed to stand at room temperature (25 ° C.) for 24 hours or more to obtain a test piece. The vertical dimension at room temperature of the test piece and the internal dimension in the vertical direction at 154 ° C. of the mold were measured, and the cure shrinkage rate was calculated by the following formula.
Curing shrinkage rate (%) = {(internal dimension at 154 ° C. of mold) − (longitudinal dimension of test piece at room temperature)} / (internal dimension of mold at 154 ° C.) × 100 (%)

Measurement of dielectric constant and dielectric loss tangent A test piece was prepared in the same manner as the measurement of curing shrinkage. Dielectric constant / dielectric loss tangent at 1 GHz using a cavity resonance method for a test piece stored for 24 hours in a room at 23 ° C. and 50% humidity after heating and vacuum drying using a network analyzer “E8362C” manufactured by Agilent Technologies, Inc. Was measured.

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

Claims (6)

Compound (A) having one phenolic hydroxyl group in the molecular structure, phenolic hydroxyl group-containing resin (B) using phenolic hydroxyl group-containing compound (b1) and divinyl compound (b2) as essential reaction materials, and aromatic An active ester resin comprising a polycarboxylic acid or an acid halide (C) thereof as an essential reaction raw material. The phenolic hydroxyl group-containing resin (B) and the phenolic hydroxyl group-containing compound (b1) are represented by the following structural formula (2).

[Wherein X is a structural moiety represented by any of the following structural formulas (X-1) to (X-4).

(In the formula, each R ¹ is independently an aliphatic hydrocarbon group, an alkoxy group, a halogen atom, an aryl group, or an aralkyl group, and i is an integer of 0 or 1 to 4. Y is the number of carbon atoms. Any one of an alkylene group of 1-4, an oxygen atom, a sulfur atom, and a carbonyl group, j is an integer of 1-4)
The active ester resin according to claim 1, which has a molecular structure knotted at a structural site (α) represented by: A curable resin composition comprising the active ester resin according to claim 1 or 2 and a curing agent. A cured product of the curable resin composition according to claim 3. A printed wiring board using the curable composition according to claim 3. A semiconductor sealing material comprising the curable composition according to claim 3.

Images