JP6332719B1 - Active ester resin and its cured product - Google Patents

Abstract

To provide an active ester resin having a low curing shrinkage rate, excellent dielectric properties in a cured product, and high solvent solubility, a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor sealing material . A novolak resin (A) having a naphthol compound (a) as a reaction raw material and containing a component having 3 or more nuclei as an essential component, a compound having one phenolic hydroxyl group in the molecule ( An active ester resin comprising B) and an aromatic polycarboxylic acid or an acid halide (C) thereof as an essential reaction raw material.

Description

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

  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. In addition, as an industrial utility value, handling properties such as excellent solubility in various general-purpose solvents are also important performances.

  As a resin material having a relatively low dielectric constant and dielectric loss tangent in a cured product, a technique using an active ester resin obtained by esterifying dicyclopentadiene phenol resin and α-naphthol with phthalic acid chloride as a curing agent for an epoxy resin. It 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

  Therefore, the problem to be solved by the present invention is an active ester resin having a low cure shrinkage ratio, excellent dielectric properties in a cured product, and high solvent solubility, a curable resin composition containing the same, a cured product thereof, An object of the present invention is to provide a printed wiring board and a semiconductor sealing material.

  As a result of intensive studies to solve the above problems, the present inventors have found that an active ester resin using a naphthol compound as a reaction raw material and a novolac resin containing a component having 3 or more nuclei as an essential reaction raw material has a cure shrinkage rate. The present invention has been completed by finding that it is low, has excellent dielectric properties in a cured product, and has high solvent solubility.

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

  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, an active ester resin having a low cure shrinkage ratio, excellent dielectric properties and the like in a cured product and high solvent solubility, a curable resin composition containing the same, a cured product thereof, a printed wiring board, and a semiconductor encapsulation A stop material can be provided.

1 is a GPC chart of the active ester resin (1) obtained in Example 1. FIG. FIG. 2 is a 13C-NMR chart of the active ester resin (1) obtained in Example 1. FIG. 3 is an MS spectrum of the active ester resin (1) obtained in Example 1. FIG. 4 is a GPC chart of the active ester resin (2) obtained in Example 2. FIG. 5 is a GPC chart 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 a novolak type resin using a naphthol compound (a) as a reaction raw material, a novolak type resin (A) containing a component having 3 or more nuclei as an essential component, and phenol in the molecule. A compound (B) having one ionic hydroxyl group and an aromatic polycarboxylic acid or its acid halide (C) are used as essential reaction raw materials.

  Regarding the novolak resin (A), the naphthol compound (a) may be any compound as long as it has one hydroxyl group on the naphthalene ring, and its specific structure, presence or absence of other substituents, etc. are particularly limited. Not. In the present invention, one type of naphthol compound (a) may be used alone, or two or more types may be used in combination. Specific examples of the naphthol compound (a) include 1-naphthol, 2-naphthol, and compounds having one or more substituents on the aromatic nucleus. Substituents on the aromatic nucleus are, for example, methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl Group, aliphatic hydrocarbon group such as dodecyl 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 An aryl group such as phenylmethyl group, phenylethyl group, naphthylmethyl group, naphthylethyl group, and the like. Among these, 1-naphthol or 2-naphthol is preferable because it becomes an active ester resin having a low curing shrinkage and excellent dielectric properties in the cured product.

  The novolak type resin (A) uses the naphthol compound (a) as a reaction raw material, but other phenolic hydroxyl group-containing compounds (a ′) may be used in combination depending on the desired resin performance. good. Examples of the other phenolic hydroxyl group-containing compound (a ′) include phenol, anthracenol, and compounds having one or more substituents on the aromatic nucleus thereof. Substituents on the aromatic nucleus are, for example, methyl, ethyl, vinyl, propyl, butyl, pentyl, hexyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl Group, aliphatic hydrocarbon group such as dodecyl 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 An aryl group such as phenylmethyl group, phenylethyl group, naphthylmethyl group, naphthylethyl group, and the like.

  When the other phenolic hydroxyl group-containing compound (a ′) is used in combination with the naphthol compound (a), the present invention has a low curing shrinkage ratio, excellent dielectric properties in the cured product, and high solvent solubility. Therefore, the ratio of the naphthol compound (a) is preferably 50 mol% or more, more preferably 80 mol% or more, and more preferably 90 mol% or more. It is particularly preferred.

  The novolac resin (A) contains a component having 3 or more nuclei as an essential component. The number of nuclei is the number of structural sites derived from the naphthol compound (a) or the other phenolic hydroxyl group-containing compound (a ′) contained in one molecule. The component can be represented by the following general formula (1), and the component having 4 nuclei can be represented by the following general formula (2-1) or (2-2).

［式中Ａｒは前記ナフトール化合物（ａ）或いは前記その他のフェノール性水酸基含有化合物（ａ’）由来の構造部位である。］

[In the formula, Ar is a structural site derived from the naphthol compound (a) or the other phenolic hydroxyl group-containing compound (a ′). ]

［式中Ａｒは前記ナフトール化合物（ａ）或いは前記その他のフェノール性水酸基含有化合物（ａ’）由来の構造部位である。］

[In the formula, Ar is a structural site derived from the naphthol compound (a) or the other phenolic hydroxyl group-containing compound (a ′). ]

  For the component having 3 or 4 nuclei, Ar in the general formulas (1), (2-1), and (2-2) is a structural site derived from the naphthol compound (a) or the other phenol. Any of the structural sites derived from the functional hydroxyl group-containing compound (a ′) may be used, but since the curing shrinkage rate is low and the effect of excellent dielectric properties in the cured product becomes more remarkable, the general formula (1), It is more preferable that all Ar in (2-1) and (2-2) are structural sites derived from the naphthol compound (a).

  Since the novolac resin (A) has a low cure shrinkage and the effect of excellent dielectric properties in the cured product becomes more prominent, it contains a component having 3 or 4 nuclei in the range of 1 to 50%. It is preferable to contain, and it is more preferable to contain in 5 to 30% of range. The content of the component having 3 nuclei is preferably in the range of 1 to 30%, more preferably in the range of 5 to 20%. The content of the component having 4 nuclei is preferably in the range of 1 to 15%, and more preferably in the range of 1 to 10%.

  Furthermore, the novolac resin (A) more preferably contains a component having 2 nuclei since the curing shrinkage of the resulting active ester resin can be further reduced. The content of the component having 2 nuclei is the ratio of the content (N2) of the component having 2 nuclei to the content (N3) of the component having 3 nuclei [(N3) / (N2)] is preferably in the range of 0.10 to 2.00, more preferably in the range of 0.20 to 1.00.

  In the present invention, the content of each component in the novolac resin (A) 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 method for producing the novolac resin (A) is not particularly limited. For example, the naphthol compound (a) and the other phenolic hydroxyl group-containing compound (a And a method in which formaldehyde is reacted with 40-200 ° C. in the presence of no catalyst or an acid catalyst or an alkali catalyst. After completion of the reaction, an excessive amount of the compound (a) or the compound (a ′) may be distilled off as desired. Further, the unreacted compound (a) or compound (a ′) in the reaction mixture may be used as it is as the compound (B) having one phenolic hydroxyl group in the molecule described later.

  The formaldehyde may be used as a formalin solution or as paraformaldehyde. Since the amount of formaldehyde charged is easy to control the reaction, the amount of formaldehyde is in the range of 0.01 to 0.9 mol with respect to a total of 1 mol of the compound (a) and the compound (a ′). Is preferred.

  Examples of the acid catalyst include inorganic acids such as hydrochloric acid, sulfuric acid, and phosphoric acid, organic acids such as methanesulfonic acid, paratoluenesulfonic acid, and oxalic acid, and Lewis acids such as boron trifluoride, anhydrous aluminum chloride, and zinc chloride. Is mentioned. These may be used alone or in combination of two or more. It is preferable that the usage-amount of these acid catalysts is 0.1-5 mass% with respect to the total mass of a reaction raw material.

  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. Moreover, you may use as about 3.0-50% aqueous solution. Among these, sodium hydroxide or potassium hydroxide having high catalytic ability is preferable. It is preferable that the usage-amount of these alkali catalysts is the range of 0.1-20 mass% with respect to the total mass of a reaction raw material.

  You may perform the synthesis reaction of the said novolak-type resin (A) in an organic solvent as needed. The organic solvent used here is not particularly limited as long as it is an organic solvent that can be used under the above temperature conditions. Specific examples include methyl cellosolve, ethyl cellosolve, toluene, xylene, and methyl isobutyl ketone. . When using these organic solvents, it is preferable to use in the range of 10-500 mass% with respect to the total mass of a reaction raw material.

  In the synthesis reaction of the novolac resin (A), various antioxidants and reducing agents may be used for the purpose of suppressing the coloring of the resulting novolac resin (A). Examples of the antioxidant include hindered phenol compounds such as 2,6-dialkylphenol derivatives, divalent sulfur compounds, and phosphite compounds containing a trivalent phosphorus atom. Examples of the reducing agent include hypophosphorous acid, phosphorous acid, thiosulfuric acid, sulfurous acid, hydrosulfite, salts thereof, and zinc.

  After completion of the reaction, the target novolac resin (A) can be obtained by neutralizing the reaction mixture or washing with water, and then distilling off unreacted reaction raw materials and by-products.

  The hydroxyl group equivalent of the novolac resin (A) is preferably in the range of 110 to 250 g / equivalent because it is an active ester resin that has high solvent solubility and can be easily used for various applications. Moreover, it is preferable that the softening point of the said novolak-type resin (A) is the range of 40-130 degreeC.

  The compound (B) having one phenolic hydroxyl group in the molecule 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 this invention, the compound (B) which has one phenolic hydroxyl group in molecular structure may be used individually by 1 type, and may be used in combination of 2 or more types. The compound (B) 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. A hydrogen group; an alkoxy group such as a methoxy group, an ethoxy group, a propyloxy 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 anthryl group, and an aromatic nucleus thereof. 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, 1-naphthol or 2-naphthol is preferable because it becomes an active ester resin having a low curing shrinkage and excellent dielectric properties in the cured product.

  The aromatic polycarboxylic acid or its acid halide (C) reacts with the phenolic hydroxyl group of the novolak resin (A) and the compound (B) having one phenolic hydroxyl group in the molecule to form an ester bond. The specific structure is not particularly limited as long as it is an aromatic compound capable of forming, 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 reaction of the novolac resin (A), the compound (B) having one phenolic hydroxyl group in the molecule, and the aromatic polycarboxylic acid or acid halide (C) thereof is carried out, for example, in the presence of an alkali catalyst. , And can be carried out by heating and stirring under a temperature condition of about 40 to 65 ° C. 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 novolac resin (A), the compound (B) having one phenolic hydroxyl group in the molecule, and the aromatic polycarboxylic acid or its acid halide (C) depends on the desired molecular design. Can be changed as appropriate. Among them, since it becomes an active ester resin having high solvent solubility and easy to use for various purposes, the number of moles of hydroxyl group (A _OH ) of the novolac resin (A) and the phenolic hydroxyl group in the molecule are one. It is preferable that the ratio [(A _OH ) / (B _OH )] to the number of moles of hydroxyl groups (B _OH ) of the compound (B) having a ratio of 10/90 to 75/25 is 20/80 It is more preferable that the ratio is ˜50 / 50. In addition, the total number of carboxyl groups or acid halide groups of the aromatic polycarboxylic acid or acid halide (C) thereof is 1 mol in total and the number of moles of hydroxyl groups of the novolak resin (A) and phenolic in the molecule. It is preferable that the total of the compound (B) having one hydroxyl group and the number of moles of the hydroxyl group is 0.9 to 1.1 mol.

  The active ester resin of the present invention contains an ester compound (BC) of the compound (B) having one phenolic hydroxyl group in the molecule and the aromatic polycarboxylic acid or its acid halide (C). May be. The ester compound (BC) includes, for example, the novolac resin (A), the compound (B) having one phenolic hydroxyl group in the molecule, and the aromatic polycarboxylic acid or acid halide (C) thereof. By preparing the reaction ratio, it can be produced as one component of an active ester resin.

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

（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、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 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. Is an integer of 0 or 1-3.)

  When active ester resin contains the said ester compound (BC), it is preferable that the content is less than 40% of active ester resin, and it is more preferable that it is the range of 0.5-35%.

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

  The functional group equivalent of the active ester resin of the present invention is preferably in the range of 150 to 350 g / equivalent because it becomes an active ester resin having a low cure shrinkage 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. The functional group equivalent of the active ester resin is a value calculated from the charged amount of the reaction raw material.

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

  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. . The weight average molecular weight (Mw) of the active ester resin is a value calculated from the area ratio of the GPC chart measured under the same conditions as the component analysis of the novolac resin (A).

  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 dimer of acid 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 active ester resin, the epoxy resin, and the curing agent composition for other epoxy resins of the present invention are blended in a proportion of 1 mol in total for the epoxy groups in the epoxy resin. It is preferable that it is a ratio from which the total of the functional group in an agent will be 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 is characterized by high heat resistance and moisture absorption resistance in a cured product and excellent dielectric properties. 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 encapsulating material containing the active ester resin of the present invention, a curing agent, an inorganic filler, and other optional components may be prepared by mixing the compound using, for example, an extruder, a kneader, or a roll. it can. 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 equipped with 1-naphthol 288 parts by mass, 2-naphthol 288 parts by mass, toluene 576 parts by mass. , 81 parts by mass of 37% formalin aqueous solution and 10 parts by mass of 49% sodium hydroxide aqueous solution were charged. While stirring the contents of the flask, the temperature was raised to 75 ° C., and the mixture was stirred at 75 ° C. for 1 hour for reaction. After completion of the reaction, the mixture was neutralized by adding 13 parts by mass of 35% hydrochloric acid, and then washed three times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 568 parts by mass of a mixture (1) containing unreacted naphthol and novolac resin (A-1). The obtained mixture (1) had a hydroxyl equivalent of 147 g / equivalent. The content of the component having 2 nuclei calculated from the area ratio of the GPC chart of the mixture (1) is 32.6%, the content of the component having 3 nuclei is 12.2%, The content of the component having the number of 4 is 3.1%, the ratio of the content of the component having the number of nuclei of 2 (N2) and the content of the component having the number of nuclei of 3 (N3) [(N3 ) / (N2)] was 0.37.

  141 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, and the system was dissolved 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 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 285 parts by mass of an active ester resin (1). The functional group equivalent of the active ester resin (1) was 212 g / equivalent, and the softening point measured based on JIS K7234 was 124 ° C. A GPC chart of the obtained active ester resin (1) is shown in FIG. 1, 13C-NMR in FIG. 2, and MS in FIG. The content of the ester compound (BC) in the active ester resin (1) calculated from the area ratio of the GPC chart was 28.7%, and the weight average molecular weight (Mw) was 1219.

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 432 parts by mass of 1-naphthol, 144 parts by mass of 2-naphthol, and 576 parts by mass of toluene. , 81 parts by mass of 37% formalin aqueous solution and 10 parts by mass of 49% sodium hydroxide aqueous solution were charged. While stirring the contents of the flask, the temperature was raised to 75 ° C., and the mixture was stirred at 75 ° C. for 1 hour for reaction. After completion of the reaction, the mixture was neutralized by adding 13 parts by mass of 35% hydrochloric acid, and then washed three 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 (2) containing unreacted naphthol and a novolac resin (A-2). The obtained mixture (2) had a hydroxyl equivalent of 147 g / equivalent. The content of the component having 2 nuclei calculated from the area ratio of the GPC chart of the mixture (2) is 19.7%, the content of the component having 3 nuclei is 14.1%, The content of the component having the number 4 is 6.5%, the ratio of the content (N2) of the component having the number of nuclei 2 to the content (N3) of the component having the number of nuclei 3 [(N3 ) / (N2)] was 0.72.

  141 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, and the system was dissolved while substituting with nitrogen under reduced pressure. Next, 206 parts by mass of the mixture (2) obtained above was charged, and the system was dissolved while substituting under reduced pressure nitrogen. 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 became 7, and then toluene and the like were distilled off under heating and reduced pressure conditions to obtain 287 parts by mass of an active ester resin (2). The functional group equivalent of the active ester resin (2) was 212 g / equivalent, and the softening point measured according to JIS K7234 was 131 ° C. The GPC chart of the obtained active ester resin (2) is shown in FIG. The content of the ester compound (BC) in the active ester resin (2) calculated from 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) In a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer, 576 parts by mass of 1-naphthol, 81 parts by mass of water, 81 parts by mass of 37% formalin aqueous solution Prepared the department. While stirring the contents of the flask, the temperature was raised to 95 ° C., and the reaction was carried out by stirring at 95 ° C. for 2 hours. After completion of the reaction, water and the like were distilled off under heating and reduced pressure conditions to obtain 570 parts by mass of a mixture (3) containing unreacted naphthol and novolac resin (A-3). The obtained mixture (3) had a hydroxyl equivalent of 147 g / equivalent. The content of the component having 2 nuclei calculated from the area ratio of the GPC chart of the mixture (3) is 33.4%, the content of the component having 3 nuclei is 11.1%, The content of the component having the number of 4 is 3.6%, the ratio of the content of the component having the number of nuclei of 2 (N2) and the content of the component having the number of nuclei of 3 (N3) [(N3 ) / (N2)] was 0.33.

  141 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, and the system was dissolved while substituting with nitrogen under reduced pressure. Next, 206 parts by mass of the mixture (3) obtained above was charged, and the system was dissolved while substituting 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 282 parts by mass of an active ester resin (3). The functional group equivalent of the active ester resin (3) was 212 g / equivalent, and the softening point measured based on JIS K7234 was 131 ° C. FIG. 5 shows a GPC chart of the obtained active ester resin (3). The content of the ester compound (BC) in the active ester resin (3) calculated from the area ratio of the GPC chart was 27.5%, and the weight average molecular weight (Mw) was 1285.

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 purge, the inside of the system was controlled to 60 ° C. or lower, and 210 g 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 ′) 2-Naphthol 576 parts by mass, toluene 576 parts by mass, 37% formalin aqueous solution in a flask equipped with a thermometer, dropping funnel, condenser, fractionator, and stirrer 81 parts by mass and 10 parts by mass of a 49% aqueous sodium hydroxide solution were charged. While stirring the contents of the flask, the temperature was raised to 75 ° C., and the mixture was stirred at 75 ° C. for 1 hour for reaction. After completion of the reaction, the mixture was neutralized by adding 13 parts by mass of 35% hydrochloric acid, and then washed three times with 200 parts by mass of water. Toluene and the like were distilled off under heating and reduced pressure conditions to obtain 520 parts by mass of a mixture (1 ′) containing unreacted naphthol and a novolac resin (A′-1). The hydroxyl group equivalent of the mixture (1 ′) was 147 g / equivalent. The content of the component having 2 nuclei calculated from the area ratio of the GPC chart of the mixture (1 ′) is 40.9%, the content of the component having 3 nuclei is 0%, the number of nuclei Is the ratio of the content of the component having the number of nuclei (N2) and the content of the component having the number of nuclei of 3 (N3) [(N3) / ( N2)] was 0.00.

  141 parts by mass of isophthalic acid chloride and 1000 parts by mass of toluene were charged into a flask equipped with a thermometer, a dropping funnel, a condenser tube, a fractionating tube, and a stirrer, and the system was dissolved 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 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 became 7, and then toluene and the like were distilled off under heating and reduced pressure conditions to obtain an active ester resin (2 '). The functional group equivalent of this active ester resin (2 ') was 212 g / equivalent from the charging 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 are sealed in a sample bottle and heated to 80 ° C. And dissolved. Then, it cooled to 25 degreeC and evaluated whether the crystal | crystallization precipitated. It was determined as A when no crystals were precipitated and as B when crystals were precipitated. The results are shown in Table 1.

Examples 4 to 6 and Comparative Examples 1 and 2
Each component was mix | blended in the ratio shown in following Table 2, and curable resin composition (1) was obtained. About the obtained curable resin composition (1), the cure shrinkage rate was measured in the following way. The results are shown in Table 2. In Comparative Example 2 using the active ester resin (2 ′), since the crystallinity was high, a test piece could not be prepared and an evaluation test could not be performed.

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 conductive resin composition (1) 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 (%)

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

Examples 7 to 9 and Comparative Examples 3 and 4
Each component was mix | blended in the ratio shown in following Table 3, and curable resin composition (2) was obtained. About the obtained curable resin composition (2), the dielectric loss tangent value in hardened | cured material was measured in the following way. The results are shown in Table 3. In Comparative Example 2 using the active ester resin (2 ′), since the crystallinity was high, a test piece could not be prepared and an evaluation test could not be performed.

Measurement of dielectric loss tangent The curable resin composition (2) was poured into a mold using a press machine and molded at a temperature of 175 ° C. for 10 minutes. The molded product was taken out from the mold and cured at a temperature of 175 ° C. for 5 hours. The molded product after curing was cut into a size of 1 mm × 100 mm × 1.6 mm and used as a test piece. Using a network analyzer “E8362C” manufactured by Agilent Technologies, the dielectric loss tangent at 1 GHz of a test piece stored in a room at 23 ° C. and a humidity of 50% for 24 hours was measured by a cavity resonance method after heating and vacuum drying.

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

Claims (10)

A novolak resin (A) having a naphthol compound (a) as a reaction raw material and containing a component having 3 or more nuclei as an essential component, a compound having one phenolic hydroxyl group in the molecule ( B), and aromatic polycarboxylic acid or its acid halide (C) as an essential reaction raw material, the number of moles of hydroxyl group (AOH) of the novolac resin (A) and a phenolic hydroxyl group in the molecule An active ester resin characterized in that the ratio [(AOH) / (BOH)] with respect to the number of moles of hydroxyl groups (BOH) of one compound (B) is 10/90 to 75/25 . The active ester resin according to claim 1, wherein the novolac resin (A) contains a component having 3 or 4 nuclei in an amount of 1 to 50%. The active ester resin according to claim 1, wherein the naphthol compound (a) and the compound (B) having one phenolic hydroxyl group in the molecule are the same compound. The total number of carboxyl groups or acid halide groups of the aromatic polycarboxylic acid or acid halide thereof (C) is 1 mol, and the number of moles of hydroxyl groups of the novolac resin (A) and phenolic hydroxyl groups in the molecule. 2. The active ester resin according to claim 1, wherein the total amount of the compound (B) having one compound and the number of moles of hydroxyl groups is 0.9 to 1.1 mol. The active ester resin according to claim 1, comprising an ester compound (BC) of the compound (B) having one phenolic hydroxyl group in the molecule and the aromatic polycarboxylic acid or its acid halide (C). The active ester resin according to claim 5, wherein the content of the ester compound (BC) is in the range of 0.5 to 35%. A curable resin composition comprising the active ester resin according to any one of claims 1 to 6 and a curing agent. A cured product of the curable resin composition according to claim 7 . A printed wiring board using the curable resin composition according to claim 7 . The semiconductor sealing material using the curable resin composition of Claim 7 .

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