JP6254475B2 - Epoxy resin curing agent, production method, composition, cured product and use thereof - Google Patents

Description

  The present invention relates to an epoxy resin curing agent, a composition using the same, a cured product, and use thereof. More specifically, the present invention relates to an epoxy resin curing agent using an aryloxysilane oligomer, a composition using the same, a cured product, and use thereof.

  In accordance with recent performance improvements such as higher functionality and higher density of information communication equipment, printed wiring boards are also required to have performance adapted to them. Peripheral materials such as copper-clad laminates and interlayer insulation films are used as insulating materials for forming printed wiring boards, but epoxy materials are widely used from the viewpoints of price and adhesion. In particular, in recent years, multilayered wiring boards have been developed in accordance with the reduction in thickness, size, and performance of electronic devices.

  In recent years, with the trend toward thinning, higher elastic modulus is required from the viewpoint of low warpage. On the other hand, from the viewpoint of heat generation of devices due to high integration of circuits and use in high temperature environments, The demand for high heat resistance is also increasing. In such a case, it is common to design to increase the glass transition temperature of the material.

  In recent years, there has been an increasing demand for materials that achieve low dielectric loss from the viewpoint of high-speed transmission. When a conventional curing agent having active protons such as phenols is used, a cured product having an alcoholic hydroxyl group is obtained. However, since this hydroxyl group causes dielectric loss, an approach for reducing the hydroxyl group has been attempted. For example, an approach using a curing agent obtained by protecting a polyphenol with an acyl group has been proposed. (Patent Documents 1 to 5)

JP-A-7-53675 JP-A-8-208807 JP-A-10-168283 JP-A-2005-145911 WO2013 / 081081

  Although silyl-protected oligomers are easy to cure, there are limitations to the design that increases the glass transition temperature. Specifically, low transmission loss can be realized by using an oligomeric reaction product of a bifunctional phenol and a bifunctional silane as a curing agent, but if a trifunctional raw material is used in combination to provide heat resistance, the reaction product Since it becomes easy to gel, trifunctional raw materials cannot be used together at a high use ratio, and there is a limit to improvement in heat resistance.

  As a result of extensive research on further improvement of dielectric properties and heat resistance required for the above materials and their compatibility, the present inventors have found that aryloxysilane oligomers derived from specific bifunctional phenols and bifunctional silanes are used. It has been found that the curing agent to be used exhibits characteristics superior to those of conventional curing agents, and has reached the present invention. Specifically, it exhibits a low dielectric constant, a low dielectric loss tangent, and a high glass transition temperature, and these characteristics are extremely useful as an interlayer insulating material including a semiconductor sealing material.

The present invention is represented by the following general formula (1), 2 has a structure derived from the bifunctional phenol compound, equivalent to a hydroxyl group and aryloxy silyl group and reactive functional groups in the range of 200 to 400 g / eq, the molecular weight of the difunctional phenol compound is in the range of 250 to 400, to provide an epoxy resin curing agent consisting of aryloxyalkyl oligomer.

(In the formula, R ¹ is the same or different hydrocarbon group having 1 to 12 carbon atoms, Ar is a bifunctional phenol compound residue, and n is an integer of 1 to 20.)

  The epoxy resin curing agent in which Ar in the general formula (1) is the following general formula (2) or the following general formula (3) is a preferred embodiment of the present invention.

(In the formula, Ar ¹ is the same or different alkyl group having 1 to 4 carbon atoms, methoxy group, benzene ring to which 1 to 4 fluorine atoms may be bonded, Ar ² is the same or different alkyl group having 1 to 4 carbon atoms, respectively. Group, methoxy group, benzene ring to which 1 to 3 fluorine atoms may be bonded, X ¹ is a divalent carbon constituting a direct bond or a 5- to 7-membered ring hydrocarbon having 5 to 15 carbon atoms and optionally having a substituent. Atoms and X ² are the same or different direct bonds, divalent carbon atoms constituting an hydrocarbon having 1 to 15 carbon atoms, or oxygen atoms.)

  The epoxy resin curing agent in which the bifunctional phenol compound represented by the general formula (1) has a structure of any one of the following general formula (4), general formula (5), and general formula (6) This is a preferred embodiment.

(In the formula, R ² , R ³ , R ⁴ and R ⁵ are methyl groups, R ⁶ and R ⁷ are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, phenyl groups and naphthyl groups, and a, b , C and d are 0 to 4, e is 0 to 10, and f and g are 0 to 3.)

  The present invention also provides an epoxy resin curing agent in which the general formula (1) is synthesized by condensing a dialkoxysilane compound represented by the following general formula (7) and a bifunctional phenol represented by the general formula (8). Provide a method.

(Wherein R ¹ and Ar are the same as in formula (1), and R ⁹ is the same or different alkyl group having 1 to 4 carbon atoms.)

  Moreover, this invention provides the epoxy resin composition containing an above described epoxy resin hardening | curing agent and an epoxy resin.

  An epoxy resin composition in which the epoxy resin composition further contains a curing accelerator is a preferred embodiment of the present invention.

  An epoxy resin composition in which the epoxy resin composition further contains an inorganic filler is a preferred embodiment of the present invention.

Moreover, this invention provides the epoxy resin hardened | cured material formed by thermosetting the said epoxy resin composition.
Furthermore, this invention provides the interlayer insulation material created with the said epoxy resin composition.

  The present invention provides an epoxy resin curing agent comprising an aryloxysilane oligomer having both excellent dielectric properties and heat resistance, and a method for producing the same. The present invention also provides an epoxy resin curing agent that satisfies a low dielectric constant, a low dielectric loss tangent, and a high glass transition temperature, a composition using the same, and a cured product thereof.

2 is an NMR chart of the phenoxysilane oligomer obtained in Example 1. 3 is an NMR chart of the phenoxysilane oligomer obtained in Example 2. 3 is an NMR chart of the phenoxysilane oligomer obtained in Example 3.

The present invention has a structure derived from bifunctional phenol compound, reactive functional group equivalent (hydroxyl group and aryloxy silyl group reactive functional group) is in the range of 200 to 400 g / eq, molecular weight of the difunctional phenol compound There is a range of 250 to 400, consisting of aryloxy silane oligomer, to provide an epoxy resin curing agent represented by the general formula (1).

The epoxy resin curing agent used in the present invention contains an aryloxysilane oligomer having the basic skeleton of the general formula (1) in a proportion of 50 to 100 wt%, and R ^{1 in} the formula is the same or different. And a hydrocarbon group having 1 to 12 carbon atoms such as methyl, ethyl, isopropyl, n-propyl, isobutyl, n-butyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexyl, benzyl Substituted or unsubstituted alkyl groups such as vinyl, phenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-methylphenyl, 2-, 3- or 4-ethylphenyl, 2-, 3- or 4-isopropylphenyl, 2-, 3- or 4-isobutylphenyl, 2-, 3- or 4-tert-butylphenyl Mention may be made of substituted or unsubstituted aryl groups such as phenyl, 2-, 3- or 4-phenylphenyl, α- or β-naphthyl. Although the curing rate and the dielectric properties of the cured product can be adjusted by changing the type of R ¹ , it is preferable that R ¹ is a methyl group or a phenyl group in view of the availability of raw materials.

  The aryloxysilane oligomer can be synthesized by a reaction between a bifunctional phenol and a dialkoxysilane according to Japanese Patent Application Laid-Open No. 2005-145911 (Patent Document 4). Alcohols are produced as a by-product in the reaction, but alkoxysilanes that produce alcohol as a by-product from the viewpoint of synthesis, such as diethoxydimethylsilane, dipropoxydimethylsilane, dibutoxydimethylsilane, dimethoxymethyl Examples include phenylsilane and dimethoxydiphenylsilane. In the silylation of polyhydric phenols with dialkoxysilanes, the alkoxysilyl group of dialkoxysilanes is 0.5 to 1.5 equivalents, particularly 0.7 to 1 with respect to 1 equivalent of hydroxyl groups of the polyhydric phenols. From the viewpoint of characteristics, it is preferable to perform silylation at a raw material ratio of 0.0 equivalent.

  In the general formula (1), Ar is a bifunctional phenol compound having a molecular weight of 250 to 400 which may have a substituent, and is represented by the following general formula (2) or the following general formula (3). It is what is done.

In the above formula, Ar ¹ is the same or different alkyl group having 1 to 4 carbon atoms, methoxy group, benzene ring to which 1 to 4 fluorine atoms may be bonded, Ar ² is the same or different alkyl group having 1 to 4 carbon atoms. Group, methoxy group, benzene ring to which 1 to 3 fluorine atoms may be bonded, X ¹ is a divalent carbon constituting a direct bond or a 5- to 7-membered ring hydrocarbon having 5 to 15 carbon atoms and optionally having a substituent. Atoms and X ² are the same or different direct bonds, divalent carbon atoms constituting an hydrocarbon having 1 to 15 carbon atoms, or oxygen atoms. More specifically, bisphenol TMC, bisphenol Z, bisphenol fluorenes, dihydroxyxanthenes and the like can be exemplified. Among these, from the viewpoint of achieving both excellent heat resistance and dielectric properties, bisphenol fluorenes represented by the following general formula (4), bisphenols having an alicyclic structure represented by the following general formula (5), It is more preferable to use dihydroxyxanthenes represented by the formula (6).

(In the formula, R ² , R ³ , R ⁴ and R ⁵ are methyl groups, R ⁶ and R ⁷ are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, phenyl groups and naphthyl groups, and a, b , C and d are 0 to 4, e is 0 to 10, and f and g are 0 to 3.)

  In the general formula (1) of the aryloxysilane oligomer, the value of n is calculated by measuring the general formula (1) by proton NMR and determining the protection rate (reaction rate) of the silane raw material against the phenolic hydroxyl group. be able to. The value of n is an integer of 1 to 20, and is generally obtained as a mixture having different values of n based on the preparation method. In such a mixture, if the average value of n is too large, the melt viscosity becomes too high, so that the processability of the epoxy resin composition is impaired, and conversely, if it is too small, good dielectric properties are difficult to obtain. Accordingly, a suitable average value of n depends on the type of raw material used and the mixing ratio with other kinds of curing agents, but may be in the range of 1-20, preferably 3-15, more preferably 5-5. A range of 10 is desirable.

  Silylation of a bifunctional phenol compound with a dialkoxysilane compound is carried out by at least part of the hydroxyl group of the bifunctional phenol compound represented by the general formula (8) by the disiloxy group of the dialkoxysilane compound represented by the general formula (7). However, in order to sufficiently exhibit excellent properties as an epoxy resin curing agent, it is desirable that most hydroxyl groups are substituted with disiloxy groups. Therefore, the dialkoxysilane compound is used in an amount of 0.2 to 1.5 equivalents, preferably 0.6 to 1.0 equivalents, based on 1 equivalent of hydroxyl group in the bifunctional phenols used as a raw material. Good. Even when the reaction conditions are such that the amount of the bifunctional phenol compound used is excessive and the unreacted bifunctional phenol compound remains, the unreacted bifunctional alcohol-containing aryloxysilane oligomer as the reaction mixture remains as it is. It can also be used as an epoxy resin curing agent.

  The reaction between the dialkoxysilane compound and the bifunctional phenol compound is carried out in the presence of a catalyst. The catalyst is preferably one that is highly active with a small amount of addition, or that is easily distilled off from the reaction product at high temperature or under reduced pressure. Specifically, tertiary amines such as N, N′-dimethylbenzylamine, 1,4-diazabicyclo [2.2.2] octane, 1,8-diazabicyclo [5.4.0] undecene-7, Carboxylic acids such as propionic acid, butyric acid, isobutyric acid, valeric acid, isovaleric acid, pivalic acid, and succinic acid, tetraethyl orthotitanate, tetrapropyl orthotitanate, tetraisopropyl orthotitanate, tetrabutyl orthotitanate, tetra orthotitanate A metal alkoxide such as isobutyl is used. The amount of the catalyst used varies depending on the type of catalyst used. For example, the amount is 0.0005 to 1.0 mol, preferably 0.001 to 0.5 mol, per mol of the bifunctional phenol compound used as a raw material. Is good.

  The above reaction can be carried out without solvent, but there is no problem even if a solvent is used. In the case of using a solvent, it is preferable that the solvent does not have reactivity with the bifunctional phenol compound and the dialkoxysilane compound and is easily distilled off after completion of the reaction. Therefore, specifically, it is preferable to use a hydrocarbon solvent such as octane, nonane, decane, decalin, dodecane, toluene, xylene, tetralin, cyclohexylbenzene. These may be used alone or in combination of two or more.

  The reaction time depends on the type of raw material used, but usually requires about 1 to 100 hours. In the above reaction, since the dialkoxysilane compound and the bifunctional phenol compound to be used have a high boiling point, the reaction temperature may be set to a reaction temperature at which the catalyst or solvent to be used does not evaporate. Therefore, specifically, a temperature range of about 120 to 220 ° C. is preferable.

  After completion of the reaction, the target aryloxysilane oligomer can be obtained as a concentration residue by removing the catalyst by concentration, and simultaneously removing the solvent when the solvent is used. By this operation, the target product is not thermally decomposed, and the aryloxysilane oligomer can be obtained with high purity by a simple operation.

  The aryloxysilane oligomer obtained in this manner is useful as an epoxy resin curing agent, and gives an epoxy resin cured product having both a low dielectric loss tangent and a high glass transition temperature. That is, it is suitable for various insulating materials that have low dielectric loss and require heat resistance. For example, an embodiment that is an interlayer insulating material of a multilayer printed wiring board is a preferred embodiment of the present invention.

  As the epoxy resin curing agent to be used, an aryloxysilane oligomer may be used alone or in combination with another kind of epoxy resin curing agent. Specifically, dihydric or higher polyhydric phenols such as phenol novolac resin, cresol novolak resin, phenol aralkyl resin, naphthol aralkyl resin, triphenolmethane type novolak resin, dicyclopentadiene modified phenol resin, and these polyhydric phenols These are preferably used in combination with a phenolic curing agent including a hydroxyl group-protected type such as an active ester having a hydroxyl group protected with acyl, and these may be used in combination. Of these, the use of polyhydric phenols having a hydroxyl equivalent weight of 200 g / eq or more, or hydroxyl-protected phenolic curing agents such as active esters is particularly preferred. The ratio of the aryloxysilane oligomer in the entire epoxy resin curing agent including these is preferably 50 to 100 wt% in consideration of obtaining good dielectric properties.

  Known epoxy resins can be used in the present invention. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, biphenyl type epoxy resin, phenol biphenyl aralkyl type epoxy resin, aralkyl resin epoxy with xylylene bonds such as phenol and naphthol Epoxides of dicyclopentadiene-modified phenolic resins, dihydroxynaphthalene type epoxy resins, glycidyl ether type epoxy resins such as triphenolmethane type epoxy resins, glycidyl ester type epoxy resins, glycidylamine type epoxy resins and other bivalent or more epoxies An epoxy resin having a group is exemplified. These epoxy resins may be used alone or in combination of two or more. In particular, in view of obtaining good dielectric properties, epoxy equivalents such as phenol-biphenyl aralkyl type epoxy resins, epoxides of aralkyl resins with xylylene bonds such as phenol and naphthol, and epoxides of dicyclopentadiene-modified phenol resins It is preferable to use one having a large.

  In curing the epoxy resin, it is preferable to use a curing accelerator in combination. As such a curing accelerator, a known curing accelerator for curing an epoxy resin with a phenolic curing agent can be used. For example, a tertiary amine compound, a quaternary ammonium salt, an imidazole, a phosphine compound, a phosphonium salt. And so on. More specifically, tertiary amine compounds such as triethylamine, triethylenediamine, benzyldimethylamine, 2,4,6-tris (dimethylaminomethyl) phenol, 1,8-diazabicyclo (5,4,0) undecene-7 , 2-methylimidazole, 2,4-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, imidazoles such as 2-phenyl-4-methylimidazole, triphenylphosphine, tributylphosphine, tri (p -Phosphine compounds such as methylphenyl) phosphine and tri (nonylphenyl) phosphine, phosphonium salts such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphoniumtetranaphthoic acid borate, and triphenylphosphonio Enorato, it may be mentioned betaines like organic phosphorus compounds such as the reaction product of benzoquinone and triphenyl phosphine. In particular, the use of tertiary amine compounds, imidazoles, phosphonium salts, and betaine-like organic phosphorus compounds is preferable from the viewpoint of smoothly curing with a polycondensation type aryloxysilane compound.

  The compounding ratio of the epoxy resin curing agent and the epoxy resin of the present invention is such that the equivalent ratio of the reactive functional group of the epoxy resin curing agent / the epoxy group of the epoxy resin is 0.5 to 1.5, particularly 0.8 to 1.2. It is preferable that it exists in the range. It is preferable to use a hardening accelerator in the range of 0.1-5 weight part with respect to 100 weight part of epoxy resins.

  Although the epoxy resin composition of the present invention depends on the blending components and the composition ratio thereof, curing proceeds at a curing temperature performed by blending using a known phenol-based curing agent, for example, in a temperature range of 100 to 250 ° C. However, it is also possible to produce a cured product at 180 ° C. or lower, which is difficult to sufficiently cure by blending with a known active ester used for the purpose of obtaining good dielectric properties.

  In the epoxy resin composition of the present invention, a solvent, an inorganic filler, a colorant, a thickener, a silane coupling agent, a flame retardant, a low-stress agent, or the like may be added or reacted in advance as necessary. it can.

  The epoxy resin composition of the present invention is particularly suitable as an interlayer insulating material for multilayer printed wiring boards. For example, by dissolving the epoxy resin composition of the present invention in a solvent, it can be used as an insulating varnish for application to a circuit board to form an insulating layer, and the varnish-like epoxy resin composition is applied to glass fiber. A prepreg for the application can be obtained by impregnating and heat-treating, and an adhesive sheet for the application can be obtained by heat-treating the varnish-like epoxy resin composition on a support film to form a film. . Any of these forms can be used as an interlayer insulating layer in a multilayer printed wiring board.

  The epoxy resin composition and epoxy resin cured product using the epoxy resin curing agent of the present invention are useful for molding materials, various binders, coating materials, laminated materials and the like. These epoxy resin compositions and cured epoxy resins have small dielectric loss and excellent heat resistance.

  The present invention will be described more specifically with reference to examples and comparative examples below, but the present invention is not limited to these examples.

[Example 1]
Bisphenol TMC155.2 g and dimethoxydiphenylsilane 117.3 g were charged into a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, and the temperature was raised to 150 to 160 ° C. while stirring. Next, 0.82 g of tetraisopropyl orthotitanate was charged, the methanol produced by the reaction was removed from the system, held for 76 hours, and then cooled to allow a phenoxysilane oligomer (cured) having a theoretical functional group equivalent of 242 g / eq. Agent 1) was obtained.
The number of repetitions n of formula (1) of the obtained phenoxysilane oligomer was calculated by the following method, but the number of repetitions n calculated from NMR measurement was 5.4.
The NMR chart of the obtained phenoxysilane oligomer is shown in FIG.
Calculation of the number of repetitions n The phenoxysilane oligomer was subjected to NMR measurement under the following conditions, and calculated based on the ratio of the reacted raw material and the raw material charging ratio obtained from the results.
NMR measurement conditions:
Solvent: Heavy C ₂ H ₂ Cl ₄
Measuring instrument: JEOL (JEOL Ltd.)
Frequency: 400MHz
Integration count: 16
Internal standard: None (based on the chemical shift of tetrachloroethane)

[Example 2]
Bisphenolfluorene (150.7 g) and dimethoxydiphenylsilane (100.9 g) were charged into a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, and the temperature was raised to 150 to 160 ° C. while stirring. Next, 0.75 g of 1,8-diazabicyclo (5,4,0) undecene-7 (DBU) was charged, methanol generated by the reaction was removed out of the system, kept for 66 hours, and then cooled. A phenoxysilane oligomer (curing agent 2) having a theoretical functional group equivalent of 262 g / eq was obtained. The number of repetitions n calculated from NMR measurement in the same manner as in Example 1 was 8.0.
The NMR chart of the obtained phenoxysilane oligomer is shown in FIG.

[Example 3]
Bisphenol TMC 68.3 g, bisphenol fluorene 77.1 g, and dimethoxydiphenylsilane 103.2 g were charged into a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, and the temperature was raised to 150 to 160 ° C. while stirring. Warm up. Next, 9.73 g of N, N′-dimethylbenzylamine was charged, methanol generated by the reaction was removed from the system, kept for 90 hours, and then cooled to obtain a phenoxysilane having a theoretical functional group equivalent of 252 g / eq. An oligomer (curing agent 3) was obtained. The number of repetitions n calculated from NMR measurement in the same manner as in Example 1 was 8.3.
The NMR chart of the obtained phenoxysilane oligomer is shown in FIG.

[Comparative Example 1]
Bisphenol F (100.1 g) and dimethoxydiphenylsilane (117.3 g) were charged into a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, and the temperature was raised to 150 to 160 ° C. while stirring. Next, 6.08 g of N, N′-dimethylbenzylamine was charged, methanol produced by the reaction was removed from the system, kept for 64 hours, and then cooled to obtain a phenoxysilane having a theoretical functional group equivalent of 187 g / eq. An oligomer (curing agent 4) was obtained.

[Comparative Example 2]
In a four-necked 300 mL flask equipped with a nitrogen gas inlet tube, a thermometer, and a stirrer, 93.1 g of biphenol and 117.3 g of dimethoxydiphenylsilane were charged and heated to a temperature of 150 to 160 ° C. while stirring. Next, 5.81 g of N, N′-dimethylbenzylamine was charged, methanol generated by the reaction was removed from the system, held for 72 hours, and then cooled, so that phenoxysilane having a theoretical functional group equivalent of 180 g / eq was obtained. An oligomer (curing agent 5) was obtained.

  The physical properties of the phenoxysilane oligomers prepared in Examples 1 to 3 are shown in Table 1 in comparison with the phenoxysilane oligomers prepared in Comparative Examples 1 and 2.

[Example 4]
Epoxy resin represented by the following general formula (9) (NC-3000H manufactured by Nippon Kayaku Co., Ltd., phenol biphenyl aralkyl type, epoxy equivalent 290 g / eq), curing agent 1 obtained in Example 1, curing accelerator About the composition which consists of 2-ethyl-4-methylimidazole in the ratio shown in Table 2, the test piece for physical-property evaluation was created by thermosetting at 180 degreeC for 3 hours. The physical properties of the obtained test pieces were measured and the results are shown in Table 2.

(In the formula, G is a glycidyl group, n is a number of 1 to 10)

[Example 5]
The same operation as in Example 4 was performed, except that the curing agent 2 obtained in Example 2 was used instead of the curing agent 1 used in Example 4 and the blending ratios described in Table 2 were used. The evaluation results are shown in Table 2.

[Example 6]
The same operation as in Example 4 was performed except that the curing agent 3 obtained in Example 3 was used in place of the curing agent 1 used in Example 4 and the blending ratios described in Table 2 were used. The evaluation results are shown in Table 2.

[Comparative Example 3]
The same operation as in Example 4 was performed except that the curing agent 4 obtained in Comparative Example 1 was used instead of the curing agent 1 used in Example 4 and the blending ratios described in Table 2 were used. The evaluation results are shown in Table 2.

[Comparative Example 4]
The same operation as in Example 4 was performed except that the curing agent 5 obtained in Comparative Example 2 was used instead of the curing agent 1 used in Example 4 and the blending ratios described in Table 2 were used. The evaluation results are shown in Table 2.

The physical properties in the present invention were measured by the following methods.
(1) Glass transition point By TMA, the linear expansion coefficient of the test piece was measured at a heating rate of 10 ° C / min, and the inflection point of the linear expansion coefficient was taken as the glass transition temperature.
Measuring instrument: Thermomechanical analyzer TMA / SS7100 manufactured by Hitachi High-Tech Science Co., Ltd.
Sample size: 5mm x 5mm x 2mm
Atmosphere: Measurement temperature in nitrogen: 25-300 ° C
Temperature increase rate: 10 ° C./min.
Measurement mode: Compression (2) Dielectric characteristics The dielectric constant and dielectric loss tangent were measured under the following conditions by the cavity resonance method using a network analyzer HP8510C manufactured by Agilent Technologies.
Sample size: 2.5mm x 2mm x 40mm
Pretreatment: room temperature 22 ± 1 ° C, humidity 60 ± 5% for 90 hours storage Measurement environment: room temperature 22 ° C, humidity 60%
Frequency: 1GHz

  From the results in Table 2, the cured products using the curing agents 1 to 3 having a functional group equivalent of 200 g / eq or more of Examples 1 to 3 are the curing agents 4 and 5 obtained in Comparative Examples 1 and 2 which are conventional materials. It can be seen that the glass transition point is 10 ° C. or higher, the dielectric constant and the dielectric loss tangent are low, and excellent performance is exhibited as compared with the case where is used.

According to the present invention, an insulating material suitable for an interlayer insulating material using an epoxy resin composition having both excellent dielectric properties and heat resistance is provided.
The insulating material using the specific epoxy resin composition of the present invention has made it possible to provide an insulating material for a multilayer printed wiring board having both excellent dielectric properties and practical properties.
The epoxy resin composition and the cured product thereof provided by the present invention are useful for insulating material applications for multilayer printed wiring boards for high frequency signals that require low transmission loss.

  According to the present invention, an epoxy resin curing agent capable of forming an epoxy resin cured product excellent in low dielectric loss tangent and high glass transition temperature and an epoxy resin composition containing the same are provided, and a molding material, various binders, a coating material, Useful for laminates. Specifically, it can be applied to various insulating materials such as die-bonding materials and device encapsulating sheets. In particular, it is an interlayer insulating material for multilayer printed wiring boards represented by prepregs, interlayer insulating films, and interlayer insulating varnishes. The embodiment is a preferred embodiment of the present invention.

Claims (9)

Represented by the following general formula (1), 2 has a structure derived from the bifunctional phenol compound, equivalent to a hydroxyl group and aryloxy silyl group and reactive functional groups in the range of 200 to 400 g / eq, the bifunctional phenol An epoxy resin curing agent comprising an aryloxysilane oligomer, wherein the molecular weight of the compound is in the range of 250 to 400 .
(Wherein R ¹ is the same or different hydrocarbon group having 1 to 12 carbon atoms, Ar is a bifunctional phenol compound residue, and n is an integer of 1 to 20) The epoxy resin curing agent according to claim 1, wherein Ar in the general formula (1) is the following general formula (2) or general formula (3).
(In the formula, Ar ¹ is the same or different alkyl group having 1 to 4 carbon atoms, methoxy group, benzene ring to which 1 to 4 fluorine atoms may be bonded, Ar ² is the same or different alkyl group having 1 to 4 carbon atoms, respectively. Group, methoxy group, benzene ring to which 1 to 3 fluorine atoms may be bonded, X ¹ is a divalent carbon constituting a direct bond or a 5- to 7-membered ring hydrocarbon having 5 to 15 carbon atoms and optionally having a substituent. Atoms and X ² are the same or different direct bonds, divalent carbon atoms constituting an hydrocarbon having 1 to 15 carbon atoms, or oxygen atoms.) The epoxy resin curing agent according to claim 1, wherein the bifunctional phenol compound is any one of the following general formula (4), general formula (5), and general formula (6).
(In the formula, R ² , R ³ , R ⁴ and R ⁵ are methyl groups, R ⁶ and R ⁷ are hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, phenyl groups and naphthyl groups, and a, b , C and d are 0 to 4, e is 0 to 10, and f and g are 0 to 3.) The epoxy resin curing agent according to claim 1, which is synthesized by condensing a dialkoxysilane compound represented by the following general formula (7) and a bifunctional phenol compound represented by the general formula (8): Production method.
(Wherein R ¹ and Ar are the same as in formula (1), and R ⁹ is the same or different alkyl group having 1 to 4 carbon atoms.)   The epoxy resin composition containing the epoxy resin hardening | curing agent and epoxy resin in any one of Claims 1-3.   Furthermore, the epoxy resin composition of Claim 5 containing a hardening accelerator.   Furthermore, the epoxy resin composition of Claim 5 or 6 containing an inorganic filler.   The epoxy resin hardened | cured material formed by thermosetting the epoxy resin composition in any one of Claims 5-7.   The interlayer insulation material created with the epoxy resin composition in any one of Claims 5-7.