JP2017101099A - Thermosetting resin composition, thermosetting resin film, printed wiring board, and semiconductor device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a thermosetting resin composition capable of forming an insulating film, which is excellent in dielectric characteristics, has high flame retardancy, and has high adhesion, without using a conventional halogen-based flame retardant.SOLUTION: There is provided a thermosetting resin composition which contains (A) aromatic condensed phosphoric ester, (B) melamine cyanurate, and (C) a resin having a relative dielectric constant at a frequency of 1.9 GHz of 2.9 or less, where the total of the (A) component and the (B) component is 45 pts.mass or more with respect to 100 pts.mass of the (C) component, and the (A) component is more than the (B) component. Preferably, the thermosetting resin composition has relative dielectric constant at a frequency of 1.9 GHz of 3.0 or less.SELECTED DRAWING: None

Description

  The present invention relates to a thermosetting resin composition, a thermosetting resin film, a printed wiring board, and a semiconductor device. In particular, the present invention relates to a flame retardant thermosetting resin composition, a thermosetting resin film, a printed wiring board, and a semiconductor device.

  In recent years, the frequency of transmission signals has been increasing in the semiconductor field. There are applications where flame retardancy is required for low dielectric constant adhesive films that can cope with high frequency transmission signals.

  Thermosetting polyphenylene ether (PPE) or the like is known as a material that can handle high frequencies, and halogen-based flame retardants, phosphorus-based flame retardants, nitrogen-based flame retardants, and the like are known as flame retardant materials. Conventionally, halogen-based flame retardants used have a strong halogen-free requirement from the viewpoint of environmental problems, and the use of phosphorus-based flame retardants, nitrogen-based flame retardants, and the like has been studied.

  First, a resin component containing a predetermined amount of polyphenylene ether, a predetermined amount of thermoplastic elastomer, and a predetermined amount of polyolefin resin, and one or both of a phosphorus-based flame retardant and a nitrogen-based flame retardant with respect to 100 parts by mass of the resin component. A flame retardant resin sheet containing ˜100 parts by mass and a flat cable using the same have been reported (Patent Document 1).

  However, since the flame retardant resin sheet is premised on use for a flat cable, there is a possibility that the flame retardancy is not sufficient for printed wiring board applications.

  Next, curability containing a predetermined vinyl compound in which the terminal of a bifunctional phenylene ether oligomer having a polyphenylene ether skeleton in the molecule is vinylated and a predetermined bismaleimide compound having two or more maleimide groups in the molecule A resin composition has been reported (Patent Document 2). In this curable resin composition, a phosphorus-based flame retardant is used.

  However, the bismaleimide compound used in the curable resin composition is excellent in heat resistance, but the film produced from the curable resin composition becomes rigid, has poor film moldability, and adheres to the film. There is a problem that power is low.

International Publication No. 2011/043129 JP 2009-161725 A

  The present invention provides a thermosetting resin composition that can form an insulating film having excellent dielectric properties, high flame retardancy, and high adhesion without using a conventional halogen flame retardant. Objective.

The present invention relates to a thermosetting resin composition, a thermosetting resin film, a printed wiring board, and a semiconductor device that have solved the above problems by having the following configuration.
[1] (A) an aromatic condensed phosphate ester, (B) melamine cyanurate, and (C) a resin having a relative dielectric constant of 2.9 or less at a frequency of 1.9 GHz, The thermosetting resin composition characterized in that the total of component (A) and component (B) is 45 parts by mass or more and component (A) is greater than component (B) relative to 100 parts by mass of component.
[2] The thermosetting resin composition according to [1], wherein the relative dielectric constant at a frequency of 1.9 GHz is 3.0 or less.
[3] The thermosetting resin composition according to the above [1] or [2], wherein the component (A) is bis-dixylenyl phosphate.
[4] A thermosetting resin film using the thermosetting resin composition according to any one of [1] to [3].
[5] A printed wiring board using the cured product of the thermosetting resin composition according to any one of [1] to [3] or the cured product of the thermosetting resin film according to [4].
[6] A semiconductor device using the cured product of the resin composition according to any one of [1] to [3] or the cured product of the thermosetting resin film according to [4].

  According to the present invention [1], there is provided a thermosetting resin composition capable of forming an insulating film having excellent dielectric properties, high flame retardancy, and high adhesion without using a halogen-based flame retardant. be able to.

  According to the present invention [4], it is possible to provide an insulating film formed of a thermosetting resin composition having excellent dielectric properties, high flame retardancy, and high adhesive strength.

  According to the present invention [5], the cured product of the thermosetting resin composition or the cured product of the thermosetting resin film can provide a printed wiring board having excellent dielectric properties and high flame retardancy. it can. According to the present invention [6], a cured product of the thermosetting resin composition or a cured product of the thermosetting resin film has excellent dielectric characteristics and high flame retardancy, so that it is a semiconductor suitable for high frequency applications. An apparatus can be provided.

[Thermosetting resin composition]
The thermosetting resin composition of the present invention comprises (A) an aromatic condensed phosphate ester, (B) melamine cyanurate, and (C) a resin having a relative dielectric constant of 2.9 or less at a frequency of 1.9 GHz. The total of the component (A) and the component (B) with respect to 100 parts by mass of the component (C) is 45 parts by mass or more, and the component (A) is more than the component (B). Here, (A) component and (B) component are added as a flame retardant. The component (A) and the component (B) are unlikely to deteriorate the dielectric characteristics. In the thermosetting resin composition of the present invention, the combination of the component (A) and the component (B) makes it possible to use the component UL (A) or the component (B) in comparison with the case where the component (A) or the component (B) is used alone. It is possible to reduce the amount of flame retardant added to satisfy the flame retardancy equivalent to VTM-0 of UL94 in the standard vertical combustion test. Since a flame retardant reduces physical properties other than the flame retardancy of the resin composition (for example, lowers adhesiveness and cured film strength), it is preferable that the amount added is small.

  The aromatic condensed phosphate ester (A) imparts flame retardancy to the thermosetting resin composition. As the aromatic condensed phosphate ester, bisdixylenyl phosphate is preferable. Specifically, resorcinol bis-dixylenyl phosphate represented by the chemical formula (1):

P-cresol bis-dixylenyl phosphate represented by the chemical formula (2):

Biphenol bis-dixylenyl phosphate represented by chemical formula (3):

Resorcinol bis-diphenyl phosphate represented by chemical formula (4):

Bisphenol A bis-diphenyl phosphate represented by chemical formula (5):

Is more preferable. Here, resorcinol bis-dixylenyl phosphate is solid at room temperature (powder) and dissolved in resin, and p-cresol bis-dixylenyl phosphate and biphenol bis-dixylenyl phosphate are solid at room temperature (powder). Resorcinol bis-diphenyl phosphate and bisphenol A bis-diphenyl phosphate do not dissolve in the resin and are liquid. By using powdered bisdixylenyl phosphate, it is possible to reduce the occurrence of blooming over time after the thermosetting resin film is formed, as compared with other aromatic condensed phosphate esters that are liquid.

The melamine cyanurate as the component (B) imparts flame retardancy to the thermosetting resin composition. Melamine cyanurate (C ₃ H ₆ N ₆ .C ₃ H ₃ N ₃ O ₃ ) has the chemical formula (6):

It is represented by

  The resin having a relative dielectric constant of 2.9 or less at a frequency of 1.9 GHz, which is the component (C), imparts high-frequency characteristics (that is, low dielectric constant), heat resistance, and adhesiveness to the thermosetting resin composition. Here, the high frequency characteristic means a property of reducing transmission loss in a high frequency region, and the component (C) has a very high frequency characteristic because the relative dielectric constant (ε) is 2.9 or less. . The component (C) preferably contains (C1) a thermosetting resin and (C2) a styrenic block copolymer in which the unsaturated double bond of the main chain in the molecule is hydrogenated.

  The thermosetting resin as the component (C1) imparts adhesiveness, high frequency characteristics, and heat resistance to the thermosetting resin composition. As the component (C1), a resin having a styrene group at the terminal and an epoxy resin are preferable, and a resin having a styrene group at the terminal is more preferable.

  As the resin having a styrene group at the terminal, the following general formula (7):

(Where
R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , R ₇ may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group,
— (O—X—O) — is represented by the structural formula (8), in which R ₈ , R ₉ , R ₁₀ , R ₁₄ , and R ₁₅ may be the same or different and are each a halogen atom or a carbon number 6 or less alkyl group or phenyl group, R ₁₁ , R ₁₂ and R ₁₃ may be the same or different, and are a hydrogen atom, a halogen atom or an alkyl group or phenyl group having 6 or less carbon atoms,
-(YO)-is one type of structure represented by the structural formula (9) or two or more types of structures represented by the structural formula (9) arranged at random, where R ₁₆ , R ₁₇ may be the same or different, and is a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R ₁₈ and R ₁₉ may be the same or different, and may be a hydrogen atom, halogen atom, or 6 or less carbon atoms. An alkyl group or a phenyl group,
Z is an organic group having 1 or more carbon atoms, and may contain an oxygen atom, a nitrogen atom, a sulfur atom, or a halogen atom in some cases,
a and b each represents an integer of 0 to 300, at least one of which is not 0;
A thermosetting polyphenylene ether oligomer (hereinafter, referred to as modified PPE) having a phenyl group bonded to a vinyl group at both ends, which is represented by c and d are integers of 0 or 1, is preferable. When the modified PPE is used as the component (C1), in addition to excellent high-frequency characteristics, heat resistance is excellent, and the thermosetting resin composition after curing hardly changes over time. Long-term reliability of a printed wiring board and a semiconductor device having a conductive resin composition can be maintained. Furthermore, since the number of hydrophilic groups in the resin is small, it has a feature of being excellent in hygroscopicity and chemical resistance. This modified PPE is as described in JP-A-2004-59644.

In the structural formula (8) for — (O—X—O) — of the modified PPE represented by the general formula (7), R ₈ , R ₉ , R ₁₀ , R ₁₄ and R ₁₅ are preferably carbon atoms. It is an alkyl group having 3 or less, and R ₁₁ , R ₁₂ and R ₁₃ are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms. Specifically, structural formula (10) is mentioned.

In Structural Formula (9) for — (Y—O) —, R ₁₆ and R ₁₇ are preferably an alkyl group having 3 or less carbon atoms, and R ₁₈ and R ₁₉ are preferably a hydrogen atom or a carbon atom. It is an alkyl group having a number of 3 or less. Specifically, structural formula (11) or (12) is mentioned.

  Z includes an alkylene group having 3 or less carbon atoms, specifically a methylene group.

  a and b each represent an integer of 0 to 300, preferably at least one of which is not 0, and preferably represents an integer of 0 to 30.

  The resin having a styrene group at the end preferably has an average molecular weight molecular weight of 800 to 3,500, and more preferably a modified PPE of the general formula (7) having a molecular weight of 800 to 3000. More preferably, the number average molecular weight is 800 to 2500. The number average molecular weight is a value using a standard polystyrene calibration curve by gel permeation chromatography (GPC).

  The epoxy resin may be a liquid epoxy resin or a solid epoxy resin. Epoxy resins include aminophenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, naphthalene type epoxy resin, biphenyl type epoxy resin, hydrogenated bisphenol type epoxy resin, alicyclic epoxy resin, alcohol ether type epoxy. Resin, cycloaliphatic epoxy resin, fluorene epoxy resin, siloxane epoxy resin and the like. From the viewpoint of fluidity of thermosetting resin composition and flexibility of thermosetting resin film, liquid bisphenol A type epoxy Resins, liquid bisphenol F type epoxy resins, liquid naphthalene type epoxy resins, and liquid biphenyl type epoxy resins are preferred. From the viewpoint of heat resistance and durability, a solid epoxy resin is preferable.

  Commercially available epoxy resins include bisphenol A type epoxy resins (eg, LX-01 manufactured by Daiso, YDF8170 manufactured by Nippon Steel Chemical, 828, 828EL manufactured by Mitsubishi Chemical), aminophenol type epoxy resins (eg, JER630 manufactured by Mitsubishi Chemical, JER630LSD), bisphenol F type epoxy resin (Example: YDF870GS manufactured by Nippon Steel Chemical Co., Ltd.), naphthalene type epoxy resin (Example: HP 4032D manufactured by DIC), biphenyl type epoxy resin (Example: NC-3000-H manufactured by Nippon Kayaku), siloxane Epoxy resin (eg, TSL9906 manufactured by Shin-Etsu Chemical Co., Ltd.) and the like.

  (C1) A component may be individual or may use 2 or more types together.

  The component (C2) is a styrene block copolymer in which unsaturated double bonds in the main chain in the molecule are hydrogenated. As the hydrogenated styrene block copolymer, a styrene-ethylene / butylene-styrene block copolymer is used. (SEBS), styrene- (ethylene-ethylene / propylene) -styrene block copolymer (SEEPS), styrene-ethylene / propylene-styrene block copolymer (SEPS), and the like, and SEBS and SEEPS are preferable. This is because SEBS and SEEPS have excellent dielectric properties, are compatible with polyphenylene ether (PPE), modified PPE, and the like, which are options for the component (C1), and can form a thermosetting resin composition having heat resistance. Furthermore, since the styrenic block copolymer contributes to lowering the elasticity of the thermosetting resin composition, it gives flexibility to the thermosetting resin film, and the cured product of the thermosetting resin composition has 3 GPa or less. Suitable for applications where low elasticity is required.

  The weight average molecular weight of the component (C2) is preferably 30,000 to 200,000, and more preferably 80,000 to 120,000. The weight average molecular weight is a value obtained by gel permeation chromatography (GPC) using a standard polystyrene calibration curve.

  (C2) A component may be individual or may use 2 or more types together.

  It is preferable that the thermosetting resin composition further contains (C3) acrylate monomer from the viewpoint of improving the adhesive strength.

  When an epoxy resin is used as (C1), the thermosetting resin composition further contains a curing catalyst for curing. Examples of the curing catalyst include imidazole. Moreover, when using resin which has a styrene group at the terminal as (C1), it is preferable from a curable viewpoint of a thermosetting resin composition to contain a curing catalyst like an organic peroxide.

  Next, 45-90 mass parts is preferable with respect to 100 mass parts of (C) component, and, as for the sum total of (A) component and (B) component, 50-85 mass parts is more preferable.

  (A) It is preferable that it is 60-85 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and it is more preferable that it is 65-80 mass parts. By setting the ratio of the flame retardant within this range, the synergistic effect of the component (A) and the component (B) can be obtained, and the absolute amount of the flame retardant necessary for providing the flame retardant effect can be reduced. .

  The component (C1) is preferably 15 to 55 parts by mass with respect to 100 parts by mass of the component (C) from the viewpoints of high frequency characteristics, heat resistance, and chemical resistance of the thermosetting resin composition.

  The component (C2) is preferably 40 to 80 parts by mass with respect to 100 parts by mass of the component (C) from the viewpoint of high frequency characteristics and low elasticity of the thermosetting resin composition.

  As for (C3) component, 1-5 mass parts is preferable with respect to 100 mass parts of (C) component. As for a curing catalyst, 0.1-4 mass parts is preferable with respect to 100 mass parts of (C) component.

  In addition, the thermosetting resin composition is a range that does not impair the effects of the present invention, a filler, a coupling agent such as a silane coupling agent, a tackifier, an antifoaming agent, a flow regulator, a film forming auxiliary agent, Additives such as dispersion aids can be included.

  The thermosetting resin composition can be produced by dissolving or dispersing raw materials such as the components (A), (B), and (C) constituting the resin composition in an organic solvent. The apparatus for dissolving or dispersing these raw materials is not particularly limited, but a stirrer, a dissolver, a reiki machine, a three roll mill, a ball mill, a planetary mixer, a bead mill, etc. equipped with a heating device should be used. Can do. Moreover, you may use combining these apparatuses suitably.

  Examples of the organic solvent include aromatic solvents such as toluene and xylene, and ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone. The organic solvents may be used alone or in combination of two or more. From the viewpoint of workability, the thermosetting resin composition preferably has a viscosity range of 200 to 3000 mPa · s. The viscosity is a value measured using an E-type viscometer at a rotation speed of 10 rpm and 25 ° C.

  The obtained thermosetting resin composition preferably has a relative dielectric constant (ε) at a frequency of 1.9 GHz of 3.0 or less. Since the component (A) and the component (B) are flame retardants that do not relatively increase the relative dielectric constant (ε) and dielectric loss tangent (tan δ) of the thermosetting resin composition, the ratio of the thermosetting resin composition The dielectric constant (ε) and the dielectric loss tangent (tan δ) can be kept low.

[Thermosetting resin film]
Next, a method for forming a thermosetting resin film will be described. The thermosetting resin film is formed into a desired shape from the thermosetting resin composition. Specifically, the thermosetting resin film can be obtained by applying the above-mentioned thermosetting resin composition on a support and drying it. The support is not particularly limited, and examples thereof include metal foils such as copper and aluminum, organic films such as polyester resins, polyethylene resins, and polyethylene terephthalate resins (PET). The support may be release-treated with a silicone compound or the like. The thermosetting resin composition can be used in various shapes, and the shape is not particularly limited.

  The method for applying the thermosetting resin composition to the support is not particularly limited, but the gravure method, the slot die method, and the doctor blade method are preferable from the viewpoint of thinning and controlling the film thickness. By the slot die method, an uncured film of a thermosetting resin composition having a thickness after heat curing of 5 to 300 μm, that is, a thermosetting resin film can be obtained.

  The drying conditions can be appropriately set according to the type and amount of the organic solvent used in the thermosetting resin composition, the thickness of the coating, and the like, for example, at 50 to 120 ° C. for about 1 to 60 minutes. It can be. The thermosetting resin film thus obtained has good storage stability. In addition, a thermosetting resin film can be peeled from a support body at a desired timing.

  The thermosetting resin film can be cured, for example, at 150 to 230 ° C. for 30 to 180 minutes. The curing of the thermosetting resin film may be performed after sandwiching the thermosetting resin film between the substrates on which the wiring made of copper foil or the like is formed, and the thermosetting resin film on which the wiring made of copper foil or the like is formed, You may carry out after laminating | stacking suitably. The thermosetting resin film can also be used as a coverlay film for protecting the wiring on the substrate, and the curing conditions at that time are the same. The thermosetting resin composition can be similarly cured.

  The thermosetting resin film of the present invention can impart high flame retardancy after curing even if the amount of the flame retardant is small. For this reason, content of a flame retardant can be decreased rather than before and the thermosetting resin film after hardening can be made tough. Here, when there is much content of the flame retardant in a thermosetting resin film, the thermosetting resin film after hardening will become weak easily, and cured film strength will fall. A decrease in the strength of the cured film is not preferable because it causes, for example, generation of cracks and a decrease in adhesiveness. Conventionally, the influence of the amount of the flame retardant is more likely to occur in a film than in a prepreg (a sheet in which a fiber is impregnated with a resin) used in a printed circuit board.

[Printed wiring board]
The printed wiring board of the present invention is produced by curing the above-described thermosetting resin composition or the above-described thermosetting resin film. This printed wiring board has excellent dielectric properties and high flame retardancy due to the cured product of the thermosetting resin composition or the cured product of the thermosetting resin film. Among printed wiring boards, flexible copper clad laminates (FCCL) for flexible printed circuit boards (FPC), copper clad laminates (CCL) for multilayer boards (CCL), Or it is suitable for build-up materials. The manufacturing method of a printed wiring board is not specifically limited, The same method as the case where a printed wiring board is produced using a general prepreg can be used.

[This conductor device]
The semiconductor device of the present invention is manufactured by using the above-mentioned thermosetting resin composition or the above-mentioned thermosetting resin film and curing it. This semiconductor device is suitable for high-frequency applications because it has excellent dielectric properties and high flame retardancy due to the cured product of the thermosetting resin composition or the cured product of the thermosetting resin film. Here, the semiconductor device refers to all devices that can function by utilizing semiconductor characteristics, and includes electronic components, semiconductor circuits, modules incorporating these, electronic devices, and the like.

  The present invention will be described with reference to examples, but the present invention is not limited thereto. In the following examples, parts and% indicate parts by mass and mass% unless otherwise specified.

[Examples 1-7, Comparative Examples 1-10]
<Preparation of thermosetting resin composition>
In the composition shown in Tables 1-3, resin, elastomer, soluble condensed (A) component aromatic condensed phosphate ester (1) and toluene are weighed into a container, heated and dissolved using a heating stirrer, (B) component melamine cyanurate, curing catalyst, and additives are weighed in and mixed with a rotating / revolving stirrer (Mazerustar) for 3 minutes, and then dispersed using a bead mill. The thermosetting resin composition was adjusted by adjusting the viscosity with toluene. When the aromatic condensed phosphate ester (2), which is an insoluble component (A), is used, the resin, elastomer and toluene are weighed into a container and heated and dissolved using a heating stirrer. After cooling to the same level, the rest was adjusted as described above.

〔Evaluation method〕
<1. Flame Retardancy Test>
The obtained thermosetting resin composition was applied on a 50 μm-thick polyethylene terephthalate (PET) film to which a release agent was applied, using an applicator so that the dried coating film had a thickness of 25 ± 5 μm. And dried at 80 ° C. for 10 minutes to obtain a thermosetting resin film. The obtained thermosetting resin film was press-cured with a vacuum press (180 ° C. × 60 minutes, pressure: 0.5 MPa), then cut to 200 × 50 mm, and the PET film was peeled off to prepare a test sample. . In accordance with the UL94 VTM test method of the vertical combustion test of the US UL standard, the flame retardancy of the test sample was evaluated. Tables 1 to 3 show the results.

<2. Measurement of relative permittivity (ε) and dielectric loss tangent (tan δ)>
1. In the same manner as the flame retardancy test, a thermosetting resin composition was applied on a 50 μm-thick PET film to which a release agent was applied so that the dried coating film had a thickness of 25 ± 5 μm, and dried. The cured thermoset resin film was obtained. After the cured thermosetting resin film was cut into 130 × 40 mm, the PET film was peeled off to prepare a sample for measuring relative dielectric constant / dielectric loss tangent. The relative permittivity (ε) and dielectric loss tangent (tan δ) of the measurement sample were measured with a split post dielectric resonator (SPDR) at a dielectric resonance frequency of 1.9 GHz. The relative dielectric constant is preferably 3.0 or less and the dielectric loss tangent is preferably 0.0040 or less. Tables 1 and 2 show the results. Similarly, the relative dielectric constant (ε) of the component (C) used in the examples was measured.

<3. Peel strength test>
1. In the same manner as the flame retardancy test, a thermosetting resin composition was applied on a 50 μm-thick PET film to which a release agent was applied so that the dried coating film had a thickness of 25 ± 5 μm, and dried. The thermosetting resin film thus obtained was cut to 100 × 100 mm, and the PET film was peeled off. A 12 μm thick copper foil glossy surface is laminated on one side of the peeled thermosetting resin film, and a 12 μm thick polyimide film is laminated on the other side, followed by press curing (180 ° C. × 60 minutes, pressure: 0). .5 MPa) and bonded to produce a peel strength test sample. The peel strength test sample thus prepared was cut to a width of 10 mm, and the peel strength was measured by peeling off the copper foil and the polyimide film with an autograph. For the measurement results, the average value of each N = 5 was calculated. The peel strength is preferably 5.0 N / cm or more. Table 3 shows the results.

  As can be seen from Tables 1 and 2, Examples 1 to 7 were good results in all of flame retardancy, relative dielectric constant (ε), and dielectric loss tangent (tan δ). Although not shown in the table, the relative dielectric constant (ε) of all the components (C) was 2.9 or less. In Example 1, when the flame retardant (component (A) + component (B)) is removed, the relative dielectric constant (ε) is 2.5, and the dielectric loss tangent (tan δ) is 0.0028. The increase in relative dielectric constant (ε) and dielectric loss tangent (tan δ) was small. On the other hand, Comparative Example 1 which contained a large amount of component (A) and did not use component (B) had a poor flame retardant test result. In Comparative Example 2 using the same amount of (A) and (B), the result of the flame retardancy test was bad. The result of the flame retardance test was bad in Comparative Example 3 in which the total of the component (A) and the component (B) with respect to 100 parts by mass of the component (C) was less than 45 parts by mass. In Comparative Example 4 using ammonium polyphosphate instead of the components (A) and (B), the relative dielectric constant and dielectric loss tangent were high. Comparative Example 5 using melamine / melam / melem double salt polyphosphate instead of component (A) and Comparative Example 6 using phosphaphenanthrene compound (1) have poor flame retardant test results. The dielectric constant and dielectric loss tangent were high. In Comparative Example 7 using the phosphaphenanthrene compound (2) in place of the component (A), the result of the flame retardancy test was bad. Comparative Example 8 using the phosphazene compound (1) instead of the component (A) had a high dielectric loss tangent. In Comparative Example 9 in which the phosphazene compound (2) was used in place of the component (A), the result of the flame retardancy test was poor and the dielectric loss tangent was high.

  As can be seen from Table 3, Examples 1 and 4 had high peel strength. In contrast, Comparative Example 10 that contained a large amount of the component (A) and did not use the component (B) had a low peel strength. Although not shown in Table 3, the peel strengths of Examples 1 to 7 were all 5.0 N / cm or more.

  As described above, the thermosetting resin composition of the present invention uses an insulating film having high flame retardancy and high adhesive strength, using a material having excellent dielectric characteristics without using a halogen-based flame retardant. It can be formed and is very useful. The printed wiring board of the present invention has excellent dielectric properties and high flame retardancy due to the cured product of the thermosetting resin composition or the cured product of the thermosetting resin film. The semiconductor device of the present invention is suitable for high-frequency applications because it has excellent dielectric properties and high flame retardancy due to the cured product of the thermosetting resin composition or the cured product of the thermosetting resin film.

Claims (6)

  (A) aromatic condensed phosphate ester, (B) melamine cyanurate, and (C) resin having a relative dielectric constant of 2.9 or less at a frequency of 1.9 GHz, and (C) component 100 mass The thermosetting resin composition, wherein the sum of the component (A) and the component (B) is 45 parts by mass or more, and the amount of the component (A) is greater than that of the component (B).   The thermosetting resin composition according to claim 1, wherein a relative dielectric constant at a frequency of 1.9 GHz is 3.0 or less. The thermosetting resin composition according to claim 1 or 2, wherein the component (A) is bisdixylenyl phosphate.   A thermosetting resin film using the thermosetting resin composition according to claim 1.   The printed wiring board using the hardened | cured material of the thermosetting resin composition of any one of Claims 1-3, or the hardened | cured material of the thermosetting resin film of Claim 4.   The semiconductor device using the hardened | cured material of the resin composition of any one of Claims 1-3, or the hardened | cured material of the thermosetting resin film of Claim 4.