KR102570161B1 - Thermosetting resin composition, thermosetting resin film, printed wiring board and semiconductor device - Google Patents

Abstract

It is an object of the present invention to provide a thermosetting resin composition capable of forming an insulating film having excellent dielectric properties, high flame retardancy, and high adhesion without using a conventional halogen-based flame retardant. (A) an aromatic condensed phosphate ester, (B) melamine cyanurate, and (C) a resin having a relative permittivity of 2.9 or less at a frequency of 1.9 GHz, and (A) component with respect to 100 parts by mass of (C) component The total amount of component (B) is 45 parts by mass or more, and component (A) is a thermosetting resin composition characterized by more than component (B). A thermosetting resin composition having a relative dielectric constant of 3.0 or less at a frequency of 1.9 GHz is preferable.

Description

Thermosetting resin composition, thermosetting resin film, printed wiring board and semiconductor device

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

Recently, in the field of semiconductors, high-frequency transmission signals are being promoted. There are applications in which flame retardance is required for a low dielectric constant adhesive film capable of responding to high frequency transmission signals.

Thermosetting polyphenylene ether (PPE) and the like are known as materials capable of responding to 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 used halogen-based flame retardants have a strong demand for halogen-free from the viewpoint of environmental problems, and 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 5 to 100% of 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 parts by mass and a flat cable using the same have been reported (Patent Document 1).

However, since the said flame retardant resin sheet is premised on use for a flat cable, there exists a possibility that flame retardance may not be enough for a printed wiring board use.

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

However, although the bismaleimide compound used in the curable resin composition has excellent heat resistance, there are problems in that a film produced from the curable resin composition becomes rigid, poor film formability, and low adhesive strength.

International Publication No. 2011/043129 Japanese Unexamined Patent Publication No. 2009-161725

An object of the present invention is to provide a thermosetting resin composition capable of forming an insulating film having excellent dielectric properties, high flame retardancy, and high adhesion without using a conventional halogen-based flame retardant.

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 structures.

[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, with respect to 100 parts by mass of component (C) (A) ) component and (B) component are 45 parts by mass or more in total, and (A) component is more than (B) component, the thermosetting resin composition characterized by the above-mentioned.

[2] The thermosetting resin composition according to [1] above, wherein the dielectric constant at a frequency of 1.9 GHz is 3.0 or less.

[3] The thermosetting resin composition according to [1] or [2] above, wherein the component (A) is bisdisylenylphosphate.

[4] A thermosetting resin film using the thermosetting resin composition according to any one of [1] to [3] above.

[5] A printed wiring board using a cured product of the thermosetting resin composition according to any one of [1] to [3] above or a cured product of the thermosetting resin film according to [4] above.

[6] A semiconductor device using a cured product of the resin composition according to any one of [1] to [3] above or a cured product of the thermosetting resin film according to [4] above.

According to the present invention [1], it is possible to provide a thermosetting resin composition capable of forming an insulating film having excellent dielectric properties, high flame retardancy, and high adhesive strength without using a halogen-based flame retardant.

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], a printed wiring board having excellent dielectric properties and high flame retardancy can be provided by a cured product of the thermosetting resin composition or a cured product of the thermosetting resin film.

According to the present invention [6], since the cured product of the thermosetting resin composition or the cured product of the thermosetting resin film has excellent dielectric properties and high flame retardancy, a semiconductor device suitable for high-frequency applications can be provided.

[Thermosetting resin composition]

The thermosetting resin composition of the present invention contains (A) an aromatic condensed phosphate ester, (B) melamine cyanurate, and (C) a resin having a relative permittivity of 2.9 or less at a frequency of 1.9 GHz, and 100 parts by mass of component (C) The total of component (A) and component (B) is 45 parts by mass or more, and component (A) is more than component (B). Here, (A) component and (B) component are added as a flame retardant. Component (A) and component (B) are difficult to deteriorate dielectric properties. The thermosetting resin composition of the present invention, by using component (A) and component (B) in combination, compared to the case of using component (A) or component (B) alone, respectively, UL94 of the vertical burning test of the US UL standard The addition amount of the flame retardant to satisfy flame retardancy equivalent to VTM-0 can be reduced. Since the flame retardant lowers physical properties other than flame retardancy of the resin composition (for example, lowers adhesiveness or cured film strength), it is preferable that the addition amount is small.

The aromatic condensed phosphoric acid ester as component (A) imparts flame retardancy to the thermosetting resin composition. As the aromatic condensed phosphoric acid ester, bisdixylenyl phosphate is preferable, specifically resorcinol bis-disylenyl phosphate represented by formula (1):

p-cresolbis-disylenylphosphate represented by formula (2):

Biphenolbis-disylenylphosphate represented by formula (3):

Resorcinolbis-diphenylphosphate represented by formula (4):

Bisphenol A bis-diphenylphosphate represented by formula (5):

is more preferable. Here, resorcinol bis-disylenyl phosphate is solid (powder) at room temperature and dissolved in the resin, and p-cresol bis-disylenyl phosphate and biphenol bis-disylenyl phosphate are solid (powder) at room temperature, Insoluble in resin, resorcinol bis-diphenylphosphate and bisphenol A bis-diphenylphosphate are liquid. By using the powdery bisdisylenylphosphate, compared to other liquid aromatic condensed phosphoric acid esters, blooming due to lapse of time after formation of the thermosetting resin film can be reduced.

(B) Component melamine cyanurate 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 formula (6):

represented by

Component (C), a resin having a relative dielectric constant of 2.9 or less at a frequency of 1.9 GHz, imparts high-frequency characteristics (ie, low dielectric constant), heat resistance, and adhesiveness to the thermosetting resin composition. Here, high-frequency characteristics refer to properties that reduce transmission loss in a high-frequency region, and component (C) has very excellent high-frequency characteristics because the dielectric constant (ε) is 2.9 or less. Component (C) preferably includes (C1) a thermosetting resin and (C2) a styrenic block copolymer in which unsaturated double bonds in the main chain of the molecule are hydrogenated.

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

The resin having a styrene group at the terminal includes the following formula (7):

(In the expression,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and 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;

-(OXO)- is represented by structural formula (8), wherein R ₈ , R ₉ , R ₁₀ , R ₁₄ , and R ₁₅ may be the same or different, and are a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group, and R ₁₁ , R ₁₂ , R ₁₃ may be the same or different, and are a hydrogen atom, a halogen atom, or an alkyl group having 6 or less carbon atoms or a phenyl group;

-(YO)- is one type of structure represented by Structural Formula (9), or two or more types of structures represented by Structural Formula (9) arranged randomly, wherein R ₁₆ and R ₁₇ may be the same or different, and halogen atom or an alkyl group or phenyl group having 6 or less carbon atoms, R ₁₈ and R ₁₉ 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;

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 represent integers from 0 to 300 in which at least either one is not 0;

(c and d represent an integer of 0 or 1) is preferably an oligomer of thermosetting polyphenylene ether having at both ends a phenyl group to which a vinyl group is bonded (hereinafter, referred to as modified PPE). In the case of using modified PPE as component (C1), in addition to being excellent in high-frequency characteristics, it is excellent in heat resistance, and the thermosetting resin composition after curing is less likely to change over time, and long-term of printed wiring boards and semiconductor devices having this thermosetting resin composition. reliability can be maintained. In addition, since the number of hydrophilic groups in the resin is small, it is characterized by excellent hygroscopicity and chemical resistance. This modified PPE is as described in Unexamined-Japanese-Patent No. 2004-59644.

In structural formula (8) for -(OXO)- of modified PPE represented by formula (7), R ₈ , R ₉ , R ₁₀ , R ₁₄ , R ₁₅ are preferably alkyl groups of 3 or less carbon atoms, and R ₁₁ , R ₁₂ , 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 -(YO)-, R ₁₆ and R ₁₇ are preferably alkyl groups having 3 or less carbon atoms, and R ₁₈ and R ₁₉ are preferably hydrogen atoms or alkyl groups having 3 or less carbon atoms. Specifically, structural formula (11) or (12) is mentioned.

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

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

The resin having a styrene group at the terminal preferably has an average molecular weight of 800 to 3,500, more preferably a modified PPE of the formula (7) having an average molecular weight of 800 to 3,000. More preferably, it is a number average molecular weight of 800 to 2,500. 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. As the epoxy resin, 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 , cyclic aliphatic epoxy resins, fluorene type epoxy resins, siloxane type epoxy resins, etc., from the viewpoint of the fluidity of the thermosetting resin composition and the flexibility of the thermosetting resin film, liquid bisphenol A type epoxy resin, 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, it is preferable if it is a solid epoxy resin.

Examples of commercially available epoxy resins include bisphenol A-type epoxy resins (e.g., LX-01 manufactured by Daiso, YDF8170 manufactured by Nippon-Stetsu Chemical, 828 and 828EL manufactured by Mitsubishi Chemical), aminophenol-type epoxy resins (eg, JER630 and JER630LSD manufactured by Mitsubishi Chemical). ), bisphenol F-type epoxy resin (e.g. YDF870GS manufactured by Shin-Nittetsu Chemical), naphthalene-type epoxy resin (e.g. HP4032D manufactured by DIC), biphenyl-type epoxy resin (e.g. NC-3000-H manufactured by Nippon Kayaku), siloxane-based epoxy Resin (for example, Shin-Etsu Chemical TSL9906) etc. are mentioned.

(C1) The component may be used alone or in combination of two or more.

Component (C2) is a styrenic block copolymer in which unsaturated double bonds in the main chain of the molecule have been hydrogenated, and examples of the hydrogenated styrenic block copolymer include styrene-ethylene/butylene-styrene block copolymer (SEBS) and styrene- (Ethylene-ethylene/propylene)-styrene block copolymer (SEEPS), styrene-ethylene/propylene-styrene block copolymer (SEPS), etc. are mentioned, and SEBS and SEEPS are preferable. This is because SEBS and SEEPS have excellent dielectric properties, good compatibility with polyphenylene ether (PPE), modified PPE, etc., which are optional components (C1), and can form a thermosetting resin composition having heat resistance. In addition, since the styrenic block copolymer also contributes to lower elasticity of the thermosetting resin composition, it imparts flexibility to the thermosetting resin film and is suitable for applications requiring low elasticity of 3 GPa or less in the cured product of the thermosetting resin composition.

(C2) It is preferable that it is 30,000-200,000, and, as for the weight average molecular weight of component, it is more preferable that it is 80,000-120,000. The weight average molecular weight is a value using a standard polystyrene calibration curve by gel permeation chromatography (GPC).

(C2) The component may be used alone or in combination of two or more.

If the thermosetting resin composition further contains the (C3) acrylate monomer, it is preferable from the viewpoint of improving the adhesive force.

In the case of using an epoxy resin as (C1), the thermosetting resin composition further contains a curing catalyst for curing. Imidazole etc. are mentioned as this curing catalyst. Moreover, when using resin which has a styrene group at the terminal as (C1), if a curing catalyst like an organic peroxide is included, it is preferable from a curable viewpoint of a thermosetting resin composition.

Next, the total of component (A) and component (B) is preferably 45 to 90 parts by mass, and more preferably 50 to 85 parts by mass with respect to 100 parts by mass of component (C).

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

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

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

Component (C3) is preferably 1 to 5 parts by mass based on 100 parts by mass of component (C). The curing catalyst is preferably 0.1 to 4 parts by mass based on 100 parts by mass of component (C).

In addition, the thermosetting resin composition may contain additives such as fillers, coupling agents such as silane coupling agents, tackifiers, antifoaming agents, flow regulators, film formation aids, and dispersion aids within a range that does not impair the effects of the present invention.

The thermosetting resin composition can be prepared by dissolving or dispersing raw materials such as 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 equipped with a heating device, a dissolver, a Leica machine, a three-roll mill, a ball mill, a planetary mixer, a bead mill, and the like can be used. Moreover, you may use these apparatuses combining suitably.

Examples of the organic solvent include, for example, toluene and xylene as aromatic solvents, and methyl ethyl ketone and methyl isobutyl ketone as examples of ketone solvents. An organic solvent may be used individually or in combination of 2 or more types. From the viewpoint of workability, the thermosetting resin composition preferably has a viscosity in the range of 200 to 3,000 mPa·s. The viscosity is a value measured at a rotational speed of 10 rpm and at 25°C using an E-type viscometer.

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

[Thermosetting resin film]

Next, the formation method of a thermosetting resin film is demonstrated. A thermosetting resin film is formed into a desired shape from a thermosetting resin composition. Specifically, the thermosetting resin film can be obtained by applying the thermosetting resin composition described above on a support and then 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 subjected to release treatment with a silicone-based compound or the like. In addition, the thermosetting resin composition can be used in various shapes, and the shape is not particularly limited.

The method of 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 film thickness control. By the slot die method, an uncured film of a thermosetting resin composition having a thickness of 5 to 300 µm after thermal curing, that is, a thermosetting resin film can be obtained.

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

Curing of the thermosetting resin film can be performed under conditions of 30 to 180 minutes at 150 to 230°C, for example. Curing of the thermosetting resin film may be performed after sandwiching the thermosetting resin film between substrates on which wires are formed by copper foil or the like, or after properly laminating the thermosetting resin film on which wires are formed by copper foil or the like. In addition, the thermosetting resin film can be used as a coverlay film for protecting wiring on a substrate, and the curing conditions at that time are also the same. In addition, a thermosetting resin composition can also be cured in the same way.

The thermosetting resin film of the present invention can impart high flame retardancy after curing with a small amount of the flame retardant. For this reason, content of a flame retardant can be reduced more 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 becomes easy to weaken and the cured film strength will fall. A decrease in the strength of the cured film is undesirable because it causes, for example, cracking or deterioration in adhesiveness. Film is more likely to be affected by the amount of flame retardant than prepreg (sheet in which fibers are impregnated with resin) conventionally used for printed circuit boards.

[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 is excellent in dielectric properties and has 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 circuits (FPC), copper clad laminates (CCL) for multilayer boards, or build-up materials are suitable. The manufacturing method of a printed wiring board is not specifically limited, The method similar to the case of manufacturing a printed wiring board using a general prepreg can be used.

[Semiconductor device]

The semiconductor device of the present invention is produced by curing the above-described thermosetting resin composition or the above-described thermosetting resin film. This semiconductor device is suitable for high-frequency applications because the cured product of the thermosetting resin composition or the cured product of the thermosetting resin film has excellent dielectric properties and high flame retardancy. Here, a semiconductor device refers to an overall device that can function by utilizing semiconductor characteristics, and includes electronic parts, semiconductor circuits, modules combining them, electronic devices, and the like.

Example

The present invention will be described by examples, but the present invention is not limited thereto. Incidentally, in the following examples, parts and % represent parts by mass and % by mass unless otherwise specified.

[Examples 1 to 7, Comparative Examples 1 to 10]

<Preparation of thermosetting resin composition>

In the formulations shown in Tables 1 to 3, resin, elastomer, aromatic condensed phosphoric acid ester (1) and toluene, which are soluble components (A), are weighed into a container, heated and dissolved using a heating stirrer, and cooled to room temperature. , Into (B) component melamine cyanurate, curing catalyst, and additives were weighed and mixed with a rotating/revolution type stirrer (Mazelstar) for 3 minutes, then dispersed using a bead mill, and the viscosity was adjusted with toluene Thus, a thermosetting resin composition was prepared. In the case of using aromatic condensed phosphoric acid ester (2) as insoluble component (A), resin, elastomer and toluene are weighed into a container, heated and dissolved using a heating stirrer, and added after cooling to room temperature After that, it was prepared in the same way as above.

[Assessment Methods]

<1. Flame retardancy test>

The obtained thermosetting resin composition was applied onto a polyethylene terephthalate (PET) film having a thickness of 50 μm treated with a release agent using an applicator so that the dry coating film had a film thickness of 25±5 μm, and dried at 80° C. for 10 minutes, followed by drying the thermosetting resin composition. got the film After press hardening (180 degreeC x 60 minutes, pressure: 0.5 MPa) of the obtained thermosetting resin film with a vacuum press machine, it cut out to 200 x 50 mm, peeled the PET film, and produced the test sample. Based on the UL94 VTM test method of the vertical burning test of the American UL standard, the flame retardance of the test sample was evaluated. A result is shown to Tables 1-3.

<2. Measurement of relative permittivity (ε) and dielectric loss tangent (tanδ)>

1. In the same way as in the flame retardancy test, a thermosetting resin composition was applied, dried, and cured on a PET film having a thickness of 50 μm treated with a release agent so that a dry coating film had a film thickness of 25 ± 5 μm, and the cured thermosetting resin film was got it After cutting the cured thermosetting resin film into 130 × 40 mm, the PET film was peeled off to prepare a sample for measuring relative permittivity and dielectric loss tangent. The dielectric constant (ε) and the dielectric loss tangent (tan δ) of the sample for measurement were measured at a dielectric resonance frequency of 1.9 GHz by a split post dielectric resonator (SPDR). It is preferable that the dielectric constant is 3.0 or less and the dielectric loss tangent is 0.0040 or less. The results are shown in Tables 1 and 2. Similarly, the dielectric constant (ε) of component (C) used in the examples was measured.

<3. Peel strength test>

1. In the same way as in the flame retardancy test, the thermosetting resin composition was applied on a PET film having a thickness of 50 μm treated with a release agent so that the dry coating film had a film thickness of 25 ± 5 μm, and the resulting thermosetting resin film was dried to 100 × 100 mm. It cut|disconnected and peeled the PET film. A 12 μm-thick copper foil glossy surface was laminated on one side of the peeled thermosetting resin film and a 12 μm-thick polyimide film was laminated on the other side, and press cured with a vacuum press (180° C. × 60 minutes, pressure: 0.5 MPa). ) and adhered, and a sample for a peel strength test was produced. The prepared sample for a peel strength test was cut to a width of 10 mm, and the copper foil and the polyimide film were peeled off using an autograph to measure the peel strength. For the measurement results, an 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 gave good results in terms of flame retardancy, relative permittivity (ε), and dielectric loss tangent (tan δ). Although not described in the table, the relative permittivity (ε) of all components (C) was 2.9 or less. Further, in Example 1, the relative permittivity (ε) when the flame retardant ((A) component + (B) component) is subtracted is 2.5, the dielectric loss tangent (tan δ) is 0.0028, and the relative permittivity (ε) due to the addition of the flame retardant is ), the increase in dielectric loss tangent (tanδ) was small. On the other hand, Comparative Example 1 containing a large amount of component (A) and not using component (B) had poor flame retardancy test results. Comparative Example 2 using the same amounts of (A) and (B) had poor flame retardancy test results. Comparative Example 3 in which the total of component (A) and component (B) was less than 45 parts by mass with respect to 100 parts by mass of component (C) had a poor flame retardancy test result. Comparative Example 4 using ammonium polyphosphate instead of component (A) and component (B) had high dielectric constant and dielectric loss tangent. Instead of component (A), Comparative Example 5 using polyphosphate melamine/melam/melem double salt and Comparative Example 6 using phosphaphenanthrene-based compound (1) had poor flame retardancy test results, relative permittivity and dielectric loss tangent were high. Comparative Example 7 using the phosphaphenanthrene-based compound (2) instead of component (A) had poor flame retardancy test results. Comparative Example 8 using the phosphazene compound (1) instead of component (A) had a high dielectric loss tangent. Comparative Example 9 using the phosphazene compound (2) instead of component (A) had poor flame retardancy test results and a high dielectric loss tangent.

As can be seen from Table 3, Examples 1 and 4 had high peel strength. On the other hand, Comparative Example 10 containing a large amount of component (A) and not using component (B) had low peel strength. In addition, although not described in Table 3, the peeling strengths of Examples 1 to 7 were all 5.0 N/cm or more.

The thermosetting resin composition of the present invention does not use a halogen-based flame retardant, uses a material having excellent dielectric properties, can form an insulating film having high flame retardancy and high adhesion, 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 the cured product of the thermosetting resin composition or the cured product of the thermosetting resin film has excellent dielectric properties and high flame retardancy.

Claims (6)

(A) bisdiaryl phosphate;
(B) melamine cyanurate;
(C) (C1) a resin having a relative permittivity of 2.9 or less at a frequency of 1.9 GHz, including a thermosetting resin and (C2) a styrenic block copolymer in which unsaturated double bonds in the main chain of the molecule are hydrogenated;
(C) The total of component (A) and component (B) relative to 100 parts by mass of component is 45 parts by mass or more,
The content of component (A) is 60 to 85 parts by mass relative to 100 parts by mass of the total of component (A) and component (B),
Component (C1) contains a resin having a styrene group at least at its terminal;
The content of component (C1) is 15 to 55 parts by mass relative to 100 parts by mass of component (C),
A thermosetting resin composition characterized in that the content of component (C2) is 40 to 80 parts by mass with respect to 100 parts by mass of component (C). According to claim 1,
A thermosetting resin composition having a relative dielectric constant of 3.0 or less at a frequency of 1.9 GHz. According to claim 1 or 2,
(A) The thermosetting resin composition whose component is bisdisylenyl phosphate. A thermosetting resin film using the thermosetting resin composition of claim 1 or 2. A printed wiring board using a cured product of the thermosetting resin composition according to claim 1 or 2 or a cured product of the thermosetting resin film according to claim 4. A semiconductor device using a cured product of the thermosetting resin composition according to claim 1 or 2 or a cured product of the thermosetting resin film according to claim 4.