KR20210098990A - Resin composition for millimeter wave substrates, adhesive film for millimeter wave substrates, millimeter wave substrates, millimeter wave radar substrates, and semiconductor devices - Google Patents

Abstract

To provide a resin composition for millimeter wave substrates, in which a cured product of the resin composition is excellent in high frequency characteristics, has a small temperature dependence of tan ?, and can be used as an insulator for millimeter wave radars excellent in flame retardancy. A resin composition comprising (A) a hydrogenated styrene-based elastomer, (B) a crosslinkable compound having a biphenyl skeleton, and (C) a flame retardant comprising a metal phosphinic acid salt, wherein the component (C) comprises the component (A) and It is 15-50 mass parts with respect to a total of 100 mass parts of (B) component and (C) component, and the rate of change of the value at 120 degreeC with respect to the value at 25 degreeC of the dielectric loss tangent at 10GHz of hardened|cured material is 30% It is a resin composition for millimeter wave board|substrates characterized by the following.

Description

Resin composition for millimeter wave substrates, adhesive film for millimeter wave substrates, millimeter wave substrates, millimeter wave radar substrates, and semiconductor devices

The present invention relates to a resin composition for a millimeter wave substrate, an adhesive film for a millimeter wave substrate, a millimeter wave substrate, a millimeter wave radar substrate, and a semiconductor device.

Generally, in a printed wiring board for a high frequency use, a thing with small transmission loss is calculated|required. Conventionally, even in high-frequency applications, it is sufficient if the transmission loss in the 1GHz band is small, and in the adhesive layer of the printed wiring board, the coverlay, or the substrate itself, if the value of the dielectric loss tangent (tanδ), which is an index of the degree of transmission loss, is at a level of 0.01 or less, it is a problem It didn't happen. For this reason, it was allowed even if the value of tan δ slightly fluctuated (drift) due to temperature change. For example, when the value of tanδ at room temperature is 0.0100 and the value at high temperature is 0.0110, the amount of change is 0.0010, and the rate of change of tanδ is within 10%.

However, in recent years, characteristics in a high frequency band of 3 GHz or more have been demanded, and in order to reduce transmission loss, for example, a smaller value such as 0.003 or less for tan δ is required. As a result, even with a small change in the tanδ value, the rate of change of tanδ is large. For example, when the value of tanδ at room temperature is 0.0030 and the value at high temperature is 0.0040, the amount of change is 0.0010, but the rate of change of tanδ is 33.3% grows to For this reason, a material with a smaller rate of change of tan δ with a change in temperature has come to be demanded.

In particular, in the case of substrates for millimeter wave circuits (hereinafter referred to as millimeter wave boards), there is a demand for a higher frequency band and a small rate of change of tanδ with temperature change (that is, a material with small temperature dependence of tanδ). become stricter There are similarly strict requirements for an on-vehicle millimeter wave radar using a millimeter wave radar board (hereinafter referred to as millimeter wave radar board).

Moreover, in addition to the request|requirement for the temperature dependence of tan-delta being small in a board|substrate use, further flame retardance may be calculated|required. In this case, the use of a flame retardant is necessary, but now it is a premise that it is non-halogen, so a halogen-based flame retardant cannot be used.

Here, as "a resin composition for a printed wiring board that exhibits excellent stability with excellent dielectric properties in a high frequency band and low drift of dielectric properties with respect to temperature changes" (paragraphs 0012 and 0015 of Patent Document 1, etc.), "molecular A resin composition for a printed wiring board, comprising: a cyanate ester compound and/or a prepolymer thereof having two or more cyanato groups in the molecule; and an epoxy resin containing at least one epoxy resin having a biphenyl skeleton in the molecule.” This is disclosed (patent document 1).

However, this resin composition for a printed wiring board has a high relative permittivity (ε) at 25°C of 3.5 or more and a value of tan δ of 0.004 or more, so even if the temperature dependence of tan δ is small, for example, use in millimeter wave substrate applications. is difficult In addition, the specifically disclosed flame retardant is a halogen-based flame retardant.

Japanese Patent Laid-Open No. 2010-212689

The present invention has been made in view of the above circumstances, and its object is that the cured product of the resin composition has excellent high-frequency characteristics, has a small temperature dependence of tanδ, and can be used as an insulator for millimeter wave substrates with excellent flame retardancy. To provide a resin composition for a substrate.

The present invention relates to a resin composition for a millimeter wave substrate, an adhesive film for a millimeter wave substrate, a millimeter wave substrate, a millimeter wave radar substrate, and a semiconductor device, which have solved the above problems by having the following structures.

[1] A resin composition comprising (A) a hydrogenated styrene-based elastomer, (B) a crosslinkable compound having a biphenyl skeleton, and (C) a flame retardant comprising a metal phosphinic acid salt,

(C) component is 15-50 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C)component,

The resin composition for millimeter wave substrates characterized in that the rate of change of the value at 120°C with respect to the value at 25°C of the dielectric loss tangent at 10 GHz of the cured product is 30% or less.

[2] The resin composition for millimeter wave substrates according to the above [1], wherein the metal phosphinic acid salt of component (C) is 5 parts by mass or more.

[3] The resin composition for millimeter wave substrates according to the above [1] or [2], wherein the dielectric loss tangent at 10 GHz is 0.0030 or less.

[4] The resin composition for millimeter wave substrates according to any one of [1] to [3], wherein the component (A) is 50 to 80 parts by mass based on 100 parts by mass in total of the component (A) and the component (B). .

[5] The resin composition for millimeter wave substrates according to any one of [1] to [4], wherein the component (A) is a styrene-ethylene/butylene-styrene block copolymer.

[6] An adhesive film for millimeter wave substrates comprising the resin composition for millimeter wave substrates according to any one of [1] to [5].

[7] A millimeter wave substrate comprising a cured product of the resin composition for millimeter wave substrates according to any one of [1] to [5].

[8] A millimeter wave radar substrate comprising a cured product of the resin composition for millimeter wave substrates according to any one of [1] to [5].

[9] A semiconductor device comprising the millimeter wave substrate according to the above [7] or the millimeter wave radar substrate according to the above [8].

According to the present invention [1], there is provided a resin composition for millimeter wave substrates, which can be used as an insulator for millimeter wave boards, in which the cured product of the resin composition has excellent high frequency characteristics, low temperature dependence of tanδ, and excellent flame retardancy. can do.

ADVANTAGE OF THE INVENTION According to this invention [7], it is excellent in a high frequency characteristic, the temperature dependence of tan-delta is small, and the millimeter-wave board|substrate excellent in flame retardance can be provided. ADVANTAGE OF THE INVENTION According to this invention [8], it is excellent in a high frequency characteristic, and the temperature dependence of tan-delta is small, and the millimeter-wave radar substrate excellent in flame retardance can be provided.

According to the present invention [9], there is provided a highly reliable semiconductor device comprising a millimeter wave substrate or millimeter wave radar substrate (hereinafter also referred to as a substrate) having excellent high frequency characteristics, small temperature dependence of tanδ, and excellent flame retardancy. can provide

EMBODIMENT OF THE INVENTION Hereinafter, preferred embodiment of this invention is described in detail. However, this invention is not limited to the following embodiment. In addition, in this specification, the frequency range used for a millimeter-wave board|substrate or millimeter-wave radar board shall refer to 3GHz - 300GHz.

[Resin composition for millimeter wave substrate]

The resin composition for milliwave substrates (hereinafter referred to as resin composition for substrates) of the present invention comprises (A) a hydrogenated styrene-based elastomer, (B) a crosslinkable compound having a biphenyl skeleton, and (C) a metal phosphinic acid salt. As a resin composition comprising a flame retardant comprising:

(C) component is 5-50 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C)component,

It is characterized in that the rate of change of the value at 120°C with respect to the value at 25°C of the dielectric loss tangent at 10GHz of the cured product is 30% or less.

The hydrogenated styrene-based elastomer as component (A) contributes to film properties, heat resistance, and the like. In addition, it provides excellent electrical properties, low dielectric constant, and low dielectric loss tangent in a high frequency band. In addition, the temperature dependence of tan δ is small. Moreover, since (A) component has moderate flexibility which the resin composition for board|substrates after hardening can relieve|moderate stress from the outside, it can relieve|moderate the stress which arises in a board|substrate. As component (A), styrene-ethylene/butylene-styrene block copolymer (SEBS), styrene-ethylene/propylene-styrene block copolymer (SEPS), styrene-(ethylene-ethylene/propylene)-styrene block copolymer ( SEEPS), and a styrene-ethylene/butylene-styrene block copolymer (SEBS) is preferable from the viewpoint of heat resistance. It is preferable that the weight average molecular weights of (A) component are 30,000-200,000. Let the weight average molecular weight be the value using the analytical curve by standard polystyrene by the gel permeation chromatography method (GPC). (A) A component may be individual or may use 2 or more types together.

The crosslinkable compound which has a biphenyl skeleton as component (B) can make Tg of hardened|cured material high, can make it hard to produce the change with time of the resin composition for board|substrates after hardening, and can maintain long-term reliability of a board|substrate. In addition, the temperature dependence of tan δ is small. Examples of the crosslinkable compound having a biphenyl skeleton include a polyether compound having a phenyl group to which a vinyl group is bonded at both ends (hereinafter referred to as modified PPE), an epoxy resin having a biphenyl skeleton, and the like. Since the number of the hydrophilic groups in resin is small, the epoxy resin which has modified PPE or a biphenyl skeleton has small hygroscopicity and is excellent in moisture resistance. Moreover, they are excellent in insulation, and even if the thickness of the board|substrate formed from the resin composition for board|substrates is thin, the reliability of a board|substrate can be maintained.

As a polyether compound having a phenyl group bonded to a vinyl group at both terminals, Formula (1):

(During the meal,

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , and R ₇ may be the same or different and represent a hydrogen atom, a halogen atom, an alkyl group, a halogenated alkyl group or a phenyl group,

-(OXO)- is represented by Structural Formula (2), wherein R ₈ , R ₉ , R ₁₀ , R ₁₄ , R ₁₅ may be the same or different, and represent 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 represent a hydrogen atom, a halogen atom, an alkyl group having 6 or less carbon atoms, or a phenyl group;

-(YO)- represents one type of structure represented by Structural Formula (3), or two or more types of structures represented by Structural Formula (3) arranged at random, wherein R ₁₆ and R ₁₇ may be the same or different, and halogen an 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, an alkyl group or a phenyl group having 6 or less carbon atoms,

Z is an organic group having 1 or more carbon atoms, and in some cases contains an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom,

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

and c and d represent an integer of 0 or 1) (hereinafter referred to as modified PPE).

In the structural formula (2) for -(OXO)- of the modified PPE represented by the formula (1), R ₈ , R ₉ , R ₁₀ , R ₁₄ , R ₁₅ are preferably an alkyl group having 3 or less carbon atoms, and R ₁₁ , R ₁₂ , and R ₁₃ are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms. Structural formula (4) is mentioned specifically,.

In the structural formula (3) for -(YO)-, R ₁₆ and R ₁₇ are preferably an alkyl group having 3 or less carbon atoms, and R ₁₈ , R ₁₉ are preferably a hydrogen atom or an alkyl group having 3 or less carbon atoms. Structural formula (5) or (6) is mentioned specifically,.

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

a and b represent the integer of 0-300 in which at least either one is not 0, Preferably the integer of 0-30 is represented.

The modified PPE of Formula (1) whose number average molecular weights are 1000-4500 is preferable. A more preferable number average molecular weight is 1000-3000. The said modified PPE may be used individually or in combination of 2 or more types.

An epoxy resin having a biphenyl skeleton is preferable from the viewpoint of improving the adhesive strength of the resin composition for substrates and making the temperature dependence of tan δ smaller than that of epoxy resins having other structures. Moreover, it is preferable that epoxy equivalent is 150-300, and does not contain a hydroxyl group in a molecule|numerator. However, the epoxy resin which has a biphenyl skeleton does not need to be contained. In a certain aspect, the resin composition for board|substrates does not contain an epoxy resin substantially.

It is preferable when (B) component further contains an initiator or a hardening|curing agent. Examples of the initiator for modified PPE include an organic peroxide, and the curing agent for an epoxy resin having a biphenyl skeleton include a phenol-based curing agent, an amine-based curing agent, an imidazole-based curing agent, and an acid anhydride-based curing agent. In particular, if it is an imidazole type hardening|curing agent, it is preferable from a viewpoint of making small the temperature dependence of sclerosis|hardenability with respect to the epoxy resin which has a biphenyl skeleton, adhesiveness, and tan δ. (B) A component may be individual or may use 2 or more types together.

(C) As a flame retardant containing a phosphinic acid metal salt as a component, M _e (POOR ²⁰ R ²¹ ) _f (wherein M is Li, Na, K, Mg, Ca, Sr, Ba, Al, Ge, Sn, Sb, Bi, Zn, Ti, Zr, Mn, Fe, or Ce, R ²⁰ and R ²¹ are each an aliphatic hydrocarbon group or aromatic hydrocarbon group having 1 to 5 carbon atoms, and e and f are integers from 1 to 9) can be heard Among these, aluminum phosphinate is preferable, aluminum dialkylphosphinate is more preferable, and aluminum diethylphosphinate is still more preferable from a viewpoint of a flame retardance and a viewpoint of reducing the temperature dependence of tan ?.

(C) As a flame retardant which can be used other than a phosphinic acid metal salt as a component, it is non-halogen, and the flame retardant with small temperature dependence of tan-delta is mentioned. Specific examples thereof include biphenolbis-disylenyl phosphate and 10-(2,5-dihydroxyphenyl)-10-H-9-oxa-10-phosphaphenanthrene-10-oxide. (C) A component may be individual or may use 2 or more types together.

(A) It is preferable in it being 50-80 mass parts with respect to a total of 100 mass parts of (A) component and (B) component, and, as for (A) component, it is more preferable in it being 55-80 mass parts. When content of (A) component becomes more than content of (B) component, the peeling strength of the resin composition for board|substrates becomes high easily, and heat-resistant reliability (for example, at 125 degreeC for 1000 hours or more) becomes easy to improve.

Moreover, (A) component is preferable in it being 32.5-70 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C)component, It is preferable in it being 40-70 mass parts, It is preferable in it being 40-70 mass parts It is more preferable in it being 64 mass parts.

(C)component is 15-50 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C)component from a flame retardance provision and a viewpoint of a high frequency characteristic.

Here, when (C)component is only a phosphinic acid metal salt, it is preferable in it being 20-35 mass parts of phosphinic acid metal salts with respect to a total of 100 mass parts of (A) component, (B) component, and (C)component.

When (C) component consists of a phosphinic acid metal salt and another flame retardant, a phosphinic acid metal salt is 5 mass parts or more and 15 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C)component. Less than, 20-40 mass parts of other flame retardants, and the sum total of the flame retardant which is (C)component is 25-50 mass parts, from a viewpoint of a flame retardance, a high frequency characteristic, adhesiveness, and heat resistance.

On the other hand, the resin composition for a substrate is an additive such as an inorganic filler, a silane coupling agent, an antifoaming agent, a dispersing aid, an antioxidant, an antifoaming agent, a leveling agent, a thixotropic agent, an anti-blooming agent, an anti-blocking agent, etc. Organic solvents may be included.

As an inorganic filler, a general inorganic filler can be used from a viewpoint of improving the physical property of hardened|cured material. _{SiO 2} in terms of low coefficient of thermal expansion _{, talc, kaolin, BaSO 4} , CaCO ₃ , MgO, Al ₂ O ₃ , SiO ₂ , AlN, BN, diamond filler, ZnO, SiC in terms of obtaining desired properties of the cured product It is preferable that it is at least 1 or more types of inorganic fillers selected from. These fillers may be surface-treated.

Although the average particle diameter of the inorganic filler (if not granular, its average maximum diameter) is not particularly limited, it is preferably 0.05 to 20 µm in order to prevent a decrease in moisture resistance of the cured resin product due to moisture absorption on the surface of the filler particles, and It is preferable in order to obtain a coating film of thickness. When the average particle diameter of the inorganic filler is less than 0.05 µm, since the specific surface area is large, the amount of moisture absorbed to the surface of the inorganic filler increases, and there is a possibility that the moisture resistance of the cured resin product may deteriorate. If it is more than 20 micrometers, compared with the thickness of a required coating film, it is too large, and there exists a possibility that the film thickness of a desired thickness may not be obtained. In addition, in use in a substrate of a fine pattern, since the filler is too large compared to the size of the pattern, there is a fear that the dielectric loss may increase due to the localization of the filler material and resin on the pattern. The average particle diameter of the inorganic filler is more preferably 1 to 10 µm, and further preferably the maximum particle diameter is 10 µm or less. By setting the maximum particle size to 10 µm or less, it becomes easy to prevent an increase in dielectric loss in a frequency band of 10 GHz or more. Here, the average particle diameter and the maximum particle diameter of the inorganic filler are measured with a laser scattering diffraction type particle size distribution analyzer. An inorganic filler may be individual or may use 2 or more types together.

Examples of the organic solvent include aromatic solvents such as toluene and xylene, ketone solvents such as methyl ethyl ketone and methyl isobutyl ketone, and further, cyclohexanone, dimethylformamide, 1-methyl- High boiling point solvents, such as 2-pyrrolidone, etc. are mentioned. The organic solvent may be used individually or in combination of 2 or more type. In addition, the usage-amount of the organic solvent is not specifically limited, What is necessary is just to adjust so that it may become each preferable viscosity according to the coating method of a resin composition. Specifically, an organic solvent can be used so that solid content may be 20-80 mass %.

The resin composition for substrates can be obtained by dissolving or dispersing the raw material containing the components (A) to (C) in an organic solvent. Although it is not specifically limited as an apparatus for dissolving or dispersing these raw materials, A stirrer equipped with a heating device, a dissolver, a grinder, a three roll mill, a ball mill, a planetary mixer, a bead mill, etc. can be used. . Moreover, you may use combining these apparatuses suitably.

The resin composition for board|substrates can be thermosetted for 30-180 minutes at 130-220 degreeC, for example. The resin composition for board|substrates can select suitably according to the desired application|coating method that the value measured at 10 rpm and 25 degreeC using an E-type viscometer is a viscosity of 0.1-100 Pa.s.

As for the resin composition for board|substrates, the rate of change of the value at 120 degreeC with respect to the value at 25 degreeC of tan-delta in 10GHz of hardened|cured material is 30 % or less. When the rate of change of the value at 120°C with respect to the value at 25°C of tanδ at 10GHz is greater than 30%, the market demand is not satisfied. The rate of change of the value at 120°C with respect to the value at 25°C of tan δ at 10 GHz is preferably 20% or less, and more preferably 10% or less.

From the viewpoint of use in the frequency band, the resin composition for substrates preferably has a dielectric loss tangent of 0.0030 or less at 10 GHz. The resin composition for a board|substrate can be used for the adhesive layer of a wiring board, a coverlay, and board|substrate itself.

[Products using the resin composition for millimeter wave substrates]

The adhesive film for millimeter wave substrates of the present invention includes the above-described resin composition for millimeter wave substrates. This adhesive film for millimeter wave board|substrates is formed with the resin composition for board|substrates.

After apply|coating the resin composition for board|substrates to a desired support body, the adhesive film for millimeter wave board|substrates can be obtained by drying. The support body is not specifically limited, Organic films, such as metal foils, such as copper and aluminum, a polyester resin, a polyethylene resin, a polyethylene terephthalate resin, etc. are mentioned. The support may be subjected to a release treatment with a silicone-based compound or the like.

Although the method of apply|coating the resin composition for board|substrates to a support body is not specifically limited, From a viewpoint of thin film formation and film thickness control, the micro gravure method, the slot die method, and the doctor blade method are preferable. By the slot die method, the adhesive film for millimeter wave board|substrates whose thickness after thermosetting is 10-300 micrometers, for example can be obtained.

Drying conditions can be suitably set according to the kind and quantity of the organic solvent used for the resin composition for board|substrates, the thickness of application|coating, etc., For example, it can be set as about 1-30 minutes at 50-120 degreeC. Thus, the obtained adhesive film for insulating millimeter wave board|substrates has favorable storage stability. On the other hand, the adhesive film for millimeter wave substrates can be peeled from a support body at a desired timing.

The adhesive film for millimeter wave board|substrates can be thermosetted for 30-180 minutes at 130-220 degreeC, for example.

It is preferable in it being 10 micrometers or more and 300 micrometers or less, and, as for the thickness of the adhesive film for millimeter wave board|substrates, it is more preferable in it being 20 micrometers or more and 200 micrometers or less. If it is less than 10 micrometers, there exists a possibility that desired insulation, the intensity|strength of a coating film, and durability may not be acquired. When it exceeds 300 micrometers, the stress at the time of hardening may become large, and there exists a possibility that problems, such as bending of a board|substrate, may arise.

The millimeter-wave board|substrate of this invention contains the hardened|cured material of the resin composition for millimeter-wave board|substrates mentioned above. That is, it includes a cured product of the above-described adhesive film for millimeter wave substrates.

The millimeter wave radar substrate of the present invention includes a cured product of the above-described resin composition for millimeter wave substrates. That is, it includes a cured product of the above-described adhesive film for millimeter wave substrates.

The semiconductor device of the present invention includes the millimeter wave substrate or the millimeter wave radar substrate.

Example

Although an Example demonstrates this invention, this invention is not limited to these. In addition, in the following examples, parts and % represent mass parts and mass % unless otherwise indicated.

The raw materials used in the Examples and Comparative Examples shown in Tables 1-3 are shown below.

G1652MU: Hydrogenated styrene-based elastomer SEBS manufactured by Kraton Polymer

OPE-2St 2200: Styrene-terminated PPE oligomer manufactured by Mitsubishi Gas Chemical (Molecular weight: Mn 2200)

YX4000HK: Biphenyl skeleton epoxy resin manufactured by Mitsubishi Chemical

OP935: Aluminum diethylphosphinate (aluminum phosphinate) manufactured by Clariant Chemicals represented by the following formula:

KBE-846: Silane coupling agent bis(triethoxysilylpropyl)tetrasulfide manufactured by Shin-Etsu Chemical

KBM-573: Silane coupling agent N-phenyl-3-aminopropyltrimethoxysilane manufactured by Shin-Etsu Chemical

Percumyl D: Nichiyu Organic Peroxide Dicumyl Peroxide

EH-2021: Modified imidazole manufactured by ADEKA

FB-3SDX: spherical silica filler manufactured by Denka (average particle size: 3.4 µm)

PX-200: Resorcinol bis-disylenyl phosphate manufactured by Daihachi Chemical Industry represented by the following formula:

PX-202: Biphenol bis-disylenyl phosphate manufactured by Daihachi Chemical Industry represented by the following formula:

TPP: Triphenyl phosphate manufactured by Daihachi Chemical Industry represented by the following formula:

FP-600: Bisphenol A bis-diphenyl phosphate manufactured by ADEKA represented by the following formula:

FP-100: phenoxycyclophosphazene manufactured by Fushimi Pharmaceutical represented by the following formula:

HCA-HQ-HS: 10-(2,5-dihydroxyphenyl)-10-H-9-oxa-10-phosphaphenanthrene-10-oxide manufactured by Sanco represented by the following formula:

HCA: 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide manufactured by Sanco represented by the following formula:

TR2003: Non-hydrogenated styrene-based elastomer SBS manufactured by JSR

[Examples 1 to 9, Comparative Examples 1 to 11]

After measuring each component by the formulation (parts by mass) shown in Tables 1 to 3, (A) component or (A') component, and (B) component are put into the heating stirrer to which a predetermined amount of toluene was previously added, , while rotating the stirring blade at a rotational speed of 35 rpm at 70° C. and atmospheric pressure, dissolution mixing was performed for 2 hours. Then, after cooling to room temperature, (C)component, (C') component, and another component were thrown in, the stirring blade was rotated at the rotation speed of 60 rpm, and stirring and mixing were performed for 1 hour. Next, a predetermined amount of toluene was added to the stirred material to obtain a viscosity suitable for coating, followed by stirring and dilution. Then, the resin composition was disperse|distributed using the wet atomization apparatus (The Yoshida Machinery Kogyo Co., Ltd. make, model number: Nanomizer MN2-2000AR).

The coating solution containing the resin composition obtained in this way is applied to one side of a support (PET film subjected to release treatment) and dried at 100° C. got it

[One. Flame-retardant evaluation]

Based on the VTM combustion test method of UL94, the test was done and the flame retardance was judged. The obtained adhesive film for millimeter wave board|substrates was heat-hardened at 200 degreeC x 60 minutes, 10 kgf, and after peeling from a support body, it cut out to the magnitude|size of 200 ± 5 mm in length x 50 ± 1 mm in width to obtain a test piece. Using the 50 mm side of the test piece as the base, draw a marked line with a pen along the width at a position 125 mm from the base, wrap the test piece with a rod with a diameter of 12.7 ± 0.5 mm in the longitudinal direction of the test piece, and wrap the test piece above the marked line with pressure-sensitive tape After affixing with the , the rod was pulled out, and the upper end of this cylindrical test piece was sealed with a pressure-sensitive tape so that a chimney effect would not occur. The upper end of this test piece was held by the clamp set on the stand, and the test piece was held vertically. An inner diameter: 9.5 ± 0.3 mm (0.374 ± 0.012 inch) was ignited on a Bunsen burner, and the salt was adjusted to be a blue salt without yellow, and a height: 19 mm: (3/4 inch). This salt is irradiated to the center of the lower end of the cylindrical test piece so that the distance from the burner port is 9.5 mm (3/8 inch), the first contact is carried out for 3±0.5 seconds, and then removed, and the combustion time of the test piece included) was measured. Immediately after extinguishing, the second contact flame was carried out for 3±0.5 seconds, then removed, and the combustion time (including the time of the embers) was measured. For each Example and Comparative Example, a test is performed with five test pieces, respectively, and those that satisfy the determination conditions of VTM-0 shown below are judged to be VTM-0 equivalent and passed, and the result is expressed as VTM-0 equivalent. The thing was set to "○", and the thing which was not was made into "x".

<VTM-0 Judgment Conditions>

(1) The combustion time after the first or second color transfer of each test piece is 10 seconds or less.

(2) The sum of the burning times of the 1st and 2nd times of 5 test pieces is 50 seconds or less.

(3) The total of the combustion time after the color transfer of the 2nd time is 30 second or less.

(4) Combustion does not reach the mark.

(5) There is no ignition of the cotton wool (installed below the test piece) by a falling object at the time of combustion.

※ However, since there was no falling object during combustion, no attention was paid to ignition of the cotton wool.

[2. Evaluation of dielectric constant (ε) and dielectric loss tangent (tanδ)]

After peeling the adhesive film for millimeter wave substrates from the support, it is laminated to a thickness of about 1 mm, heat-cured at 200° C. × 60 minutes, 10 kgf, and then cut to a width: about 1 mm, length: about 20 mm to form a rod. was used as a test piece of The dimension of this test piece was measured, and the dielectric constant (epsilon) and dielectric loss tangent (tan-delta) in 10 GHz and 25 degreeC were measured by the cavity resonator in a precision thermostat. The dielectric constant is preferably 3.5 or less and the dielectric loss tangent is preferably 0.003 or less.

[3. Evaluation of temperature dependence (temperature characteristics) of dielectric constant (ε) and dielectric loss tangent (tanδ)]

[2. Evaluation of dielectric constant (ε) and dielectric loss tangent (tanδ)], using a cavity resonator in a precision thermostat heated to 120 ° C. The tangent (tanδ) was measured. From this value, the change rate % with respect to the measured value at 25 degreeC was calculated|required. The rate of change is preferably ±30% or less.

[4. Evaluation of Peel Strength]

Copper foil (CF-T9FZSV, manufactured by Fukuda Metal Foil Powder Industry Co., Ltd., thickness: 18 µm) on both sides of the adhesive film for millimeter wave substrates was bonded with the roughened surface inside, and the conditions were 200° C. × 60 minutes, 30 kgf with a press machine. press hardened in This test piece was cut out to 10 mm width, it peeled from the interface with copper foil with an autograph, and the peeling strength of 180 degrees was measured (based on JISK6854-2). The average value of n=5 was made into the measured value. A peeling strength is preferable in it being 4.5 (unit: (N/cm)) or more.

[5. Evaluation of Solder Heat Resistance]

[4. Evaluation of peeling strength] similarly, what was hardened by bonding copper foil was cut out to 30 x 30 mm, and it was set as the test piece. This was placed on the surface of a solder bath heated to 260° C. for 60 seconds, and the presence or absence of expansion was visually observed. It tested with n=3, and made "(circle)" the thing in which expansion|swelling did not generate|occur|produce, and the thing which expansion|swelling generate|occur|produced was made into "x".

The mixing|blending and evaluation result of an Example and a comparative example are shown to Tables 1-3. In Tables 1-3, a filler ratio is a volume ratio (Vol%) of a silica filler with respect to all components except toluene, Computing the specific gravity of a silica filler to 2.2, and the specific gravity of another component to 1.0. In addition, an elastomer ratio is the mass ratio (%) of (A) component with respect to a total of 100 mass parts of (A) component and (B) component. Example 1 was used as a reference formulation. Example 1 makes the ratio of (A) component: (B) component 65:35 with respect to a total of 100 mass parts of (A) component and (B) component, the compounding quantity of (C)component is (A) With respect to a total of 100 mass parts of a component, (B) component, and (C) component, it shall be 30 mass parts, and it shall be 227 mass parts so that the compounding ratio of a silica filler may be 50 vol% (vol%), and KBE-846 as a silane coupling agent. (sulfide type) was used. Example 2 is obtained by subtracting the silica filler from the formulation of Example 1. Example 3 makes the compounding quantity of (C)component 20 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C)component, and (B) part of component (B) biphenyl skeleton epoxy replaced with resin. (A) Component: (B) The ratio of component is 60:(35:5). Example 4 sets the compounding quantity of (C)component into 50 mass parts with respect to a total of 100 mass parts of (A) component, (B)component, and (C)component. Example 5 sets the compounding quantity of (C)component into 15 mass parts with respect to a total of 100 mass parts of (A) component, (B)component, and (C)component. Example 6 makes the compounding quantity of (C)component 20 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C)component, (A) component: The ratio of (B) component is 80:20. Example 7 makes the compounding quantity of (C)component 20 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C)component, (A) component: The ratio of (B) component is 55:45. Example 8 makes the compounding quantity of (C)component 20 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C)component, and the silane coupling agent which is another component is KBM-573 (amino type). Example 9 uses two types of (C) flame retardants together. More specifically, the compounding quantity of (C) component is 45 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component, and a phosphinic acid metal salt is 5 mass parts, another flame retardant (HCA-HQ-HS) It is the Example combined with 40 mass parts.

As can be seen from Table 1, in all of Examples 1 to 9, the flame retardancy is equivalent to VTM-0, the temperature dependence of ε and ε is low, the temperature dependence of tanδ and tanδ is also small, the peel strength is high, and the solder heat resistance is high. This was a good result.

As can be seen from Table 2, Comparative Examples 1 to 7 substitute the component (C) of Example 1 with the same content of another phosphorus-based flame retardant (component (C')). In all of Comparative Examples 1 to 7, the flame retardancy did not achieve VTM-0, and was inferior to that of Example 1. However, in Comparative Example 2 using PX-202 and Comparative Example 6 using HCA-HQ-HS, the value of tan δ at 25°C was small, and the temperature characteristic was also good (the temperature dependence was small). However, the temperature characteristics of Comparative Example 1, Comparative Example 3, Comparative Example 4, Comparative Example 5, and Comparative Example 7 were very bad (temperature dependence was large), and Comparative Example 3, Comparative Example 4, and Comparative Example 5 had tan δ. The value at 25[deg.] C. exceeded 0.003, which was an unusable level for millimeter wave substrate applications. Moreover, the peeling strength of Comparative Example 4 and Comparative Example 7 was low.

As can be seen from Table 3, in Comparative Example 8, the component (A) of Example 1 was substituted with an unhydrogenated styrenic elastomer (component (A')), and the temperature characteristic of tan δ was poor (temperature dependence was large). ). Comparative Example 9 made the compounding quantity of (C) component of Example 1 into 55 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component, and solder heat resistance was Example 1 It was inferior, and the peel strength was low. In Comparative Example 10, the compounding amount of the component (C) of Example 1 was 10 parts by mass with respect to a total of 100 parts by mass of the component (A), component (B) and component (C), and the flame retardancy was VTM-0. did not achieve Comparative Example 11 does not mix a flame retardant except for component (C) in Example 1, and the flame retardancy did not achieve VTM-0. On the other hand, the temperature characteristic was favorable (the temperature dependence was small).

As described above, in the resin composition for millimeter wave substrates of the present invention, the cured product of the resin composition has excellent high frequency characteristics, low temperature dependence of tanδ, and excellent flame retardancy, and is used as an insulator for millimeter wave radar. This is possible, and it is very useful for manufacturing highly reliable millimeter wave substrates, millimeter wave radar boards, and semiconductor devices.

Claims (9)

A resin composition comprising (A) a hydrogenated styrene-based elastomer, (B) a crosslinkable compound having a biphenyl skeleton, and (C) a flame retardant comprising a metal phosphinic acid salt,
(C) component is 15-50 mass parts with respect to a total of 100 mass parts of (A) component, (B) component, and (C) component,
The resin composition for millimeter wave substrates characterized in that the rate of change of the value at 120°C with respect to the value at 25°C of the dielectric loss tangent at 10 GHz of the cured product is 30% or less. The method of claim 1,
(C) The resin composition for millimeter wave board|substrates in which the phosphinic acid metal salt of component is 5 mass parts or more. 3. The method according to claim 1 or 2,
A resin composition for millimeter wave substrates having a dielectric loss tangent of 0.0030 or less at 10 GHz. 4. The method according to any one of claims 1 to 3,
(A) The resin composition for millimeter wave board|substrates whose component is 50-80 mass parts with respect to a total of 100 mass parts of (A) component and (B) component. 5. The method according to any one of claims 1 to 4,
(A) The resin composition for millimeter wave board|substrates whose component is a styrene-ethylene/butylene-styrene block copolymer. An adhesive film for a millimeter wave substrate comprising the resin composition for millimeter wave substrates according to any one of claims 1 to 5. A millimeter wave substrate comprising a cured product of the resin composition for millimeter wave substrates according to any one of claims 1 to 5. A millimeter wave radar substrate comprising a cured product of the resin composition for millimeter wave substrates according to any one of claims 1 to 5. A semiconductor device comprising the millimeter wave substrate of claim 7 or the millimeter wave radar substrate of claim 8 .