JP2021070752A - Low dielectric resin composition - Google Patents

Abstract

To provide a low dielectric resin composition that gives a cured product of low hardness while having a low relative dielectric constant and a low dielectric loss tangent.SOLUTION: A low dielectric resin composition contains (a) a maleimide compound having at least two maleimide groups in one molecule, (b) an organo hydrogen siloxane having at least two hydrosilyl groups in one molecule, and (c) a hydrosilylation catalyst.SELECTED DRAWING: None

Description

The present invention relates to a low dielectric resin composition.

In recent years, the speed and capacity of signals used in mobile communication devices such as mobile phones, their base station devices, servers, network infrastructure devices such as routers, and electronic devices such as large computers have been increasing year by year. .. Along with this, printed wiring boards mounted on these electronic devices are required to support high frequencies such as in the 20 GHz region, and low relative permittivity and low dielectric loss tangent substrate materials that can reduce transmission loss are required. There is. In addition to the electronic devices mentioned above, practical applications and practical plans for new systems that handle high-frequency wireless signals are in progress in the ITS field (automobiles, transportation system-related) and indoor short-range communication fields, and prints to be mounted on these devices. Low transmission loss substrate materials are also required for wiring boards.

Thermosetting resins such as modified polyphenylene ether resin, maleimide resin, and epoxy resin, and thermoplastic resins such as fluororesin, styrene resin, and liquid crystal polymer are known as materials having a low specific dielectric constant and low dielectric tangent. Patent Documents 1 to 6). However, all of these materials are hard and suitable for applications requiring high elasticity, high Tg, and high melting point such as printed wiring boards, but it has been difficult to reduce the hardness.

Japanese Unexamined Patent Publication No. 2019-001965 Japanese Unexamined Patent Publication No. 2019-099710 Japanese Unexamined Patent Publication No. 2018-028044 Japanese Unexamined Patent Publication No. 2018-177931 Japanese Unexamined Patent Publication No. 2018-135506 Japanese Unexamined Patent Publication No. 2011-032463

Therefore, an object of the present invention is to provide a low-dielectric resin composition that gives a cured product having a low hardness while having a low relative permittivity and a low dielectric loss tangent.

As a result of intensive studies to solve the above problems, the present inventors have found that the following low-dielectric resin composition can achieve the above object, and have completed the present invention.

（式（１）中、Ａは独立して環状構造を含む４価の有機基を示す。Ｂは独立してヘテロ原子を含んでもよい炭素数６以上のアルキレン基である。Ｑは独立してヘテロ原子を含んでもよい炭素数６以上のアリーレン基である。ＷはＢまたはＱで示される基を示す。ｎは０〜１００の数を、ｍは０〜１００の数を表す。）

（式（１’）中、ｎは２〜１０の数を表す。）

＜３＞
式（１）中のＡで示される有機基が下記構造式で示される４価の有機基のいずれかである＜２＞に記載の低誘電樹脂組成物。

（上記構造式中の置換基が結合していない結合手は、式（１）において環状イミド構造を形成するカルボニル炭素と結合するものである。）

＜４＞
式（１）中のＢが独立してヘテロ原子を含んでもよい炭素数６以上のアルキレン基であり、かつ炭素数５以上の脂肪族環を１個以上有する基である＜２＞または＜３＞に記載の低誘電樹脂組成物。

＜５＞
（ｂ）成分が下記式（２）で表されるオルガノハイドロジェンシロキサン
（Ｒ¹ ₃ＳｉＯ_1/2）_r（Ｒ¹ ₂ＳｉＯ_2/2）_s（Ｒ¹ＳｉＯ_3/2）_t（ＳｉＯ_4/2）_u （２）
（式（２）中、Ｒ¹は互いに独立に、水素原子、炭素数１〜１２の一価飽和炭化水素基、及び、炭素数６〜１２の芳香族炭化水素基から選ばれる基であり、Ｒ¹のうち少なくとも２個は水素原子である。ｒは０〜１００の数、ｓは０〜３００の数、ｔは０〜２００の数、ｕは０〜２００の数であり、２≦ｒ＋ｓ＋ｔ＋ｕ≦８００である。）
である＜１＞〜＜４＞のいずれか１つに記載の低誘電樹脂組成物。

＜６＞
式（２）中のＲ¹のうち少なくとも１個は炭素数６〜１２の芳香族炭化水素基である＜５＞に記載の低誘電樹脂組成物。

＜７＞
（ａ）成分中のマレイミド基の合計個数に対して（ｂ）成分中のヒドロシリル基の合計個数が０．４〜４．０である＜１＞〜＜６＞のいずれか１つに記載の低誘電樹脂組成物。
<1>
(A) A maleimide compound having at least two maleimide groups in one molecule,
(B) Organohydrogensiloxane having at least two hydrosilyl groups in one molecule, and
(C) A low-dielectric resin composition containing a hydrosilylation catalyst.

<2>
The low-dielectric resin composition according to <1>, wherein the component (a) is a maleimide compound represented by the following formula (1) or (1').

(In the formula (1), A independently represents a tetravalent organic group containing a cyclic structure. B is an alkylene group having 6 or more carbon atoms which may independently contain a hetero atom. Q is independently. It is an arylene group having 6 or more carbon atoms which may contain a hetero atom. W represents a group represented by B or Q. N represents a number from 0 to 100, and m represents a number from 0 to 100.)

(In equation (1'), n represents a number from 2 to 10.)

<3>
The low-dielectric resin composition according to <2>, wherein the organic group represented by A in the formula (1) is one of the tetravalent organic groups represented by the following structural formula.

(The bond to which the substituent in the above structural formula is not bonded is the one that bonds to the carbonyl carbon forming the cyclic imide structure in the formula (1).)

<4>
B in the formula (1) is an alkylene group having 6 or more carbon atoms which may independently contain a hetero atom, and is a group having one or more aliphatic rings having 5 or more carbon atoms <2> or <3. > The low-dielectric resin composition.

<5>
^{(B) Organohydrogensiloxane (R 1} ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO ₄ ) whose component is represented by the following formula (2) _{/ 2} ) _u (2)
(In the formula (2), R ¹ is a group selected from a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms independently of each other. At ^{least two of R 1} are hydrogen atoms. r is a number from 0 to 100, s is a number from 0 to 300, t is a number from 0 to 200, u is a number from 0 to 200, and 2 ≦ r + s + t + u. ≤800.)
The low-dielectric resin composition according to any one of <1> to <4>.

<6>
The low-dielectric resin composition according to <5>, wherein at least one ^{of R 1} in the formula (2) is an aromatic hydrocarbon group having 6 to 12 carbon atoms.

<7>
The description in any one of <1> to <6>, wherein the total number of hydrosilyl groups in the component (b) is 0.4 to 4.0 with respect to the total number of maleimide groups in the component (a). Low dielectric resin composition.

The low-dielectric resin composition of the present invention can give a cured product having a low hardness while having a low relative permittivity and a low dielectric loss tangent. Therefore, the low-dielectric resin composition of the present invention is useful as a printed wiring board, a coverlay film, an adhesive for a coverlay film, an adhesive for heat dissipation, an electromagnetic wave shield, and the like.

Hereinafter, the low-dielectric resin composition of the present invention will be described in detail.

（式（１）中、Ａは独立して環状構造を含む４価の有機基を示す。Ｂは独立してヘテロ原子を含んでもよい炭素数６以上のアルキレン基である。Ｑは独立してヘテロ原子を含んでもよい炭素数６以上のアリーレン基である。ＷはＢまたはＱで示される基を示す。ｎは０〜１００の数を、ｍは０〜１００の数を表す。）

（式（１’）中、ｎは２〜１０、好ましくは２〜５の数を表す。）
[(A) Maleimide compound having at least two maleimide groups in one molecule]
The maleimide compound of the component (a) is a main component of the low-dielectric resin composition of the present invention, and is a maleimide compound having at least two maleimide groups in one molecule. The maleimide compound is not particularly limited, but a maleimide compound represented by the following formula (1) or (1') is preferable.

(In the formula (1), A independently represents a tetravalent organic group containing a cyclic structure. B is an alkylene group having 6 or more carbon atoms which may independently contain a hetero atom. Q is independently. It is an arylene group having 6 or more carbon atoms which may contain a hetero atom. W represents a group represented by B or Q. N represents a number from 0 to 100, and m represents a number from 0 to 100.)

(In formula (1'), n represents a number of 2 to 10, preferably 2 to 5).

（上記構造式中の置換基が結合していない結合手は、式（１）において環状イミド構造を形成するカルボニル炭素と結合するものである。）
Here, the organic group represented by A in the formula (1) is a tetravalent organic group independently containing a cyclic structure, and in particular, it may be any of the tetravalent organic groups represented by the following structural formula. preferable.

(The bond to which the substituent in the above structural formula is not bonded is the one that bonds to the carbonyl carbon forming the cyclic imide structure in the formula (1).)

（上記構造式中の置換基が結合していない結合手は、式（１）において環状イミド構造を形成する窒素原子と結合するものである。）
Further, B in the formula (1) is an alkylene group having 6 to 60 carbon atoms which may independently contain a heteroatom, and preferably an alkylene group having 6 to 40 carbon atoms which may contain a heteroatom. It is a group having one or more aliphatic rings having 5 or more carbon atoms. Examples of B in the formula (1) include a linear alkylene group having 6 to 60 carbon atoms, an alkylene group having a branched chain, an alkylene group having an aliphatic ring, and the like. As the linear alkylene group represented by B in the formula (1), an alkylene group having 6 to 60 carbon atoms is preferable, an alkylene group having 8 to 40 carbon atoms is more preferable, and more specifically, − (CH). ₂ ) ₆ −, − (CH ₂ ) ₇ −, − (CH ₂ ) ₈ −, − (CH ₂ ) ₉ −, − (CH ₂ ) ₁₀ −, − (CH ₂ ) ₁₁ −, − (CH ₂ ) ₁₂ −, − (CH ₂ ) ₁₈ −, etc. can be mentioned. It is more preferable that B in the formula (1) is any of the alkylene groups having an aliphatic ring represented by the following structural formula.

(The bond to which the substituent in the above structural formula is not bonded is the one that bonds to the nitrogen atom forming the cyclic imide structure in the formula (1).)

（上記構造式中の置換基が結合していない結合手は、式（１）において環状イミド構造を形成する窒素原子と結合するものである。）
Q is an arylene group having 6 or more and 30 or less carbon atoms which may independently contain a heteroatom, and preferably an arylene group having 8 or more and 18 or less carbon atoms. It is more preferable that Q in the formula (1) is any of the arylene groups having an aromatic ring represented by the following structural formula.

(The bond to which the substituent in the above structural formula is not bonded is the one that bonds to the nitrogen atom forming the cyclic imide structure in the formula (1).)

N in the formula (1) is a number from 0 to 100, preferably a number from 0 to 70. M in the formula (1) is a number from 0 to 100, preferably a number from 0 to 70.

The weight molecular weight (Mw) of the maleimide compound is not particularly limited, but is preferably 300 to 50,000, more preferably 500 to 30,000, and even more preferably 600 to 20,000. Within this range, the maleimide compound can suitably react with the organohydrogensiloxane of the component (b) described later, and the cured product of the composition of the present invention has high strength.

The weight average molecular weight (Mw) referred to in the present specification refers to a weight average molecular weight using polystyrene as a standard substance measured by GPC measured under the following conditions.
[GPC measurement conditions]
Developing solvent: Tetrahydrofuran Flow rate: 0.6 mL / min
Column: TSK Guardcolum SuperH-L
TSKgel SuperH4000 (6.0mm ID x 15cm x 1)
TSKgel SuperH3000 (6.0mm ID x 15cm x 1)
TSKgel SuperH2000 (6.0 mm ID x 15 cm x 2)
(Both made by Tosoh)
Column temperature: 40 ° C
Sample injection volume: 20 μL (sample concentration: 0.5 mass% -tetrahydrofuran solution)
Detector: Differential Refractometer (RI)

As the maleimide compound, it may be synthesized from an amine and an acid anhydride by a conventional method, or a commercially available product may be used. Commercially available products include BMI-689, BMI-1400, BMI-1500, BMI-2300, BMI-2500, BMI-2560, BMI-3000, BMI-5000, BMI-6000, BMI-6100 (above, Designer Moleculars Inc). (Made), etc. Further, the maleimide compound may be used alone or in combination of two or more.

In the composition of the present invention, the blending amount of the maleimide compound of the component (a) is preferably 40 to 95% by mass, more preferably 60 to 90% by mass.

[(B) Organohydrogensiloxane having at least two hydrosilyl groups in one molecule]
The component (b) is an organohydrogensiloxane having at least two hydrosilyl groups in one molecule, and reacts with the maleimide of the component (a) to reduce the elasticity of the cured product of the composition of the present invention. be able to.
The organohydrogensiloxane is not particularly limited, but the kinematic viscosity at 25 ° C. measured by a Canon-Fenceke viscometer according to the method described in JIS Z 8803: 2011 is 1 to 10,000 mm ² / s. Is preferable, and 5 to 5,000 mm ² / s is more preferable. Within this range, the viscosity of the resin composition can be sufficiently lowered.
Further, as the organohydrogensiloxane, an organohydrogensiloxane represented by the following formula (2) is preferable.

(R ¹ ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO _4/2 ) _u (2)

(In the formula (2), R ¹ is a group selected from a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms independently of each other. At ^{least two of R 1} are hydrogen atoms. r is a number from 0 to 100, s is a number from 0 to 300, t is a number from 0 to 200, u is a number from 0 to 200, and 2 ≦ r + s + t + u. ≤800.)

R ¹ is a group selected from a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms independently of each other, preferably a hydrogen atom and a carbon number of carbon atoms. It is an aliphatic hydrocarbon group of 1 to 6 and an aromatic hydrocarbon group having 6 to 10 carbon atoms, more preferably a hydrogen atom, an aliphatic hydrocarbon group having 1 to 3 carbon atoms, and 6 to 6 carbon atoms. It is a group selected from 8 aromatic hydrocarbon groups.
Examples of the aliphatic hydrocarbon group include an alkyl group such as a methyl group, an ethyl group, a propyl group and a butyl group; a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group. Among these, a methyl group, a cyclohexyl group and the like are preferable, and a methyl group is particularly preferable.
Examples of the aromatic hydrocarbon group include an aryl group such as a phenyl group, a tolyl group, a naphthyl group and a biphenyl group, and an aralkyl group such as a benzyl group, a phenylethyl group and a phenylpropyl group. Among these, a phenyl group is preferable.
r is a number from 0 to 100, preferably a number from 0 to 75, even more preferably a number from 0 to 50, and even more preferably a number from 2 to 50.
s is a number from 0 to 300, preferably a number from 0 to 200, and even more preferably a number from 0 to 100.
t is a number from 0 to 200, preferably a number from 0 to 100, and more preferably a number from 0 to 50.
u is a number from 0 to 200, preferably a number from 0 to 100, and more preferably a number from 0 to 50.
However, r, s, t and u are 2 ≦ r + s + t + u ≦ 800, preferably 2 ≦ r + s + t + u ≦ 600, and more preferably 2 ≦ r + s + t + u ≦ 400. Within this range, the component (b) has good compatibility with the maleimide compound of the component (a), and the component (b) can be satisfactorily reacted with the maleimide group of the component (a).

（Ｍｅはメチル基、Ｐｈはフェニル基を表す。ｎは０〜１００、好ましくは１〜５０の数、ｍは１〜１００、好ましくは１〜５０の数、ｘは３〜３０、好ましくは３〜１０の数、ｙは１〜３０、好ましくは１〜１０の数である。） Specific structural formulas of the components (b) are illustrated below, but are not limited thereto.

(Me represents a methyl group, Ph represents a phenyl group. N is a number of 0 to 100, preferably 1 to 50, m is a number of 1 to 100, preferably 1 to 50, x is a number of 3 to 30, preferably 3. The number of 10 and y is 1 to 30, preferably 1 to 10.)

The amount of the component (a) and the component (b) to be blended is not particularly limited, but the total number of hydrosilyl groups in the component (b) is 0.4 to the total number of maleimide groups in the component (a). It is preferably 4.0, and more preferably 0.6 to 3.0. Within this range, a good cured product can be obtained.

[(C) Hydrosilylation catalyst]
The component (c) is a hydrosilylation catalyst. The catalyst is not particularly limited as long as it has an ability to allow the hydrosilylation reaction to proceed. Among them, a catalyst selected from a platinum group metal simple substance and a platinum group metal compound is preferable. For example, platinum chloride-olefin complex such as platinum (including platinum black), platinum chloride, platinum chloride acid, platinum chloride acid-divinylsiloxane complex, platinum-olefin complex such as platinum-divinylsiloxane complex, platinum-carbonyl complex and the like. Platinum catalyst, palladium catalyst, rhodium catalyst and the like can be mentioned. These catalysts may be used alone or in combination of two or more. Of these, a platinum-olefin complex such as chloroplatinic acid or a platinum-divinylsiloxane complex is particularly preferable.

The blending amount of the component (c) may be the amount of the catalyst. The amount of catalyst may be any amount as long as it can proceed with the hydrosilylation reaction, and may be appropriately adjusted according to the desired curing rate. For example, in the case of a platinum group metal catalyst, from the viewpoint of reaction rate, it is 1 to 1,000 ppm with respect to the total mass of the above components (a) and (b) on the basis of mass converted to platinum group metal atoms. The amount is preferably, and more preferably 10 to 500 ppm.

Further, the low-dielectric resin composition of the present invention may contain inorganic particles, a curing inhibitor, an adhesion aid, an antioxidant, a flame retardant and the like, if necessary. Hereinafter, each component will be described.

[Other ingredients]
Inorganic particles The inorganic particles are not particularly limited, and examples thereof include conductive particles, thermally conductive particles, phosphors, magnetic particles, white particles, hollow particles, and electromagnetic wave absorbing particles. Each of these may be used alone or in combination of two or more.

The conductive particles are not particularly limited and may be appropriately selected depending on the intended purpose. Examples thereof include metal particles and metal-coated particles. Among them, metal particles have low electric resistance and are sintered at a high temperature. It is also preferable because it can be used.

Examples of the metal particles include simple metals such as gold, silver, copper, palladium, aluminum, nickel, iron, titanium, manganese, zinc, tungsten, platinum, lead and tin, or alloys such as solder, steel and stainless steel. These include, preferably silver, copper, aluminum, iron, zinc, and solder, and more preferably silver, copper, aluminum, and solder. Each of these may be used alone or in combination of two or more.

Examples of the metal-coated particles may be those in which the surface of resin particles such as acrylic resin and epoxy resin is coated with metal, and those in which the surface of inorganic particles such as glass and ceramic is coated with metal. The metal coating method on the particle surface is not particularly limited, and examples thereof include an electroless plating method and a sputtering method.
Here, examples of the metal that coats the particle surface include gold, silver, copper, iron, nickel, and aluminum.

The conductive particles may have conductivity when electrically connected to the circuit electrode. For example, even if the particles have an insulating coating on the surface of the particles, they are conductive particles as long as the particles are deformed when electrically connected to expose the metal particles.

The shape of the conductive particles is not particularly limited, and examples thereof include spherical, scaly, flake-shaped, needle-shaped, rod-shaped, and elliptical, and among them, spherical, scaly, elliptical, and rod-shaped are preferable. Scale-like and oval-like are more preferable.

The primary particle size of the conductive particles is not particularly limited, but the median diameter measured by the laser diffraction type particle size distribution measuring device is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and 0.5. ~ 30 μm is more preferable. Within this range, it is easy to uniformly disperse the conductive particles in the resin composition, and the conductive particles do not settle, separate, or unevenly distribute over time, which is preferable.

The thermally conductive particles are not particularly limited, but in consideration of thermal conductivity, a group consisting of boron nitride, aluminum nitride, silicon nitride, beryllium oxide, magnesium oxide, zinc oxide, aluminum oxide, silicon carbide, diamond and graphene. Therefore, it is preferable to select at least one of them, and among them, boron nitride, aluminum nitride, aluminum oxide, magnesium oxide, and graphene are preferable. Each of these may be used alone or in combination of two or more.

The shape of the thermally conductive particles is not particularly limited, and examples thereof include spherical, scaly, flake-shaped, needle-shaped, rod-shaped, and elliptical, and among them, spherical, scaly, elliptical, and rod-shaped are preferable. , Scale-like, oval-like, more preferable.

The primary particle size of the thermally conductive particles is not particularly limited, but the median diameter measured by the laser diffraction type particle size distribution measuring device is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and 0. 5 to 30 μm is more preferable. Within this range, it is easy to uniformly disperse the heat conductive particles in the resin composition, and the heat conductive particles do not settle, separate, or are unevenly distributed over time, which is preferable.

As the phosphor, for example, one that absorbs light from a semiconductor light emitting diode having a nitride semiconductor as a light emitting layer and converts the wavelength into light having a different wavelength can be used. Examples of such phosphors include nitride-based phosphors and oxynitride-based phosphors that are mainly activated by lanthanoid-based elements such as Eu and Ce; lanthanoid-based elements such as Eu and transition metal-based such as Mn. Alkaline earth metal halogen apatite phosphor, alkaline earth metal halogen borate phosphor, alkaline earth metal aluminate phosphor, alkaline earth metal silicate phosphor, alkaline earth metal mainly activated by elements Alkaline earth metal, rare earth sulfide phosphor, alkaline earth metal thiogalate phosphor, alkaline earth metal silicon nitride phosphor, germanate phosphor; rare earth aluminate mainly activated by lanthanoid elements such as Ce. Fluorescent materials, rare earth silicate phosphors; Ca-Al-Si-ON-based oxynitride glass phosphors mainly activated by lanthanoid-based elements such as Eu can be mentioned. These phosphors may be used alone or in combination of two or more. Specific examples include, but are not limited to, the following phosphors.

Nitride-based phosphors mainly activated by lanthanoid elements such as Eu and Ce include M ₂ Si ₅ N ₈ : Eu, MSi ₇ N ₁₀ : Eu, M _1.8 Si ₅ O _0.2 N ₈ : Eu, M. _0.9 Si ₇ O _0.1 N ₁₀ : Eu (M is one or more selected from Sr, Ca, Ba, Mg, and Zn) and the like can be exemplified.

Alkaline earth metal halogen apatite phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include M ₅ (PO ₄ ) ₃ X: Z (M is Sr, Ca, Ba). , And one or more selected from Mg, X is one or more selected from F, Cl, Br, and I, and Z is one or more selected from Eu and Mn) and the like. It can be illustrated.

Alkaline earth metal aluminate phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include SrAl ₂ O ₄ : Z, Sr ₄ Al ₁₄ O ₂₅ : Z, CaAl _2. O ₄ : Z, BaMg ₂ Al ₁₆ O ₂₇ : Z, BaMg ₂ Al ₁₆ O _{12 : Z, BaMg Al 10} O ₁₇ : Z (Z is one or more selected from Eu and Mn) and the like can be exemplified. ..

Examples of the alkaline earth metal silicate phosphor activated mainly by lanthanoid elements such as Eu and transition metal elements such as Mn include (BaMg) Si ₂ O ₅ : Eu and (BaSrCa) ₂ SiO ₄ : Eu. Etc. can be exemplified.

Examples of the alkaline earth metal sulfide phosphor that is mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include (Ba, Sr, Ca) (Al, Ga) ₂ S ₄ : Eu and the like. It can be exemplified.

As rare earth sulfide phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn, La ₂ O ₂ S: Eu, Y ₂ O ₂ S: Eu, Gd ₂ O ₂ S: Eu and the like can be exemplified.

Alkaline earth metal thiogalate phosphors mainly activated by lanthanoid elements such as Eu and transition metal elements such as Mn include MGa ₂ S ₄ : Eu (M is from Sr, Ca, Ba, Mg, Zn). (One or more selected) and the like can be exemplified.

Examples of the alkaline earth metal silicon nitride phosphor activated mainly by lanthanoid elements such as Eu and transition metal elements such as Mn include (Ca, Sr, Ba) AlSiN ₃ : Eu, (Ca, Sr, Ba). ₂ Si ₅ N ₈ : Eu, SrAlSi ₄ N ₇ : Eu and the like can be exemplified.

Examples of the germanate phosphor mainly activated by a lanthanoid element such as Eu and a transition metal element _{such as Mn include Zn 2 GeO 4: Mn.}

Rare earth aluminate phosphors that are mainly activated by lanthanoid elements such as Ce include Y ₃ Al ₅ O ₁₂ : Ce, (Y _0.8 Gd _0.2 ) ₃ Al ₅ O ₁₂ : Ce, Y ₃ (Al _0.8 Ga). _0.2 ) ₅ O ₁₂ : A YAG-based phosphor such as Ce, (Y, Gd) ₃ (Al, Ga) ₅ O _{12 can be exemplified. Further, Tb 3} Al ₅ O ₁₂ : Ce, Lu ₃ Al ₅ O ₁₂ : Ce, etc. in which a part or all of Y is replaced with Tb, Lu, or the like can also be used.

Examples of the rare earth silicate phosphor activated mainly by a lanthanoid element such as Ce include Y ₂ SiO ₅ : Ce and Tb.

Ca-Al-Si-ON-based oxynitride glass phosphor is expressed in mol%, CaCO ₃ is converted into CaO, 20 to 50 mol%, Al ₂ O ₃ is 0 to 30 mol%, SiO. 25 to 60 mol%, AlN to 5 to 50 mol%, rare earth oxide or transition metal oxide to be 0.1 to 20 mol%, and oxynitride glass having a total of 5 components of 100 mol% as a base material. It is a phosphor. The nitrogen content of the phosphor using oxynitride glass as the base material is preferably 15% by mass or less. Further, in addition to the rare earth oxide ion, it is preferable to contain other rare earth element ions serving as a sensitizer in the state of the rare earth oxide, and co-activation in the phosphor with a content in the range of 0.1 to 10 mol%. It is preferably contained as an agent.

Examples of other phosphors include ZnS: Eu. Examples of silicate-based phosphors other than the above include (BaSrMg) ₃ Si ₂ O ₇ : Pb, (BaMgSrZnCa) ₃ Si ₂ O ₇ : Pb, Zn ₂ SiO ₄ : Mn, BaSi ₂ O ₅ : Pb and the like. Be done.
Further, the phosphor containing one or more selected from Tb, Cu, Ag, Au, Cr, Nd, Dy, Co, Ni, and Ti instead of Eu or in addition to Eu is also used. can do

Further, any fluorescent substance other than the above-mentioned fluorescent substance, which has the same performance and effect as the above-mentioned one, can be used as particles in the present invention.

The properties of the phosphor are not particularly limited, and for example, a powdery one can be used. The shape of the phosphor powder is not particularly limited, and examples thereof include a spherical shape, a scaly shape, a flake shape, a needle shape, a rod shape, and an elliptical shape. Among them, the spherical shape, the scaly shape, and the flake shape are preferable. , Flakes are more preferred.

The primary particle size of the phosphor is not particularly limited, but the median diameter measured by the laser diffraction type particle size distribution measuring device is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and 0.5 to 0.5 to 40 μm. 30 μm is more preferable. Within this range, it is easy to uniformly disperse the phosphor in the resin composition, and the phosphor does not settle, separate, or unevenly distribute over time, which is preferable.

The magnetic particles are not particularly limited, but are simple ferromagnetic metals such as iron, cobalt, and nickel, stainless steel, Fe-Cr-Al-Si alloy, Fe-Si-Al alloy, Fe-Ni alloy, and Fe-Cu. -Si alloy, Fe-Si alloy, Fe-Si-B (-Cu-Nb) alloy, Fe-Si-Cr-Ni alloy, Fe-Si-Cr alloy, Fe-Si-Al-Ni-Cr alloy, etc. Magnetic metal alloys, _{metal oxides such as hematite (Fe 2} O ₃ ) and magnetite (Fe ₃ O ₄ ), Mn-Zn-based ferrite, Ni-Zn-based ferrite, Mg-Mn-based ferrite, Zr-Mn-based ferrite, Ti Ferrites such as −Mn-based ferrite, Mn—Zn—Cu-based ferrite, barium ferrite, and strontium ferrite are preferably used. By blending the magnetic particles, magnetism can be imparted to the resin composition of the present invention, resulting in a resin composition having high magnetic permeability and low loss in the high frequency band region.

The shape of the magnetic particles is not particularly limited, and examples thereof include spherical, scaly, flake-shaped, needle-shaped, rod-shaped, elliptical, and porous, and among them, spherical, scaly, elliptical, flake-shaped, and porous. The shape is preferable, and spherical, scaly, flake-like, and porous-like shapes are more preferable.

When porous magnetic particles are obtained, they can be obtained by adding a pore-regulating agent such as calcium carbonate to granulate the particles at the time of granulation, and then firing the particles. Further, by adding a material that inhibits particle growth during the ferrite formation reaction, complicated voids can be formed inside the ferrite. Examples of such a material include tantalum oxide, zirconium oxide and the like.

The primary particle size of the magnetic particles is not particularly limited, but the median diameter measured by the laser diffraction type particle size distribution measuring device is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and 0.5 to 0.5 to 40 μm. 30 μm is more preferable. Within this range, it is easy to uniformly disperse the magnetic particles in the resin composition, and the magnetic particles do not settle over time, which is preferable.

The white particles are blended to increase the whiteness required for applications such as reflectors. For example, examples of the white pigment include titanium dioxide, rare earth oxides typified by yttrium oxide, zinc sulfate, zinc oxide, magnesium oxide and the like, and these can be used alone or in combination of several kinds. Above all, it is preferable to use titanium dioxide in order to further increase the whiteness. The unit cell of titanium dioxide includes rutile type, anatas type, and brookite type, and any of them can be used, but it is preferable to use rutile type from the viewpoint of whiteness and photocatalytic ability of titanium dioxide.

The shape of the white particles is not particularly limited, and examples thereof include a spherical shape, a scale shape, a flake shape, a needle shape, a rod shape, and an elliptical shape. Among them, a spherical shape, an elliptical shape, and a flake shape are preferable, and a spherical shape is more preferable.

The primary particle size of the white particles is not particularly limited, but the median diameter measured by the laser diffraction type particle size distribution measuring device preferably has an average particle size of 0.05 to 5 μm, and more preferably 3 μm or less. It is more preferably 1 μm or less. Within this range, it is easy to uniformly disperse the white particles in the resin composition, and the white particles do not settle, separate, or unevenly distribute over time, which is preferable.

The white particles are preferably surface-treated in order to enhance wettability, compatibility, dispersibility and fluidity with the resin, and are at least selected from silica, alumina, zirconia, polyols, and organosilicon compounds. It is more preferable that the surface is treated with one or more kinds of treatment agents, particularly two or more kinds of treatment agents.

Further, in order to improve the initial reflectance and the fluidity of the resin composition containing the white particles, titanium dioxide treated with an organosilicon compound is preferable. Examples of organosilicon compounds include chlorosilanes and silazanes, monomeric organosilicon compounds such as silane coupling agents having reactive functional groups such as epoxy groups and amino groups, and organopolysiloxanes such as silicone oils and silicone resins. Can be mentioned. In addition, other treatment agents usually used for the surface treatment of titanium dioxide such as organic acids such as stearic acid may be used, and even if the surface treatment is performed with a treatment agent other than the above, the surface treatment is performed with a plurality of treatment agents. It doesn't matter.

The hollow particles are not particularly limited, and examples thereof include silica balloons, carbon balloons, alumina balloons, and aluminosilicate balloons.

The shape of the hollow particles is not particularly limited, and examples thereof include a spherical shape, an elliptical shape, a columnar shape, and a prismatic shape. Among them, a spherical shape, an elliptical shape, and a prismatic shape are preferable, and a spherical shape and a prismatic shape are more preferable. The primary particle size of the hollow particles is not particularly limited, but the median diameter measured by the laser diffraction type particle size distribution measuring device preferably has an average particle size of 0.01 to 5 μm, and among them, 0.03 to 3 μm or less. Is more preferable, and those having a diameter of 0.05 to 1 μm or less are further preferable. Within this range, it is easy to uniformly disperse the hollow particles in the resin composition, and the hollow particles do not settle, separate, or are unevenly distributed over time, which is preferable.

By blending the hollow particles, the cured product of the resin composition of the present invention can be easily reduced in specific gravity and can be reduced in weight.

The electromagnetic wave absorbing particles are not particularly limited, and conductive particles, dielectric loss electromagnetic wave absorbing materials typified by carbon particles, ferrite, magnetic loss electromagnetic wave absorbing materials typified by soft magnetic metal powder, and the like are applied. Can be done.

By blending the electromagnetic wave absorbing particles, the resin composition of the present invention can be imparted with an electromagnetic wave absorbing ability, and a cured resin product having an electromagnetic wave shielding property such as a housing of an electronic device can be easily obtained.

Examples of the dielectric loss electromagnetic wave absorber include simple metals such as gold, silver, copper, palladium, aluminum, nickel, iron, titanium, manganese, zinc, tungsten, platinum, lead and tin, or solder, steel and stainless steel. Examples thereof include conductive particles such as carbon black, acetylene black, ketjen black, carbon nanotubes, graphene, and fullerenes, and among them, carbon black, acetylene black, ketjen black, carbon nanotubes, graphene, and fullerenes are preferable.

Examples of the magnetic loss electromagnetic wave absorber include Mg—Zn-based ferrite, Ba ₂ Co ₂ Fe ₁₂ O ₂₂ , Ba ₂ Ni ₂ Fe ₁₂ O ₂₂ , Ba ₂ Zn ₂ Fe ₁₂ O ₂₂ , and Ba ₂ Mn ₂ Fe ₁₂ O ₂₂ , Ba ₂ Mg ₂ Fe ₁₂ O ₂₂ , Ba ₂ Cu ₂ Fe ₁₂ O ₂₂ , Ba ₃ Co ₂ Fe ₂₄ O ₄₁ , BaFe ₁₂ O ₁₉ , SrFe ₁₂ O ₁₉ , BaFe ₁₂ O ₁₉ , SrFe ₁₂ O _19, etc. Ferrite particles, carbonyl iron, electrolytic iron, Fe-Cr alloy, Fe-Si alloy, Fe-Ni alloy, Fe-Al alloy, Fe-Co alloy, Fe-Al-Si alloy, Fe- Examples thereof include soft magnetic alloy particles such as Cr-Si-based alloys, Fe-Cr-Al-based alloys, Fe-Si-Ni-based alloys, and Fe-Si-Cr-Ni-based alloys. Among them, Mg-Zn-based ferrites and Ba. ₂ Co ₂ Fe ₁₂ O ₂₂ , Ba ₂ Ni ₂ Fe ₁₂ O ₂₂ , Ba ₂ Zn ₂ Fe ₁₂ O ₂₂ , Ba ₂ Mn ₂ Fe ₁₂ O ₂₂ , Ba ₂ Mg ₂ Fe ₁₂ O ₂₂ , Ba ₂ Cu ₂ Fe ₁₂ It is preferably at least one selected from O ₂₂ , Ba ₃ Co ₂ Fe ₂₄ O ₄₁ , BaFe ₁₂ O ₁₉ , SrFe ₁₂ O ₁₉ , BaFe ₁₂ O ₁₉ , and SrFe ₁₂ O _19.

These electromagnetic wave absorbing particles may be used alone or in combination of two or more.

The shape of the electromagnetic wave absorbing particles is not particularly limited, and examples thereof include spherical, scaly, flake-shaped, needle-shaped, rod-shaped, and elliptical, and among them, spherical, scaly, elliptical, and rod-shaped are preferable. Scale-like and oval-like are more preferable.

The primary particle size of the electromagnetic wave absorbing particles is not particularly limited, but the median diameter measured by the laser diffraction type particle size distribution measuring device is preferably 0.05 to 50 μm, more preferably 0.1 to 40 μm, and 0.5. ~ 30 μm is more preferable. Within this range, it is easy to uniformly disperse the electromagnetic wave absorbing particles in the resin composition, and the electromagnetic wave absorbing particles do not settle, separate, or are unevenly distributed over time, which is preferable.

The blending amount of the inorganic particles is not particularly limited and may be appropriately determined depending on the function of the inorganic particles to be imparted, but is preferably 5 to 3,000 parts by mass with respect to 100 parts by mass of the total of the components (a) to (c). Is 10 to 2,000 parts by mass, more preferably 15 to 1,500 parts by mass, and even more preferably 50 to 800 parts by mass. Within this range, the functions of the inorganic particles can be sufficiently exerted while maintaining the strength of the cured product of the resin composition.

Curing Inhibitor The resin composition of the present invention may contain a curing inhibitor in order to control the reactivity and enhance the storage stability. As the curing inhibitor, a compound selected from the group consisting of triallyl isocyanurate, alkylmalate, acetylene alcohol, its silane modified product and siloxane modified product, hydroperoxide, tetramethylethylenediamine, benzotriazole, and a mixture thereof. Can be mentioned. When the curing inhibitor is blended, the blending amount is preferably 5 to 100 times, more preferably 5 to 50 times, the molar ratio of the effective amount of the catalyst in the hydrosilylation catalyst of the component (c). Is.

Adhesive-imparting agent In order to impart adhesiveness or adhesiveness (pressure-sensitive adhesiveness), the resin composition of the present invention may contain an adhesiveness-imparting agent, if necessary. Examples of the adhesiveness-imparting agent include epoxy resin, styryl resin, acrylic resin, terpene resin, silane coupling agent and the like. Among them, an epoxy resin and a silane coupling agent are preferable for imparting adhesiveness, and a terpene resin is preferable for imparting adhesiveness (pressure sensitive adhesiveness).

The epoxy resin is not particularly limited, and is, for example, a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, 3,3', 5,5'-tetramethyl-4,4'-biphenol type epoxy resin, or 4, Biphenol type epoxy resin such as 4'-biphenol type epoxy resin, phenol novolac type epoxy resin, cresol novolac type epoxy resin, bisphenol A novolac type epoxy resin, naphthalenediol type epoxy resin, trisphenylol methane type epoxy resin, tetrakispheni Examples thereof include a roll ethane type epoxy resin and an epoxy resin obtained by hydrogenating the aromatic ring of a phenoldicyclopentadiene novolac type epoxy resin. If necessary, an epoxy resin other than the above can be used in combination in a certain amount depending on the purpose.

The styryl resin is not particularly limited, and examples thereof include styrene, p-methylstyrene, p-ethylstyrene, p-butylstyrene, 2,4,6-trimethylstyrene, p-methoxystyrene, α-methylstyrene and the like. Be done. If necessary, a certain amount of styryl resin other than the above can be used in combination depending on the purpose.

The acrylic resin is not particularly limited, but for example, acrylamide, N, N-dimethylacrylamide, acrylic acid, methyl acrylate, ethyl acrylate, propyl acrylate, n-butyl acrylate, isobutyl acrylate, t- acrylate. Butyl, isooctyl acrylate, isononyl butyl acrylate, lauryl acrylate, allyl acrylate, stearyl acrylate, isostearyl acrylate, isobonyl acrylate, cyclohexyl acrylate, benzyl acrylate, ethyl carbitol acrylate, phenoxy acrylate Ethyl, hydroxyethyl acrylate, methoxyethyl acrylate, ethoxyethyl acrylate, methoxybutyl acrylate, dicyclopentyl acrylate, dicyclohexyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, n-butyl methacrylate, methacrylic acid Isobutyl, t-butyl methacrylate, 2-ethylhexyl methacrylate, lauryl methacrylate, tridecyl methacrylate, stearyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, methacrylate Examples thereof include dicyclopentyl and dicyclohexyl methacrylate. If necessary, an acrylic resin other than the above can be used in combination in a certain amount depending on the purpose.

The terpene resin is not particularly limited, but for example, monoterpenes such as α-pinene, β-pinene, dipentene, and limonene, sesquiterpenes such as sedren and funelsen, and terpenes such as diterpenes such as avietic acid Or aromatic vinyl compounds such as styrene and α-methylstyrene and aromatic-modified terpene resins, which are copolymers of the terpenes, and phenols such as phenol, cresol, hydroquinone, naphthol, and bisphenol A. Examples thereof include a terpene phenol resin which is a copolymer with the terpenes. Further, a hydrogenated terpene resin obtained by hydrogenating these terpene resins can also be used.

The silane coupling agent is not particularly limited, but for example, n-propyltrimethoxysilane, n-propyltriethoxysilane, n-octyltrimethoxysilane, n-octyltriethoxysilane, phenyltrimethoxysilane, phenyltriethoxy, etc. Silane, Methyltrimethoxysilane, Methyltriethoxysilane, 2- [methoxy (polyethyleneoxy) propyl] -trimethoxysilane, methoxytri (ethyleneoxy) propyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-mercaptopropyltri Examples thereof include silane coupling agents such as methoxysilane, 3- (methacryloyloxy) propyltrimethoxysilane, 3-isocyanatopropyltriethoxysilane, 3-isocyanatopropyltrimethoxysilane, and glycidoxypropyltrimethoxysilane.

The content of the adhesive-imparting agent is not particularly limited, but the content in the resin composition is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, and 1 to 5% by mass. Is more preferable. Within this range, the adhesive strength or adhesive strength of the resin composition can be further improved without changing the physical properties of the resin composition.

Antioxidants The antioxidants are not particularly limited, but are, for example, n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate and n-octadecil-3- (3,5). -Di-t-butyl-4-hydroxyphenyl) acetate, neododecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, dodecyl-β- (3,5-di-t-butyl) -4-Hydroxyphenyl) propionate, ethyl-α- (4-hydroxy-3,5-di-t-butylphenyl) isobutyrate, octadecyl-α- (4-hydroxy-3,5-di-t-butylphenyl) Isobutyrate, octadecyl-α- (4-hydroxy-3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2- (n-octylthio) ethyl-3,5-di-t-butyl-4-hydroxy Phenylacetate, 2- (n-octadecylthio) ethyl-3,5-di-t-butyl-4-hydroxyphenylacetate, 2- (n-octadecylthio) ethyl-3- (3,5-di-t-) Butyl-4-hydroxyphenyl) propionate, 2- (2-stearoyloxyethylthio) ethyl-7- (3-methyl-5-t-butyl-4-hydroxyphenyl) heptanoate, 2-hydroxyethyl-7- (3) -Pharmonic antioxidants such as -methyl-5-t-butyl-4-hydroxyphenyl) propionate, dilauryl-3,3'-thiodipropionate, dimyristyl-3,3'-thiodipropionate, distearyl- Sulfur-based antioxidants such as 3,3'-thiodipropionate, ditridecyl-3,3'-thiodipropionate, pentaerythrityltetrakis (3-laurylthiopropionate), tridecylphosphite, triphenyl Phosphite, Tris (2,4-di-t-butylphenyl) phosphite, 2-ethylhexyldiphenylphosphite, diphenyltridecylphosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl Phosphite, distearyl pentaerythritol diphosphite, bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, 2-[[2,4,8,10-tetrakis (1,4,8,10-tetrakis) 1-Dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6-yl] oxy] -N, N-bis [2- [ Phosphorus such as [2,4,8,10-tetrakis (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] dioxaphosfepine-6-yl] oxy] -ethyl] ethanamin Examples include system antioxidants.

The content of the antioxidant is not particularly limited, but the content in the resin composition of the present invention is preferably 0.00001 to 5% by mass, more preferably 0.0001 to 4% by mass, and 0.001. ~ 3% by mass is more preferable. Within this range, oxidation of the resin composition can be prevented without changing the mechanical properties of the resin composition.

Flame Retardant The flame retardant is not particularly limited, and examples thereof include phosphorus-based flame retardants, metal hydrates, halogen-based flame retardants, and guanidine-based flame retardants. For example, red phosphorus, monoammonium phosphate, diammonium phosphate, triammonium phosphate, ammonium phosphate such as ammonium polyphosphate, inorganic nitrogen-containing phosphorus compounds such as phosphate amide, phosphoric acid, phosphine oxide, triphenyl phosphate. , Tricresyl phosphate, trixylenyl phosphate, cresildiphenyl phosphate, cresildi-2,6-xylenyl phosphate, resorcinolbis (diphenyl phosphate), 1,3-phenylenebis (di-2,6-xylenyl) Phosphate), bisphenol A-bis (diphenyl phosphate), 1,3-phenylene bis (diphenyl phosphate), divinyl phenylphosphonate, diallyl phenylphosphonate, bis (1-butenyl) phenylphosphonate, phenyl diphenylphosphinate, diphenylphosphine Phosphazenic compounds such as methyl, bis (2-allylphenoxy) phosphazene, dicredylphosphazene; melamine phosphate; melamine pyrophosphate; melamine polyphosphate; melam polyphosphate, 9,10-dihydro-9-oxa-10-phospha Phosphorus flame retardants such as phenanthrene-10-oxide, 10- (2,5-dihydroxyphenyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, aluminum hydroxide hydrate, Metal hydrates such as magnesium hydroxide hydrate, hexabromobenzene, pentabromotoluene, ethylenebis (pentabromophenyl), ethylenebistetrabromophthalimide, 1,2-dibromo-4- (1,2-dibromoethyl) ) Cyclohexane, tetrabromocyclooctane, hexabromocyclododecane, bis (tribromophenoxy) ethane, brominated polyphenylene ether, brominated polystyrene, 2,4,6-tris (tribromophenoxy) -1,3,5-triazine Halogen-based flame retardants such as.

The content of the flame retardant is not particularly limited, but the content in the resin composition of the present invention is preferably 0.01 to 5% by mass, more preferably 0.05 to 4% by mass, and 0.1 to 1% by mass. 3% by mass is more preferable. Within this range, flame retardancy can be imparted to the resin composition without changing the mechanical properties of the resin composition.

Manufacturing Method Regarding the manufacturing method of the resin composition of the present invention, the blending order, preparation method, etc. of the components (a), (b), (c) and various arbitrary components are not particularly limited, and each component is prepared in a predetermined amount in advance. May be mixed according to a conventional method. The defoaming operation may be performed during the mixing of each component.
The hardness of the cured product can be adjusted by a conventional method. The hardness of the cured product is preferably in the range of type E20 to type A70, preferably in the range of durometer type A80 or less, as measured in accordance with the method described in JIS K 6253-: 2012. When the hardness of the cured product is within the above range, it is suitable for applications such as adhesives.

Hereinafter, the present invention will be described in more detail with reference to Synthesis Examples, Examples and Comparative Examples, but the present invention is not limited to the following Examples. In the following examples, Me represents a methyl group, Ph represents a phenyl group, Ma value represents a maleimide equivalent, SiH value represents a hydrosilyl equivalent, and Vi value represents a vinyl equivalent.

The molecular weight shown in the following examples is the weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) using polystyrene as a standard substance. The measurement conditions are shown below.
[GPC measurement conditions]
Developing solvent: Tetrahydrofuran Flow rate: 0.6 mL / min
Column: TSK Guardcolum SuperH-L
TSKgel SuperH4000 (6.0mm ID x 15cm x 1)
TSKgel SuperH3000 (6.0mm ID x 15cm x 1)
TSKgel SuperH2000 (6.0 mm ID x 15 cm x 2)
(Both made by Tosoh)
Column temperature: 40 ° C
Sample injection volume: 20 μL (Sample concentration: 0.5 mass% -tetrahydrofuran solution)
Detector: Differential Refractometer (RI)

The Ma (maleimide) value (mol / 100 g), Vi (vinyl) value and SiH (hydrosilyl) value (mol / 100 g) shown in the following examples were ^{measured by measuring a 1} H-NMR spectrum at 400 MHz of the compound, and dimethylsulfoxide. Was calculated from the integrated value of the hydrogen atom of the maleimide group, vinyl group or hydrosilyl group obtained as an internal standard.

[Viscosity of composition]
For the compositions prepared with the formulations (parts by mass or concentration) shown in Table 1, the viscosity of the resin composition at 23 ° C. was measured using a B-type viscometer according to JIS Z 8803: 2011. The results are shown in Table 1. The blending amount of the component (c) is a value (ppm) with respect to the total mass of the components (a) and (b) below on a mass basis converted to a platinum group metal atom.

[Hardness of cured product]
The prepared composition was poured into an aluminum petri dish having a diameter of 50 mm and a thickness of 10 mm, and step-cured at 60 ° C. for 1 hour, 100 ° C. for 1 hour, and 150 ° C. for 4 hours in this order to prepare a cured product of the composition. .. The hardness of the obtained cured product was measured according to the method described in JIS K 6253-: 2012. The measurement was first performed using a durometer type A hardness tester, and if the measured value exceeded 90, the measurement was performed using a durometer type D hardness tester, and the measured values are also shown. If the measured value with the durometer type A hardness tester was 20 or less, the measurement was performed with the durometer type E hardness tester, and the measured values are also shown. The results are shown in Table 1.

[Tensile strength of cured product and elongation during cutting]
The prepared composition is poured into a concave mold coated with PTFE (polytetrafluoroethylene) having a thickness of 150 mm × 200 mm × 2 mm, and the composition is poured in the order of 60 ° C. for 1 hour, 100 ° C. for 1 hour, and 150 ° C. for 4 hours. Step curing was performed to prepare a test sample. Based on JIS K 6251: 2010, the test sample was used under the conditions of test speed 500 mm / min, distance between grippers 80 mm, and distance between gauge points 40 mm using EZ TEST (EZ-L, manufactured by Shimadzu Corporation). The tensile strength and elongation at cutting were measured. The results are shown in Table 1.

[Relative permittivity and dielectric loss tangent measurement]
Using a mold frame having a thickness of 60 mm × 60 mm × 0.1 mm, the prepared composition was sandwiched and heat-pressed at 180 ° C. for 2 hours to prepare a test sample. The produced cured product was connected to a network analyzer (E5063-2D5 manufactured by Keysight Co., Ltd.) and a strip line (manufactured by Keycom Co., Ltd.), and the relative permittivity and dielectric loss tangent at a frequency of 10 GHz were measured. The results are shown in Table 1.

(A) Component [maleimide compound (a-1)]
To 196 g of N-methylpyrrolidone, 200 g (1.0 mol) of 1,12-diaminododecane and 207 g (0.95 mol) of pyromellitic anhydride were added, and the mixture was stirred at 25 ° C. for 3 hours and at 150 ° C. for 3 hours. 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate and 204 g (2.0 mol) of acetic anhydride were added to the obtained solution, and the mixture was stirred at 80 ° C. for 1 hour. Then, 500 g of toluene was added, and after further washing with water and dehydration, the solvent was distilled off under reduced pressure to obtain a bismaleimide compound (a-1) represented by the following formula. (Ma value = 0.057 mol / 100 g) (molecular weight 3,500)

[Maleimide compound (a-2)]
Maleimide compound represented by the following formula (BMI-3000, manufactured by Designer Moleculars Inc.) (Ma value = 0.050 mol / 100 g) (molecular weight 4,000)

[Maleimide compound (a-3)]
Maleimide compound represented by the following formula (BMI-689, manufactured by Designer Moleculars Inc.) (Ma value = 0.29 mol / 100 g) (molecular weight 690)

[Maleimide compound (a-4)]
Maleimide compound represented by the following formula (BMI-1500, manufactured by Designer Moleculars Inc.) (Ma value = 0.095 mol / 100 g) (molecular weight 2,100)

[Maleimide compound (a-5)]
To 350 g of N-methylpyrrolidone, 252 g (1.0 mol) of Kayahard AA (manufactured by Nippon Kayaku Co., Ltd.) and 207 g (0.9 mol) of pyromellitic anhydride were added, and the mixture was stirred at room temperature for 3 hours at 120 ° C. The mixture was stirred for 3 hours. 196 g (2.0 mol) of maleic anhydride, 82 g (1.0 mol) of sodium acetate and 204 g (2.0 mol) of acetic anhydride were added to the obtained solution, and the mixture was stirred at 80 ° C. for 1 hour. Then, 500 g of toluene was added, and after further washing with water and dehydration, the solvent was distilled off under reduced pressure to obtain a bismaleimide compound (a-5) represented by the following formula. (Ma value = 0.11 mol / 100 g) (molecular weight 1,800)

[Maleimide (a-6)]
Maleimide compound represented by the following formula (BMI-2300, manufactured by Daiwa Kasei Co., Ltd.) (Ma value = 0.50 mol / 100 g) (molecular weight 400)

（ｋ≒１０（平均値）、ｎ≒３３（平均値）、ｍ≒３（平均値）、ｌ≒８７（平均値））
（式中、ジメチルシロキシ単位は連続したブロック構造を有することを示す） [Vinyl group-containing organopolysiloxane (a'-1)] (for comparative examples)
After dissolving 1142.1 g (87.1 mol) of phenyltrichlorosilane, 529 g (3.2 mol) of ClMe ₂ SiO (Me ₂ SiO) ₃₃ SiMe ₂ Cl, and 72.4 g (9.7 mol) of dimethylvinylchlorosilane in a toluene solvent, It was dropped into water, co-hydrolyzed, neutralized by water washing and alkaline washing, dehydrated, and then the solvent was distilled off under reduced pressure to obtain a vinyl group-containing organopolysiloxane (a'-1) represented by the following formula. .. (Vi value = 0.016 mol / 100 g) (molecular weight 63,000)

(K≈10 (average value), n≈33 (average value), m≈3 (average value), l≈87 (average value))
(In the formula, the dimethylsiloxy unit shows that it has a continuous block structure)

(B) Ingredient [Organohydrogensiloxane (b-1)]
Silicone oil containing hydrosilyl groups at both ends represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value = 0.39 mol / 100 g)

[Organohydrogensiloxane (b-2)]
Silicone oil containing side chain hydrosilyl group represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value = 0.76 mol / 100 g)

[Organohydrogensiloxane (b-3)]
Silicone oil containing a terminal hydrosilyl group represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value = 0.89 mol / 100 g)

[Organohydrogensiloxane (b-4)]
Silicone oil containing a terminal hydrosilyl group represented by the following formula (manufactured by Shin-Etsu Chemical Co., Ltd., SiH value = 0.23 mol / 100 g)

(C component)
[Hydrosilylation catalyst (c-1)]
Chloroplatinic acid-divinylsiloxane complex

[Curing catalyst (c'-1)] (for comparative example)
Dikmil Peroxide "Park Mill D" (manufactured by NOF CORPORATION)

(Other ingredients)
Adhesive-imparting agent [Acrylic resin (d-1)]
Isobornyl acrylate (manufactured by Osaka Organic Chemical Co., Ltd.) (Vi value = 0.48 mol / 100 g)

[Acrylic resin (d-2)]
Light ester 14EG (manufactured by Kyoeisha Co., Ltd.) (Vi value = 0.26 mol / 100 g)

[Epoxy resin (d-3)]
FOLDI E101 (manufactured by Nissan Chemical Industries, Ltd.)

[Terpene resin (d-4)]
YS Resin PX800 (manufactured by Yasuhara Chemical Co., Ltd.)

Inorganic particles [silica (e-1)]
SFP-30M (manufactured by Denka Co., Ltd., average particle size 0.6 μm)

[Boron Nitride (e-2)]
XGP (manufactured by Denka Co., Ltd., average particle size 30 μm)

Hardening inhibitor [acetylene alcohol (f-1)]
1-ethynyl-1-cyclohexanol (manufactured by Tokyo Chemical Industry Co., Ltd.)

Antioxidant [Phenolic Antioxidant (g-1)]
ADEKA STAB AO-60 (manufactured by ADEKA CORPORATION)
[Phenolic antioxidant (g-2)]
ADEKA STAB AO-20 (manufactured by ADEKA CORPORATION)

Flame Retardant [Guanidine Flame Retardant (h-1)]
Apinon-303 (manufactured by Sanwa Chemical Co., Ltd.)

Each component was mixed according to the formulation (part by mass or concentration) shown in Table 1, placed in a stirrer THINKY CONDITIONING MIXER (manufactured by Shinky Co., Ltd.), and defoamed by stirring for 3 minutes to prepare a resin composition. The blending amount of the component (c) is a value (ppm) with respect to the total mass of the components (a) and (b) below on a mass basis converted to a platinum group metal atom.

In Examples 1 to 12, a resin composition having a low relative permittivity and a low dielectric loss tangent and a low hardness could be produced. In Comparative Example 1, since the organohydrogensiloxane was not contained, the cured product had a high hardness. In Comparative Example 2, since the maleimide compound was not contained, the relative permittivity and the dielectric loss tangent were high.

Claims (7)

(A) A maleimide compound having at least two maleimide groups in one molecule,
(B) Organohydrogensiloxane having at least two hydrosilyl groups in one molecule, and
(C) A low-dielectric resin composition containing a hydrosilylation catalyst.
The low-dielectric resin composition according to claim 1, wherein the component (a) is a maleimide compound represented by the following formula (1) or (1').

(In the formula (1), A independently represents a tetravalent organic group containing a cyclic structure. B is an alkylene group having 6 or more carbon atoms which may independently contain a hetero atom. Q is independently. It is an arylene group having 6 or more carbon atoms which may contain a hetero atom. W represents a group represented by B or Q. N represents a number from 0 to 100, and m represents a number from 0 to 100.)

(In equation (1'), n represents a number from 2 to 10.)
The low-dielectric resin composition according to claim 2, wherein the organic group represented by A in the formula (1) is any one of the tetravalent organic groups represented by the following structural formula.

(The bond to which the substituent in the above structural formula is not bonded is the one that bonds to the carbonyl carbon forming the cyclic imide structure in the formula (1).)
According to claim 2 or 3, B in the formula (1) is an alkylene group having 6 or more carbon atoms which may independently contain a heteroatom and has one or more aliphatic rings having 5 or more carbon atoms. The low dielectric resin composition described.
^{(B) Organohydrogensiloxane (R 1} ₃ SiO _1/2 ) _r (R ¹ ₂ SiO _2/2 ) _s (R ¹ SiO _3/2 ) _t (SiO ₄ ) whose component is represented by the following formula (2) _{/ 2} ) _u (2)
(In the formula (2), R ¹ is a group selected from a hydrogen atom, a monovalent saturated hydrocarbon group having 1 to 12 carbon atoms, and an aromatic hydrocarbon group having 6 to 12 carbon atoms independently of each other. At ^{least two of R 1} are hydrogen atoms. r is a number from 0 to 100, s is a number from 0 to 300, t is a number from 0 to 200, u is a number from 0 to 200, and 2 ≦ r + s + t + u. ≤800.)
The low-dielectric resin composition according to any one of claims 1 to 4.
The low-dielectric resin composition according to claim 5, wherein at least one ^{of R 1} in the formula (2) is an aromatic hydrocarbon group having 6 to 12 carbon atoms.
The low dielectric according to any one of claims 1 to 6, wherein the total number of hydrosilyl groups in the component (b) is 0.4 to 4.0 with respect to the total number of maleimide groups in the component (a). Resin composition.