TW202020004A - Composition, cured product, laminated body, and electronic device - Google Patents

Abstract

Embodiments of the present invention pertain to a composition, a cured product, a laminated body, and an electronic device. The composition includes: an inorganic filler; a polymerizable liquid crystal compound having 2 or more functional groups; a polymerizable non-liquid crystal compound having 2 or more functional groups; and a curing agent that is capable of curing the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound. The inorganic filler content is 150-4500 parts by mass with respect to 100 parts by mass of the polymerizable liquid crystal compound. The ratio of the contained amounts between the polymerizable liquid crystal compound and the polymerizable non-liquid crystal compound (mass of polymerizable liquid crystal compound: mass of polymerizable non-liquid crystal compound) is 20:80-95:5.

Description

Compositions, hardened objects, laminates and electronic equipment

The present invention relates to a composition, a hardened product, a laminate, and an electronic device.

In recent years, semiconductor devices for power control in hybrid vehicles, electric automobiles, etc., and central processing units (CPUs) for high-speed computers have been expected High thermal conductivity of wafers and packaging materials so that the temperature of internal semiconductors does not become too high. That is, the ability to efficiently release heat generated from the semiconductor wafer to the outside becomes important. In addition, due to the increase in operating temperature, thermal strain is generated due to the difference in thermal expansion coefficient between the materials used in the wafer and the package, and the decrease in the life due to the peeling of the wiring and the peeling of the laminate substrate becomes a problem.

As a method for solving such a heat dissipation problem, a method of bringing a highly thermally conductive material (heat dissipation member) into contact with a heat-generating portion to extract heat to the outside to dissipate heat. Patent Document 1 discloses a heat dissipation member which is formed by compounding an organic material and an inorganic material, and the heat dissipation member connects the inorganic materials with a silane coupling agent and a polymerizable liquid crystal compound. [Prior Art Literature] [Patent Literature]

[Patent Literature 1] International Publication No. 2016/031888

[Problems to be solved by the invention] As described above, the heat dissipation member used in the wafer and the package and various materials constituting the same have been studied. However, for example, the heat dissipation member described in Patent Document 1 has room for improvement in thermal conductivity or adhesion to a adherend such as a metal, a metal compound, or a semiconductor layer.

The present invention has been completed in view of the above-mentioned problems, and its object is to provide a composition capable of forming a cured product excellent in thermal conductivity and adhesion to an adherend such as a metal, a metal compound, or a semiconductor layer, and uses thereof. [Means to solve the problem]

The present inventors have repeatedly studied to solve the above-mentioned problems. As a result, it was found that the above-mentioned problems can be solved according to a specific composition, and the present invention has been completed. The configuration example of the present invention is as follows. Furthermore, the present invention is not limited by the following embodiments.

[1] A composition comprising an inorganic filler, a bifunctional or higher polymerizable liquid crystal compound, a bifunctional or higher non-liquid crystal polymerizable compound, and capable of curing the polymerizable liquid crystal compound and the non-liquid crystal polymerizable compound Hardener, The content of the inorganic filler is 150 parts by mass to 4500 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. The content ratio of the polymerizable liquid crystal compound to the non-liquid crystal polymerizable compound (mass of polymerizable liquid crystal compound: mass of non-liquid crystal polymerizable compound) is 20:80 to 95:5.

[2] The composition according to [1], wherein the inorganic filler contains a composite material X selected from a polymerizable liquid crystal compound having 2 or more functions and a non-liquid crystallizable polymerizable function having 2 or more functions At least one polymerizable compound of the compound or at least a part of the polymerizable compound is hardened and coated with a hardened material. [3] The composition according to [1] or [2], which includes a composite material A formed by bonding the inorganic filler and a coupling agent. [4] The composition according to any one of [1] to [3], which includes a composite material B in which the inorganic filler is bonded at one end of a coupling agent and polymerized at the other end Sex compounds.

[5] The composition according to any one of [1] to [4], wherein the polymerizable liquid crystal compound is a compound represented by the following formula (1). R ^al -Z-(AZ) _ml -R ^a1 … (1) [In formula (1), R ^{al is} independently a polymerizable group represented by the following formula (2-1) or formula (2-2) ; A is independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl , Fluorene-2,7-diyl, bicyclic[2.2.2]oct-1,4-diyl or bicyclic[3.1.0]hex-3,6-diyl, in these rings, any -CH ₂ -It can be substituted by -O-, any -CH= can be substituted by -N=, and any hydrogen can be substituted by halogen, cyano, C 1-10 alkyl or C 1-10 halogenated alkyl. In the radical, any -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C-; Z is independently a single bond or carbon number 1 ~22 alkylene group, in the alkylene group, any -CH ₂ -may be selected from -O-, -S-, -CO-, -COO-, -OCO-, -CH=CH-, -CF= CF-, -CH=N-, -N=CH-, -N=N-, -N(O)=N- or -C≡C- substitution, any hydrogen can be substituted by halogen; m1 is 1～6 Integer. ]

[式（2-1）～式（2-2）中，R^b 分別獨立地為氫、鹵素、-CF₃ 或碳數1～5的烷基，q為0或1。][Chem 1]

[In formula (2-1) to formula (2-2), R ^{b is} independently hydrogen, halogen, -CF ₃ or a C 1-5 alkyl group, and q is 0 or 1. ]

[6] The composition according to [5], wherein in the formula (1), Z is a single bond, -(CH ₂ ) _a -, -(CF ₂ ) _a -, -O(CH ₂ ) _a -, -(CH ₂ ) _a O-, -O(CH ₂ ) _a O-, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CH =CH-COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ -, -CH=N-, -N=CH-, -N=N-, -OCF ₂ -or -CF ₂ O-, each of which a is independently an integer of 1-20.

[7] The composition according to any one of [1] to [6], wherein the inorganic filler is a nitride, a carbide, a carbon material, a silicate compound, or a metal oxide. [8] The composition according to any one of [1] to [7], wherein the inorganic filler is selected from boron nitride, aluminum nitride, boron nitride carbon, boron carbide, graphite, carbon fiber, At least one of carbon nanotubes, aluminum oxide, cordierite, zinc oxide, zirconium oxide, and titanium oxide.

[9] A hardened product which is a hardened product of the composition according to any one of [1] to [8]. [10] A laminate, which is a laminate of a layer of a cured product of the composition according to any one of [1] to [8], and a metal, metal compound, or semiconductor layer. [11] An electronic machine containing: Electronic components with heat generating parts, and The hardened product according to [9] or the laminate according to [10]. [Effect of invention]

According to the composition of one embodiment of the present invention (hereinafter also referred to as “present composition”), a hardened product excellent in thermal conductivity and excellent adhesion to an adherend such as a metal, a metal compound, or a semiconductor layer can be easily formed. Furthermore, the present composition can easily form a cured product excellent in chemical stability, hardness, mechanical strength, and the like. Therefore, the present composition is preferably used for, for example, a heat-dissipating substrate, a heat-dissipating plate (a planar heat sink), a heat-dissipating sheet (sheet-shaped radiator), a heat-dissipating coating film, a heat-dissipating adhesive, a heat-dissipating insulating substrate with electrodes, a heat-conducting electronic substrate, etc. .

"Composition" The present composition is characterized by including an inorganic filler, a bifunctional or higher polymerizable liquid crystal compound, a bifunctional or higher non-liquid crystal polymerizable compound, and capable of curing the polymerizable liquid crystal compound and the non-liquid crystal polymerizable compound Of the hardener, relative to 100 parts by mass of the polymerizable liquid crystal compound, the content of the inorganic filler is 150 parts by mass to 4500 parts by mass, and the content ratio of the polymerizable liquid crystal compound to the non-liquid crystal polymerizable compound (Quality of polymerizable liquid crystal compound: mass of non-liquid crystal polymerizable compound) is 20:80 to 95:5.

<Inorganic filler> The inorganic filler is not particularly limited, and examples thereof include nitrides, carbides, carbon materials, silicate compounds, and metal oxides. As the inorganic filler, one kind may be used, or two or more kinds different in type, particle size, shape, etc. may be used.

Examples of the inorganic filler include alumina, magnesia, beryllium oxide, silicon oxide, titanium oxide, zirconium oxide, zinc oxide, iron oxide, ferrite, copper oxide, cerium oxide, yttrium oxide, tin oxide, and tin oxide. Oxides such as bismuth oxide, cobalt oxide, calcium oxide; silicate compounds such as mullite, cordierite; boron nitride, aluminum nitride, silicon nitride, boron nitride carbon and other nitrides; boron carbide, silicon carbide, etc. Carbides; diamond, graphite, carbon fiber, carbon nanotubes, graphene and other carbon materials; magnesium hydroxide, aluminum hydroxide and other hydroxides; silicon, gold, silver, copper, platinum, iron, tin, lead, nickel, Metals such as aluminum, magnesium, tungsten, molybdenum, and stainless steel; inorganic fibers such as glass fiber; cloth containing carbon fiber or glass fiber, etc.

Among these, in terms of being able to easily obtain a composition with more excellent thermal conductivity, it is more preferably selected from boron nitride, aluminum nitride, boron nitride carbon, boron carbide, graphite, carbon fiber, and carbon nanotubes. , At least one of alumina, cordierite, zinc oxide, zirconia, and titanium oxide.

When the composition is used for applications requiring insulation, reliability is improved when using an insulating inorganic filler such as long life, and therefore, in this case, it is preferable not to use a carbon material as a conductor, Or as an oxide of a part of a semiconductor, etc., but if the desired insulation is maintained, an inorganic filler having conductivity can also be used.

As an inorganic filler, hexagonal boron nitride (h-BN) and graphite are preferred because the thermal conductivity in the planar direction is very high. In particular, the dielectric constant of h-BN is also low and the insulation is also high. This composition is preferable when it is used for applications requiring insulation. In addition, for example, if a plate-like filler such as h-BN or graphite is used, the plate-like structure can be aligned along a mold or the like during forming or hardening, for example, which is preferable.

The type, shape, size, etc. of the inorganic filler can be appropriately selected according to the purpose, and examples of the shape of the inorganic filler include a plate shape, a spherical shape, an amorphous shape, a fibrous shape, a rod shape, and a cylindrical shape.

The average particle diameter of the inorganic filler is preferably 0.1 μm to 600 μm, and more preferably 1 μm to 200 μm, in terms of easily obtaining a heat dissipation member having better thermal conductivity. If the average particle size is 0.1 μm or more, the thermal conductivity is good, and if the average particle size is 200 μm or less, the filling rate can be increased. In addition, the average particle diameter in this specification is the median diameter based on the particle size distribution measured by the laser diffraction and/or scattering method. In addition, the average particle diameter refers to the average value of the length of the long side of the filler when the shape of the filler is plate-shaped, and refers to the fiber when the shape of the filler is fibrous or rod-shaped The average of the length or the length of the rod.

The content of the inorganic filler in this composition is relative to 100 parts by mass of the polymerizable liquid crystal compound in terms of being able to easily form a thermally conductive product and a hardened product having excellent adhesion to an adherend such as a metal, a metal compound, or a semiconductor layer. It is 150 parts by mass to 4500 parts by mass, preferably 200 parts by mass to 3000 parts by mass, more preferably 300 parts by mass to 2000 parts by mass, and particularly preferably 400 parts by mass to 1400 parts by mass.

<Polymerizable liquid crystal compound of 2 or more functions> A 2 or more polymerizable liquid crystal compound (hereinafter, also simply referred to as "polymerizable liquid crystal compound") is not particularly limited, and may be a trifunctional or more or tetrafunctional or more compound. The polymerizable liquid crystal compound is preferably a compound having two or more of the following ^Ra1 . The polymerizable liquid crystal compound used in the present composition may be one kind, or two or more kinds. Furthermore, "liquid crystal compound" refers to a compound that exhibits a nematic phase or a smectic phase equivalent liquid crystal phase.

If the polymerizable liquid crystal compound is a polycyclic compound, it tends to be a compound with high heat resistance. If the linearity is high, there is little elongation or fluctuation caused by heat between the inorganic fillers, and the heat can be transferred efficiently Phonon conduction is preferred. As a result, polycyclic and highly linear compounds often exhibit liquid crystallinity, and the liquid crystal compounds have excellent thermal conductivity and are preferable.

As a polymerizable liquid crystal compound, a cured product excellent in thermal conductivity and excellent heat dissipation characteristics can be easily obtained; the present composition can be cured without being affected by the amount of filler; and the present composition and cured product excellent in heat resistance can be easily obtained In other respects, the compound (1) represented by the formula (1) is preferred. In addition, the compound (1) has high polymerization reactivity, a wide liquid crystal phase temperature range, good miscibility, and the like, and when it is further mixed with other liquid crystal compounds or polymerizable compounds, etc., it becomes easy to become uniform. The compound (1) refers to the compound represented by the formula (1), and sometimes refers to at least one of the compounds represented by the formula (1). Hereinafter, the compounds represented by other formulas are also expressed in the same manner. R ^al -Z-(AZ) _ml -R ^a1 …（1）

By appropriately selecting the type and number of the terminal group R ^al , the ring structure A, and the bonding group Z of the compound (1), the physical properties such as the liquid crystal phase expression region can be arbitrarily adjusted, and a compound having the target physical properties can be obtained. In addition, m1 is an integer of 1 to 6, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.

• The terminal groups R ^{a1 and} R ^a1 are each independently a polymerizable group represented by the following formula (2-1) or formula (2-2). The term "R ^{a1 is} independent of each other" means that the two R ^{a1s included in the} compound (1) may be the same or different. In a certain formula in this specification, when there are more than two same symbols, and when there may be more than two same symbols due to the repeating unit (for example, in -(X) _p -, when p When it is 2, the two Xs present), or when there are two or more same symbols in different formulas, the groups represented by these symbols may be the same or different.

[Chem 2]

In Formula (2-1) to Formula (2-2), R ^{b is} independently hydrogen, halogen, -CF ₃ or a C 1-5 alkyl group, and q is 0 or 1. The C 1-5 alkyl group in R ^b is preferably a C 1-3 alkyl group, more preferably a methyl group. R ^b is preferably hydrogen in terms of ease of synthesis of compound (1) and the like. q is preferably 0.

・The ring structure AA is independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6- Diyl, fluorene-2,7-diyl, bicyclo[2.2.2]oct-1,4-diyl or bicyclo[3.1.0]hex-3,6-diyl, of these rings, any of- CH ₂ -can be substituted by -O-, any -CH= can be substituted by -N=, any hydrogen can be substituted by halogen, cyano, C 1-10 alkyl or C 1-10 halogenated alkyl, the In the alkyl group (including the alkyl group in the halogenated alkyl group), any -CH ₂ -may be selected from -O-, -CO-, -COO-, -OCO-, -CH=CH-, or -C≡C- replace.

The term "arbitrary" means "at least one", but generally considering the stability of the compound, it is preferable not to include a structure that is difficult to adopt based on common knowledge in the field, such as -O-O- where oxygen is adjacent to oxygen. In addition, regarding the ring A, the phrase "any hydrogen may be substituted by halogen, cyano, a C 1-10 alkyl group or a C 1-10 halogenated alkyl group" means, for example, 1,4-phenylene When at least one of hydrogen at the 2, 3, 5 and 6 positions is substituted with a substituent such as fluorine or methyl, and when the substituent is "halogenated alkyl group having 1 to 10 carbon atoms" The aspect includes examples such as 2-fluoroethyl or 3-fluoro-5-chlorohexyl.

The compound (1) tends to have more rings, and it is more difficult to soften at higher temperatures. Therefore, it is preferable when the present composition is used as a material for heat dissipation members, but when the softening temperature is higher than the polymerization temperature At this time, it tends to be difficult to form, so it is preferable to achieve a balance between the two according to the purpose. In addition, in this specification, a six-membered ring and a fused ring including a six-membered ring are basically regarded as a ring. For example, a separate three-membered ring, four-membered ring, and five-membered ring are not regarded as rings. In addition, condensed rings such as naphthalene ring or fluorene ring are regarded as one ring.

In the case where the compound (1) has at least one 1,4-phenylene group, it tends to become a compound with a large orientation order parameter and a large magnetization anisotropy. When the compound (1) has at least two 1,4-phenylene groups, there is a tendency that the temperature range of the liquid crystal phase is wide and the transparent point is high. When the compound (1) has a group in which at least one hydrogen on the 1,4-phenylene ring is substituted with a cyano group, halogen, -CF ₃ or -OCF ₃ , there is a compound having a high dielectric anisotropy tendency. In addition, when the compound (1) has at least two 1,4-cyclohexyl groups, it tends to become a compound having a high transparent point and a low viscosity.

Examples of preferred A include 1,4-cyclohexyl, 1,4-cyclohexenyl, 2,2-difluoro-1,4-cyclohexyl, and 1,3-dioxane. 2,5-diyl, 1,4-phenylene, 2-fluoro-1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1 ,4-phenylene, 2,6-difluoro-1,4-phenylene, 2,3,5-trifluoro-1,4-phenylene, pyridine-2,5-diyl, 3- Fluopyridine-2,5-diyl, pyrimidine-2,5-diyl, pyridazine-3,6-diyl, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene -2,7-diyl, 9-methylfluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, 9-ethylfluorene-2,7-diyl, 9-fluorofluorene-2,7-diyl, 9,9-difluorofluorene-2,7-diyl, etc.

Regarding the three-dimensional configuration of 1,4-cyclohexyl and 1,3-dioxane-2,5-diyl, trans is superior to cis. 2-Fluoro-1,4-phenylene and 3-fluoro-1,4-phenylene are the same in structure, so the latter is not exemplified. This rule also applies to the relationship between 2,5-difluoro-1,4-phenylene and 3,6-difluoro-1,4-phenylene.

More preferably, A is 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,3-dioxane-2,5-diyl, 1,4-phenylene, 2-fluoro- 1,4-phenylene, 2,3-difluoro-1,4-phenylene, 2,5-difluoro-1,4-phenylene, 2,6-difluoro-1,4-ethylene Phenyl etc. Particularly preferred A is 1,4-cyclohexyl and 1,4-phenylene.

・The bonding group Z Z is independently a single bond or an alkylene group having 1 to 22 carbon atoms. In the alkylene group, any -CH ₂ -may be selected from -O-, -S-, -CO-, and -COO -, -OCO-, -CH=CH-, -CF=CF-, -CH=N-, -N=CH-, -N=N-, -N(O)=N- or -C≡C- Substitution, any hydrogen can be substituted by halogen.

In terms of becoming a compound having desired physical properties and excellent in synthesis and handling, the preferred Z is a single bond, -(CH ₂ ) _a -, -(CF ₂ ) _a -, -O(CH ₂ ) _a -, -(CH ₂ ) _a O-, -O(CH ₂ ) _a O-, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CH= CH-COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ -, -CH=N-, -N=CH-, -N=N-,- In OCF ₂ -or -CF ₂ O-, each of a is independently an integer of 1-20.

Where Z is a single bond, -(CH ₂ ) ₂ -, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -CF=CF- or -( CH ₂ ) ₄ -, especially in the case of a single bond, -(CH ₂ ) ₂ -, -CF ₂ O-, -OCF ₂ -, -CH=CH- or -(CH ₂ ) _4- , There is a tendency to become less viscous compounds. When Z is -CH=CH-, -CH=N-, -N=CH-, -N=N-, or -CF=CF-, there is a tendency to become a compound having a wide temperature range of the liquid crystal phase, in When Z is an alkyl group having about 4 to 10 carbon atoms, the melting point of the compound tends to decrease.

More preferable Z includes single bond, -(CH ₂ ) ₂ -, -(CF ₂ ) ₂ -, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -OCF ₂ -, -CH=CH-, -CF=CF-, -C≡C-, -(CH ₂ ) ₄ -, -(CH ₂ ) ₂ O-, -O(CH ₂ ) ₂ -, -(CH ₂ ) ₃ O-, -O(CH ₂ ) ₃ -, -(CH ₂ ) ₂ COO-, -OCO(CH ₂ ) ₂ -, -CH=CH-COO-, -OCO-CH =CH-etc.

Further preferred Z includes single bond, -(CH ₂ ) ₂ -, -COO-, -OCO-, -CH ₂ O-, -OCH ₂ -, -CF ₂ O-, -(CH ₂ ) ₂ O-, -O(CH ₂ ) ₂ -, -OCF ₂ -, -CH=CH-, -C≡C-, etc. Particularly preferred Z is a single bond, -(CH ₂ ) ₂ -, -(CH ₂ ) ₂ O-, -O(CH ₂ ) ₂ -, -COO-, or -OCO-.

Compound (1) may be optically active or optically inert. When the compound (1) is optically active, the compound (1) may have an asymmetric carbon and an asymmetric axis. The stereo configuration of the asymmetric carbon can be R or S. The asymmetric carbon may be located in either ^Ra1 or A, and if it has an asymmetric carbon, it tends to be a compound having excellent compatibility with other components. When the compound (1) has an asymmetric axis, it tends to become a compound with a large twist-inducing force. In addition, the optical rotation may be any kind.

The compound (1) can also be represented by the following formula (1-a) or formula (1-b). PY-(AZ) _m -R ^a (1-a) PY-(AZ) _m -YP (1-b)

In formula (1-a) and formula (1-b), A and Z independently have the same meanings as A and Z in formula (1), and -R ^a independently from -ZR ^a1 in formula (1) For the same meaning, P is independently a polymerizable group represented by formula (2-1) to formula (2-2), and Y is independently a single bond or an alkylene group having 1 to 22 carbon atoms, preferably a carbon number 1-10 alkylene groups. In these alkylene groups, any -CH ₂ -may be substituted by -O-, -S-, -CO-, -COO-, -OCO-, or -CH=CH-. Particularly preferred Y is an alkylene group substituted by -O- at one end or both ends of -CH ₂ -alkylene group having 1 to 10 carbon atoms. m is an integer of 1 to 6, preferably an integer of 2 to 6, and more preferably an integer of 2 to 4. In formula (1-b), two P are preferably the same group, and two Y are preferably the same group, and both sides of -(AZ) _m -are preferably bilaterally symmetric. However, regarding "-ZY" in formula (1-b), this group has the same meaning as Z in formula (1).

Examples of preferred compound (1) include compound (a-1) to compound (g-7) shown below. Furthermore, * in the formula represents asymmetric carbon.

[Chemical 3]

[Chem 4]

[Chemical 5]

[化6]

[化7]

[Chem 8]

[化9]

[化10]

[Chem 11]

[化12]

[Chem 13]

[化14]

In the formula (a-1) ~ formula ^{(g-7), R a} , P and Y each independently of the formula (1-a) and formula (1-b) of the R ^a, P and Y have the same meaning.

Z ^{1 is} independently a single bond, -(CH ₂ ) ₂ -, -(CF ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH ₂ O-, -OCH ₂ -, -(CH ₂ ) ₂ O-, -O(CH ₂ ) ₂ -, -(CH ₂ ) ₃ O-, -O(CH ₂ ) ₃ -, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CH=CHCOO-, -OCOCH=CH-, -(CH ₂ ) ₂ COO-, -OCO(CH ₂ ) ₂ -, -C≡C-, -C≡C-COO-, -OCO-C≡C -, -C≡C-CH=CH-, -CH=CH-C≡C-, -CH=N-, -N=CH-, -N=N-, -OCF ₂ -or -CF ₂ O- .

Z ^{2 is} independently -(CH ₂ ) ₂ -, -(CF ₂ ) ₂ -, -(CH ₂ ) ₄ -, -CH ₂ O-, -OCH ₂ -, -(CH ₂ ) ₂ O-, -O(CH ₂ ) ₂ -, -(CH ₂ ) ₃ O-, -O(CH ₂ ) ₃ -, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CH= CHCOO-, -OCOCH=CH-, -(CH ₂ ) ₂ COO-, -OCO(CH ₂ ) ₂ -, -C≡C-, -C≡C-COO-, -OCO-C≡C-,- C≡C-CH=CH-, -CH=CH-C≡C-, -CH=N-, -N=CH-, -N=N-, -OCF ₂ -or -CF ₂ O-.

Z ^{3 is} independently a single bond, a C 1-10 alkyl group, -(CH ₂ ) _a -, -O(CH ₂ ) _a O-, -CH ₂ O-, -OCH ₂ -, -(CH ₂ ) ₂ O-, -O(CH ₂ ) ₂ -, -O(CH ₂ ) ₃ -, -(CH ₂ ) ₃ O-, -COO-, -OCO-, -CH=CH-, -CH= CHCOO-, -OCOCH=CH-, -(CH ₂ ) ₂ COO-, -OCO(CH ₂ ) ₂ -, -CF=CF-, -C≡C-, -CH=N-, -N=CH- , -N=N-, -OCF ₂ -or -CF ₂ O-. Here, a is independently an integer of 1-20.

In X, any hydrogen may be substituted with halogen, a C 1-10 alkyl group, or a C 1-10 fluorinated alkyl group.

The following shows specific examples of more preferable combinations of Y and -(AZ) _m -in formula (1-a) and formula (1-b).

[化15]

[Chem 16]

[化17]

・Synthesis method of compound (1) Compound (1) can be synthesized by combining well-known methods in organic synthetic chemistry. Methods for introducing target end groups, ring structures, and bonding groups into starting materials are, for example, Houben-Wyle (Methods of Organic Chemistry), Georg Thieme Press Verlag), Stuttgart), Organic Syntheses, John Wily & Sons, Inc.), Organic Reactions, John Wily & Sons Inc. .)), Comprehensive Organic Synthesis (Pergamon Press), New Experimental Chemistry Lecture (Maruzen) and other written books. Also, refer to Japanese Patent Laid-Open No. 2006-265527.

・Content of polymerizable liquid crystal compound The content of the polymerizable liquid crystal compound in the present composition is preferably 1% by mass to 45% by mass, and more preferably 2% by mass to 30% by mass relative to 100% by mass of the present composition. When the content of the polymerizable liquid crystal compound is within the above range, it is possible to easily form a cured product that is well-balanced and excellent in thermal conductivity and adhesion to an adherend such as a metal, a metal compound, or a semiconductor layer.

<Hardener> The curing agent is not particularly limited as long as it can harden the polymerizable liquid crystal compound and the non-liquid crystal polymerizable compound, and examples thereof include acid anhydride-based hardeners, amine-based hardeners, phenol-based hardeners, and thiol-based hardeners. Agent, imidazole. Among these, the polymerizable liquid crystal compound can be easily hardened, the thermal conductivity can be easily formed, and the adhesion to the adherend such as a metal, a metal compound, or a semiconductor layer is well-balanced and an excellent cured product can be easily obtained. In other words, it is preferably an amine-based hardener. One kind of hardener may be used, or two or more kinds may be used.

As the amine-based hardener, a commonly used compound can be used without particular limitation, and a commercially available hardener can also be used. Among them, from the viewpoint of curability, a bifunctional or more multifunctional hardener is preferable, and from the viewpoint of thermal conductivity, a polyfunctional hardener having a rigid skeleton is more preferable. In particular, diamine is preferable because it can harden the polymerizable liquid crystal compound without hindering the liquid crystallinity of the polymerizable liquid crystal compound.

Specific examples of the amine-based hardener include diethylenetriamine, triethylenetetramine, tetraethylenepentamine, o-xylenediamine, m-xylenediamine, p-xylenediamine, and trimethylhexamethylene Methyldiamine, 2-methylpentamethylenediamine, diethylaminopropylamine, isophoronediamine, 1,3-bisaminomethylcyclohexane, bis(4-amine 3-methylcyclohexyl)methane, bis(4-aminocyclohexyl)methane, norbornene diamine, 1,2-diaminocyclohexane, 3,9-dipropaneamine-2,4 ,8,10-tetraoxaspiro[5,5]undecane, 4,4'-diaminodiphenylmethane, 4,4'-diamino-1,2-diphenylethane , O-phenylenediamine, m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl sulfone, 4,4'-diamino -3,3'-dimethoxybiphenyl, 4,4'-diaminophenyl benzoate, 1,5-diaminonaphthalene, 1,3-diaminonaphthalene, 1,4- Diaminonaphthalene, 1,8-diaminonaphthalene, polyoxypropylene diamine, polyoxypropylene triamine, polycyclohexyl polyamine, N-aminoethyl piperazine.

In addition, as the amine-based hardener, a compound (2) represented by the following formula (2) may also be mentioned. JZ-(XZ) _m1 -J …（2）

In formula (2), J is independently an amine group, X is independently 1,4-cyclohexyl, 1,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6- Diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclo[2.2.2]oct-1,4-diyl, or bicyclo[3.1.0]hex-3,6 -Diyl, in these rings, any -CH ₂ -may be substituted by -O-, any -CH= may be substituted by -N=, any hydrogen may be halogen, alkyl group having 1 to 10 carbons, or carbon number 1 to 10 halogenated alkyl substitution, in which any -CH ₂ -may be substituted by -O-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C- , Z is independently a single bond or an alkylene group having 1 to 22 carbon atoms. In the alkylene group, any -CH ₂ -may be selected from -O-, -S-, -CO-, -COO-, and -OCO -, -CH=CH-, -CF=CF-, -CH=N-, -N=CH-, -N=N-, -N(O)=N- or -C≡C- substitution, arbitrary Hydrogen can be substituted by halogen; m1 is an integer of 1-6.

X in formula (2) is preferably the same group as A in formula (1), Z in formula (2) is preferably the same group as Z in formula (1), in formula (2) m1 is preferably an integer of 2 to 6, and more preferably an integer of 2 to 4.

The compound (2) is more preferably a compound (2-1) represented by the following formula (2-1). JZXZ ¹ -XZJ… (2-1) [J, X and Z in formula (2-1) have the same meaning as J, X and Z in formula (2), Z ¹ in formula (2-1) It has the same meaning as Z in formula (2). ]

Compound (2-1) is preferably a compound in which Z is a single bond, preferably a compound in which X is 1,4-phenylene, and preferably a compound in which Z ¹ is a group represented by -(CH ₂ ) _n- . In particular, the structure of the compound in which n in n in Z ¹ is an even number is bilaterally symmetric and is difficult to bend. Therefore, the composition and the cured product obtained by using the compound tend to have higher thermal conductivity, which is preferable.

The use amount of the hardener is preferably an amount that is 1 mole relative to the amount of the functional group that can react with the hardener in the component (a) that can react with the hardener contained in the composition, enabling the component to react with component (a) present in the composition contained in the (b) component in the functional group capable of (a) the reaction of a mole (e.g., containing a -NH ₂ to In the case of compound 1 moles, the moles of the functional group is 2 moles) preferably from 0.6 to 1.8, more preferably from 0.8 to 1.4. Examples of the component (a) include the polymerizable liquid crystal compound or the following non-liquid crystal polymerizable compound, and examples of the component (b) include a curing agent.

<Non-liquid crystal polymerizable compound> This composition contains a bifunctional or higher non-liquid crystal polymerizable compound (hereinafter, also simply referred to as "non-liquid crystal polymerizable compound"). The non-liquid crystal polymerizable compound is a compound other than the polymerizable liquid crystal compound, and refers to a compound having a polymerizable group but not independently exhibiting a nematic phase or a smectic phase equivalent liquid crystal phase. The non-liquid crystal polymerizable compound may be a compound having 3 or more functions or 4 or more functions. One type of non-liquid crystal polymerizable compound may be used, or two or more types may be used.

The non-liquid crystal polymerizable compound is not particularly limited, and examples thereof include a compound having a group capable of reacting with a polymerizable group possessed by the polymerizable liquid crystal compound, or a compound having a reactive group possessed by the hardener. The compound of the group is preferably a compound having a group capable of reacting with the reactive group of the hardener, and more preferably ^a compound having the Ra.

Examples of non-liquid crystal polymerizable compounds include vinyl derivatives, styrene derivatives, (meth)acrylic acid derivatives, sorbic acid derivatives, fumaric acid derivatives, itaconic acid derivatives, and polyether diethers. Epoxy compounds such as glycidyl ether, diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of biphenol. In these compounds, any hydrogen may be substituted by halogen, cyano, a C 1-10 alkyl group or a C 1-10 halogenated alkyl group. In the alkyl group, any -CH ₂ -may be replaced by -O- , -CO-, -COO-, -OCO-, -CH=CH- or -C≡C-. The non-liquid crystal polymerizable compound can be synthesized by a known method in organic synthetic chemistry, and a commercially available product can also be used.

The use amount of the non-liquid crystal polymerizable compound in the present composition is not particularly limited, and it is preferably the normal use amount described in the column of the use amount of the hardener. The content ratio of the polymerizable liquid crystal compound to the non-liquid crystal polymerizable compound (the mass of the polymerizable liquid crystal compound: the mass of the non-liquid crystal polymerizable compound) is 20:80 to 95:5, preferably 20:80 to 90: 10, more preferably 25:75～80:20. If the content ratio of the polymerizable liquid crystal compound to the non-liquid crystal polymerizable compound is within the above range, a cured product excellent in thermal conductivity and excellent adhesion to a adherend such as a metal, a metal compound, or a semiconductor layer can be easily formed

<Coupling agent> In terms of obtaining a hardened product having more excellent thermal conductivity, the present composition preferably contains a coupling agent. In the case where the coupling agent is used in this manner, the coupling agent may be added when mixing the inorganic filler, the polymerizable liquid crystal compound, and the curing agent, etc. However, in terms of obtaining a cured product with more excellent thermal conductivity, it is preferable to use At least a part of the coupling agent used is used in the form of a composite material A bonded in advance with an inorganic filler. In this case, it is also preferable that the inorganic filler is bonded to one end of the coupling agent and the other end of the coupling agent The form of the composite material B to which the polymerizable compound is bonded is used. The polymerizable compound is the above-mentioned polymerizable liquid crystal compound or non-liquid crystal polymerizable compound.

The coupling agent is not particularly limited, and known coupling agents such as silane-based coupling agents, titanate-based coupling agents, aluminate-based coupling agents and the like can be used. Among these coupling agents, silane-based coupling agents are preferred. One type of coupling agent may be used, or two or more types may be used.

The coupling agent is a compound having at least two reactive groups, preferably a reactive group capable of bonding to an inorganic filler, and a reactive group capable of bonding two or more coupling agents to each other, or a polymerizable liquid crystal The compound, specifically, is a reactive group to which a functional group (for example, oxetanyl group) of the polymerizable liquid crystal compound is bonded.

Examples of the reactive group include hydrolyzable groups such as alkoxy groups; amine groups, ureido groups, oxetanyl groups, oxetanyl groups, carboxyl groups, acid anhydride groups, mercapto groups, isocyanate groups, imidazolyl groups, and vinyl groups Or (meth) acryl acetyl group and other ethylenically unsaturated bonding groups.

The combination of the reactive group capable of bonding two or more coupling agents to each other, or the combination of the functional group possessed by the polymerizable liquid crystal compound and the reactive group capable of bonding with the functional group is not particularly limited, for example Examples include a combination of an oxetanyl group and an amine group, a vinyl group, a methacryl group, a carboxyl group or an acid anhydride group and an amine group, an imidazolyl group, and an oxetanyl group. Among these, it is more preferable to combine the structure after the reaction into a structure having high heat resistance.

When a compound having an oxetanyl group or an oxetanyl group is used as the polymerizable liquid crystal compound, it is preferable to use a coupling agent having an amine group. Examples of such a coupling agent include Sila-Ace (trade name) S310, Sila-Ace S320, Sila-Ace S330, Sila-Ace S360, and Shin-Etsu manufactured by JNC Corporation. KBM-903 and KBE-903 manufactured by Chemical Industry Co., Ltd.

The use amount of the coupling agent is not particularly limited, and in terms of obtaining a hardened product having more excellent thermal conductivity, it is preferably 0.1% by mass to 10% by mass, and more preferably 0.5% by mass with respect to 100% by mass of the present composition. % ~ 5 mass%.

When the coupling agent is used in the form of the composite material A or the composite material B, the reaction amount of the coupling agent with respect to the inorganic filler mainly varies depending on the size of the inorganic filler or the reactivity of the coupling agent used, etc. It is difficult to specify, but it is preferable to bond as much coupling agent as possible to the inorganic filler, so that the reactivity of the coupling agent with the reactive group is preferably relative to the number of reactive groups the inorganic filler has. Coupling agents are used in such a way that the number of groups is the same or slightly larger. In terms of easily obtaining the present composition and hardened product excellent in thermal stability and durability, the amount of bonding of the coupling agent with respect to 100 parts by mass of the inorganic filler is preferably 0.1 part by mass or more, more preferably 0.3 part by mass Parts to 50 parts by mass, particularly preferably 0.5 parts to 25 parts by mass.

<Other ingredients> This composition may also contain inorganic fillers, polymerizable liquid crystal compounds, hardeners, non-liquid crystal polymerizable compounds and other components other than coupling agents, such as non-polymerizable compounds, polymerization initiators, solvents, stabilizers, adhesiveness Granting agent, organic filler. One of these other components may be used alone, or two or more of them may be used.

[Non-polymerizable compound] The present composition may also contain non-polymerizable compounds. The compound is not particularly limited as long as it does not react with the inorganic filler, polymerizable liquid crystal compound, hardener, non-liquid crystal polymerizable compound, and coupling agent, and preferably does not cause film formation and mechanical properties The compound with reduced strength is more preferably a polymer compound. Examples of the polymer compound include polyolefin resin, polyethylene resin, silicone resin, and wax.

The non-polymerizable compound may be a liquid crystal compound having no polymerizable group. Examples of such non-polymerizable liquid crystal compounds are found in the liquid crystal database (LiqCryst, LCI Publisher (Publisher GmbH), Hamburg, Hamburg, Germany) etc. as a date base of liquid crystal compounds Recorded. When a composition containing a non-polymerizable liquid crystal compound is polymerized, for example, a composite material of a polymer of the compound (1) and a non-polymerizable liquid crystal compound can be obtained. In one aspect of such a composite material, there is a non-polymerizable liquid crystal compound in a polymer grid such as a polymer-dispersed liquid crystal. Therefore, as the non-polymerizable liquid crystal compound, it is desirable to have a liquid crystal compound that has no fluidity in the temperature range where the cured product obtained from the present composition is used.

[Polymerization initiator] The present composition may also contain a polymerization initiator. The polymerization initiator should just use a photo radical polymerization initiator, a photo cationic polymerization initiator, a thermal radical polymerization initiator, etc. according to the component contained in this composition or a desired polymerization method. In particular, since the inorganic filler tends to easily absorb ultraviolet rays, a thermal radical polymerization initiator is preferred. Examples of preferred initiators for thermal radical polymerization include benzoyl peroxide, diisopropyl dicarbonate, tert-butyl 2-ethylhexanoate, and peroxide Tert-butyl valerate, di-tert-butyl peroxide (DTBP), tert-butyl diisobutyrate peroxide, lauryl peroxide, dimethyl 2,2'-azobisisobutyrate (MAIB), azobisisobutyronitrile (AIBN), azobiscyclohexanecarbonitrile (ACN).

[Solvent] This composition may contain a solvent. Examples of preferred solvents include benzene, toluene, xylene, mesitylene, hexane, heptane, octane, nonane, decane, tetrahydrofuran, γ-butyrolactone, and N-methylpyrrolidine. Ketones, dimethylformamide, dimethylsulfoxide, cyclohexane, methylcyclohexane, cyclopentanone, cyclohexanone, propylene glycol monomethyl ether acetate (PGMEA). There is no particular restriction on the amount of solvent used, as long as the polymerization efficiency, solvent cost, energy cost, etc. are taken into consideration and determined separately for each case.

[stabilizer] In this composition, in order to facilitate handling of the composition, a stabilizer may be added. The stabilizer is not particularly limited as long as the effect of the present invention is not impaired, and examples include antioxidants, copper inhibitors, metal deactivators, anti-aging agents, defoamers, antistatic agents, and weathering agents. As these stabilizers, known stabilizers can be used without limitation.

Examples of the antioxidant include hydroquinone, 4-ethoxyphenol, 3,5-di-tert-butyl-4-hydroxytoluene (BHT), and the like.

For example, when the hardened product of the present composition is used in contact with a metal layer, etc., and the organic component in the hardened product may be deteriorated by contact with the metal, it is preferable to add such as Japanese Patent Laid-Open No. 5- The copper inhibitors or metal deactivators listed in Gazette No. 48265. As the copper inhibitor (trade name), it is preferably Mark ZS-27 and Mark CDA-16 manufactured by ADEKA Corp.; Sanguang-Aibo manufactured by Sanko Chemical Industry Co., Ltd. Colleen (SANKO-EPOCLEAN); BASF (BASF) company made Irganox (Irganox) MD1024, etc. The amount of the copper inhibitor added is preferably 100 parts by mass with respect to the total amount of organic components contained in the present composition in terms of preventing deterioration of the organic components of the hardened part in contact with the metal, etc. It is 0.1 to 3 parts by mass.

Examples of the organic filler include fibers including polyvinyl formal, polyvinyl butyral, polyester, polyamide, and polyimide.

<Preparation method of this composition> In this composition, an inorganic filler, a polymerizable liquid crystal compound, a non-liquid crystal polymerizable compound, a curing agent, and components other than the above used as needed may be mixed. The mixing method at this time is not particularly limited, and for example, the following method may be mentioned: weighing is performed such that the mixing ratio of the inorganic filler and the polymerizable liquid crystal compound is within the above range, and after mixing using an agate mortar or the like, using a biaxial roller or the like mixing.

As described above, when preparing the present composition, as the inorganic filler, it is preferable to use the composite material A in which the inorganic filler and the coupling agent are bonded in advance, or to bond the one end of the inorganic filler and the coupling agent in advance to make A composite material B in which a polymerizable compound is bonded to the other end of the coupling agent.

As the method of bonding the inorganic filler and the coupling agent in advance, a known method can be used, but the following method is preferred. The inorganic filler and the coupling agent are mixed in the presence of a solvent, stirred with a stirrer or the like, and then dried. After the solvent is dried, a vacuum dryer or the like is used to keep it under vacuum conditions. If necessary, a purification step is performed in which a solvent is added after the holding, and ultrasonic treatment, centrifugal separation, and the like are added to thereby freely remove the coupling agent attached (unbonded) to the solid content. This refining process can be carried out multiple times. Furthermore, the purified composite material can be dried using an oven or the like.

The solvent is not particularly limited, but it is preferably a solvent capable of dissolving the coupling agent, and preferably a solvent capable of dispersing the inorganic filler. The time for mixing and stirring the inorganic filler and the coupling agent is not particularly limited, and examples thereof include 1 minute to 24 hours.

The drying conditions (eg, drying time, drying temperature, drying environment) are not particularly limited as long as the solvent used is dried, and may be appropriately set according to the solvent used. The conditions during holding under the vacuum conditions, for example, are preferably conditions like dehydration condensation. Specifically, the holding temperature is preferably 20°C to 150°C, and the holding time is preferably 1 minute to 24 hours.

The method of bonding the coupling agent bonded to the inorganic filler and the polymerizable compound is not particularly limited, and a known method can be used, but the following method is preferred. After mixing the coupling agent bonded to the inorganic filler with the polymerizable compound using an agate mortar or the like, kneading is performed using a biaxial roller or the like. Thereafter, if necessary, separation and purification are performed by ultrasonic treatment, centrifugal separation, etc. (the polymerizable compound that is not bonded to the coupling agent is removed).

In addition, in terms of obtaining a hardened product having more excellent thermal conductivity, it is preferable to use at least one polymerizable compound selected from the group consisting of a polymerizable liquid crystal compound and a non-liquid crystal polymerizable compound or the above-mentioned polymerization The composite material X formed by coating an inorganic filler with a hardened material obtained by hardening at least a part of the organic compound is more preferably a composition in which the first polymerizable compound (polymerizable liquid crystal compound or non-liquid crystal) is used in advance Polymerizable compound) or a cured material obtained by hardening at least a part of the composite material X coated with an inorganic filler, and a second polymerizable compound (polymerizable liquid crystal compound or non-liquid crystal polymerizable) is added during curing or molding, etc. Compound, except the first polymerizable compound. That is, in the case of using a polymerizable liquid crystal compound as the first polymerizable compound, the second polymerizable compound is a non-liquid crystal polymerizable compound). When producing such a composite material X, as the inorganic filler, an inorganic filler may be used alone, but the composite material A or the composite material B may also be used. In addition, when producing such a composite material X, it is preferable to use a hardener together with the first polymerizable compound. Furthermore, the coating not only includes the case where the entire surface of the inorganic filler is coated, but also includes the case where a part of the surface of the inorganic filler is coated.

The method of coating the inorganic filler (composite material A or composite material B) with a cured product obtained by curing a polymerizable compound or at least a part thereof is not particularly limited, and a known method can be used, but the following method is preferred. Using a disperser or the like, the inorganic filler, the first polymerizable compound and the hardener are stirred at a temperature of preferably 60°C to 140°C, more preferably 70°C to 125°C for about 5 minutes to 1 hour. According to this method, the inorganic filler (composite material A or composite material B) can be coated with a hardened product obtained by hardening at least a part of the polymerizable compound.

"Hardened" The hardened product of the present invention is obtained by hardening the present composition. The hardening can be carried out in a solvent or without a solvent. In addition, after the composition containing the solvent is applied to the substrate by, for example, spin coating, the solvent may be removed and then cured. The method of hardening can be appropriately selected according to the components used, the intended use, and the like, and may be thermal curing, photocuring, or heating to an appropriate temperature after photocuring to perform thermal curing.

The thermal hardening is performed, for example, by heating at a temperature of preferably 50° C. to 350° C., more preferably 60° C. to 300° C., further preferably 70° C. to 250° C. for 5 seconds to 10 hours, preferably 1 From 5 minutes to 5 hours, more preferably from about 5 minutes to 1 hour. The hardening may be performed in two or more stages, for example, it may be a method of hardening by performing the following compression molding after the pre-hardening, the pre-hardening is preferably performed at 60°C to 140°C, more Preferably, heating is performed at a temperature of 70°C to 125°C for about 5 minutes to 1 hour.

The photo-curing can be performed by, for example, light irradiation in such a manner that the cumulative illuminance is preferably 10 mJ/cm ² to 2000 mJ/cm ² , more preferably 50 mJ/cm ² to 500 mJ/cm ² .

"Laminate" The laminate of the present invention is a laminate of a hardened layer of the present composition (hereinafter also simply referred to as "hardened layer") and a metal, metal compound, or semiconductor layer. The hardened layer contained in the laminate may be one layer, or two or more layers. In addition, the metal, metal compound, or semiconductor layer contained in the laminate may be one layer, or two or more layers. When two or more hardened material layers are included, these hardened material layers may be the same or different. The same is true when two or more metal, metal compound or semiconductor layers are included. The laminate may include other conventionally known layers such as an adhesive layer. However, the adhesion between the hardened material layer and the metal, metal compound, or semiconductor layer is excellent. No other layers are included between the compound or semiconductor layers.

Examples of the metal, metal compound, or semiconductor layer include metal layers containing copper, aluminum, nickel, gold, alloys of these metals, and the like; metal compound layers containing oxides and nitrides of these metals; and silicon, Semiconductor layers such as GaAs, GaN, SiC, and germanium oxide, specifically, metal electrodes, semiconductor wafers, and the like can be mentioned. In addition, the metal, metal compound, or semiconductor layer may be a layer in which a plurality of metal (electrode), metal compound, or semiconductor layers are provided on a predetermined substrate. The shape of the metal, metal compound, or semiconductor layer is not particularly limited, and examples thereof include a plate shape and a rod shape.

The laminate preferably includes a bonded body in which a metal, metal compound or semiconductor layer, a hardened layer, and a metal, metal compound or semiconductor layer are sequentially stacked. The manufacturing method of the bonded body is not particularly limited, and the following method is preferred: the present composition is coated on one side of one metal, metal compound or semiconductor layer or two metal, metal compound or semiconductor layers to form a sequential layer The metal, metal compound or semiconductor layer, the hardened layer, and the bonded body of the metal, metal compound or semiconductor layer are arranged and compression-molded.

The temperature during compression molding is usually room temperature to 350°C, preferably room temperature to 300°C, more preferably 50°C to 250°C, and the time is usually 5 seconds to 10 hours, preferably 1 minute to 5 hours, more It is preferably 5 minutes to 1 hour, and the pressure is usually 0.01 MPa to 30 MPa, preferably 0.1 MPa to 5 MPa. If the present composition is used, the laminate and the joined body can be produced by heating at a relatively low temperature. After hardening in this way, in order to suppress stress deformation, etc., it is preferable to perform slow cooling. In addition, it may be reheated after cooling to ease deformation.

The film thickness of the laminate, especially the cured product layer in the bonded body may be appropriately changed according to the application, and in order to increase the thermal conductivity in the thickness direction of the laminate, it is preferably thin, preferably 5 μm to 2000 μm, more preferably 10 μm to 1000 μm, particularly preferably 15 μm to 500 μm.

The hardened material and the hardened material layer have high thermal conductivity, and the thermal expansion rate is from negative to positive value, chemical stability, hardness and mechanical strength according to the type of organic material and inorganic filler used, blending ratio, curing conditions, etc. Excellent. Furthermore, the mechanical strength refers to Young's modulus, tensile strength, tear strength, bending strength, bending elastic modulus, impact strength and the like. Therefore, the hardened product and the laminate can be effectively used for heat dissipation substrates, heat dissipation plates (planar heat sinks), heat sinks, heat dissipation films, heat dissipation coating films, heat dissipation adhesives, heat dissipation insulating substrates with electrodes, and heat conductive electronics Substrates, etc.

"Electronic Machine" The electronic device of the present invention includes the hardened product or the laminate, and an electronic device having a heat generating portion. The hardened product or laminate is preferably arranged in the electronic device so as to be in contact with the heat generating portion. Here, the so-called contact may be that the cured product or laminate is in direct contact with the heat generating portion, or may be in contact via an adhesive layer or the like. The form of the hardened material or the laminate may be a heat dissipation substrate, a heat dissipation plate (planar heat sink), a heat sink, a heat dissipation film, a heat dissipation coating film, a heat dissipation adhesive, a heat dissipation insulating substrate with electrodes, and a heat conductive electronic substrate Etc.

Examples of the electronic device include semiconductor elements. The hardened product or laminate contains the hardened product obtained from the present composition, and therefore has not only high thermal conductivity but also high heat resistance. Therefore, as the electronic device, as for the semiconductor device, when it is necessary to include high power More efficient heat dissipation mechanisms are particularly effective when power semiconductors including silicon, silicon carbide, gallium nitride, gallium oxide, diamond, etc. are used. Examples of electronic devices including these power semiconductors include main conversion elements of large-power inverters, power failure-free power supply devices, variable-voltage and variable-frequency control devices for AC motors, control devices for railway vehicles, and hybrids. Electric transportation equipment such as power cars and electric cars, induction heat (IH) cookers, etc. [Example]

Hereinafter, the present invention will be described in detail using examples. However, the present invention is not limited to the contents described in the following examples.

The component materials used in the examples of the present invention are as follows.

<Inorganic filler> ・Boron nitride: h-BN particles, manufactured by Momentive Performance Materials Japan (co-branded), (brand name) PolarTherm PTX-25

<Polymerizable liquid crystal compound with 2 or more functions>・"Polymerizable liquid crystal": manufactured by JNC (shares), the following formula (1-11) (polymerizable oxetanyl compound) [Chem. 18]

・「jER828」：三菱化學（股）製造，（商品名）jER828（聚合性氧雜環丙基化合物）<Non-liquid crystal polymerizable compound with 2 or more functions> ・“YX4000H”: A compound represented by formula (1-12), manufactured by Mitsubishi Chemical Corporation, (trade name) jER YX4000H [Chem. 19]

・"JER828": manufactured by Mitsubishi Chemical Corporation, (trade name) jER828 (polymerizable oxetanyl compound)

・「硬化劑2」：式（1-14）所表示的化合物（4,4'-二胺基-1,2-二苯基甲烷），和光純藥工業（股）製造 [化21]

<Hardener>・"Hardener1": Compound (4,4'-ethylenediphenylamine) represented by formula (1-13), manufactured by Tokyo Chemical Industry Co., Ltd. [Chem. 20]

・"Hardener 2": a compound represented by formula (1-14) (4,4'-diamino-1,2-diphenylmethane), manufactured by Wako Pure Chemical Industries, Ltd. [Chem. 21]

<Aluminum plate> ・"Aluminum plate": size; 1×1 cm or 4×4 cm, both with a thickness of 400 μm

[Example 1] Put 7.2 g of PTX-25, 0.621 g of polymerizable liquid crystal, 1.534 g of YX4000H, and 0 625 g of hardener 1 into a powder laboratory dispersion tester PWB manufactured by Nippon Coke & Engineering (stock) In the container of the type, with the inner temperature of the container kept at 80°C, the mixture was stirred at 500 revolutions for 10 minutes, then at 1,000 revolutions for 1 minute, then at 2000 revolutions for 1 minute, and then at 3000 revolutions for 1 minute. Then, after the internal temperature became 60°C or lower, the composition was taken out from the container.

・Preparation of samples for thermal diffusivity measurement Prepare two aluminum plates (1×1 cm, thickness 400 μm), weigh 0.01 g of the composition obtained above and sandwich it between the two aluminum plates, using a compression molding machine set at 160°C (IMC-19EC manufactured by Co., Ltd.) Pressurized to 3 MPa, maintained in a heated state for 45 minutes, then cooled, and then released the pressure to take out the sample for thermal diffusivity measurement.

<Measurement of thermal diffusivity and calculation of thermal conductivity> Using a sample for thermal diffusivity measurement, a multi-layer sample was measured using a LFA467 super-flash (HyperF1ash) thermal diffusivity device manufactured by NETZSCH Co., Ltd. The multi-layer sample analytical model (three layers) calculates the thermal diffusivity including the heat loss caused by contact thermal resistance. In the analysis of the multilayer sample, the density of the cured product was 1.6 g/cm ³ and the specific heat was 1.0 J/g･K. By multiplying the obtained thermal diffusivity by the density and specific heat, the thermal conductivity of the hardened product is calculated. The results are shown in Table 1.

・Preparation of samples for tensile test Prepare two aluminum plates (4×4 cm, thickness 400 μm), weigh 0.01 g of the composition 42 obtained above, and place them on the half surfaces (2 cm×4) of the aluminum plates 41 and 43 as shown in FIG. 1 cm) and sandwich the unmounted parts between the two aluminum plates so as not to overlap each other, using a compression molding machine set at 160°C (manufactured by Toyo Seiki Co., Ltd.), and a mini test press )-10 type small heating press) Pressurized to 2 MPa, maintained in a heated state for 45 minutes and then cooled, and then released the pressure, take out the tensile test sample.

<Tensile test> The tensile test was carried out as follows to confirm the tensile strength. Using a tensile test measuring machine (manufactured by Tensilon, RTF-1310), the tensile test sample was stretched in the direction of the arrow in FIG. 2 at a speed of 1 mm/min to measure the tension at break (N) . When it is not broken, the detection limit (500 N) or more is assumed. The results are shown in Table 1. In addition, "E" in Table 1 shows that when the tensile test sample was fixed to the tensile tester, the two aluminum plates were peeled off.

[Examples 2 to 3 and Comparative Examples 1 to 3] A composition was prepared in the same manner as in Example 1, except that the type and usage amount of each component were changed as shown in Table 1, and each sample was prepared from the composition and evaluated.

[Comparative Example 4] Put 8.0 g of PTX-25, 1.554 g of polymerizable liquid crystal, and 0.446 g of hardener 1 in a plastic bag. After shaking well, remove the composition from the bag. Except having used the obtained composition, it carried out similarly to Example 1, and evaluated.

[Comparative Example 5] In Comparative Example 4, each component type and amount of use were changed to those shown in Table 1, and the evaluation was performed in the same manner as in Comparative Example 4 except for that.

[Table 1]

By using a predetermined amount of inorganic filler, a predetermined ratio of a bifunctional or higher polymerizable liquid crystal compound and a bifunctional or higher non-liquid crystallizable polymerizable compound, and a hardener, high adhesion to metals, metal compounds, or semiconductors can be obtained. A composition (hardened material) with high thermal conductivity. On the other hand, when a bifunctional or higher polymerizable liquid crystal compound or a bifunctional or higher non-liquid crystal polymerizable compound is not used, a composition with high adhesion to metals, metal compounds or semiconductors and high thermal conductivity cannot be obtained (Hardened).

41: Aluminum plate 42: Composition (hardened material) 43: Aluminum plate

FIG. 1 is a schematic diagram when a sample for a tensile test in Examples is produced. FIG. 2 is a schematic cross-sectional schematic diagram when a tensile test is performed using the tensile test sample obtained in FIG. 1.

Claims (11)

A composition comprising an inorganic filler, a bifunctional or higher polymerizable liquid crystal compound, a bifunctional or higher non-liquid crystal polymerizable compound, and a curing agent capable of hardening the polymerizable liquid crystal compound and the non-liquid crystal polymerizable compound , The content of the inorganic filler is 150 parts by mass to 4500 parts by mass relative to 100 parts by mass of the polymerizable liquid crystal compound. The ratio of the content of the polymerizable liquid crystal compound to the non-liquid crystal polymerizable compound, that is, the mass of the polymerizable liquid crystal compound: the mass of the non-liquid crystal polymerizable compound is 20:80 to 95:5. The composition according to item 1 of the patent application scope, wherein the inorganic filler contains a composite material X selected from a group consisting of a polymerizable liquid crystal compound having 2 or more functions and a non-liquid crystal polymerizable function having 2 or more functions At least one polymerizable compound of the compound or at least a part of the polymerizable compound is hardened and coated with a hardened material. The composition as described in item 1 or 2 of the patent application scope includes a composite material A, which is formed by bonding the inorganic filler and a coupling agent. The composition as described in item 1 or item 2 of the scope of patent application includes composite material B, which is formed by bonding the inorganic filler at one end of the coupling agent and a polymerizable compound at the other end . The composition as described in item 1 or item 2 of the patent application scope, wherein the polymerizable liquid crystal compound is a compound represented by the following formula (1), R ^al -Z-(AZ) _ml -R ^a1 … (1) In formula (1), R ^{al is} independently a polymerizable group represented by the following formula (2-1) or formula (2-2); A is independently 1,4-cyclohexyl, 1 ,4-cyclohexenyl, 1,4-phenylene, naphthalene-2,6-diyl, tetrahydronaphthalene-2,6-diyl, fluorene-2,7-diyl, bicyclic [2.2. 2] Oct-1,4-diyl or bicyclo[3.1.0]hex-3,6-diyl, in these rings, at least one -CH ₂ -may be substituted by -O-, and at least one -CH= may be- N=substitution, at least one hydrogen can be substituted by halogen, cyano, C1-C10 alkyl or C1-C10 halogenated alkyl. In the alkyl group, at least one -CH ₂ -can be substituted by -O-, -CO-, -COO-, -OCO-, -CH=CH- or -C≡C- substitution; Z is independently a single bond or an alkylene group having 1 to 22 carbon atoms, in the alkylene group, At least one -CH ₂ -may be selected from -O-, -S-, -CO-, -COO-, -OCO-, -CH=CH-, -CF=CF-, -CH=N-, -N=CH- , -N=N-, -N(O)=N- or -C≡C-, at least one hydrogen can be substituted by halogen; m1 is an integer of 1 to 6,

In Formula (2-1) to Formula (2-2), R ^{b is} independently hydrogen, halogen, -CF ₃ or a C 1-5 alkyl group, and q is 0 or 1. The composition as described in item 5 of the patent application scope, wherein, in the formula (1), Z is a single bond, -(CH ₂ ) _a -, -(CF ₂ ) _a -, -O(CH ₂ ) _a -, -(CH ₂ ) _a O-, -O(CH ₂ ) _a O-, -CH=CH-, -CF=CF-, -C≡C-, -COO-, -OCO-, -CH =CH-COO-, -OCO-CH=CH-, -CH ₂ CH ₂ -COO-, -OCO-CH ₂ CH ₂ -, -CH=N-, -N=CH-, -N=N-, -OCF ₂ -or -CF ₂ O-, each of which a is independently an integer of 1-20. The composition as described in item 1 or 2 of the patent application range, wherein the inorganic filler is a nitride, a carbide, a carbon material, a silicate compound, or a metal oxide. The composition according to item 1 or 2 of the patent application scope, wherein the inorganic filler is selected from boron nitride, aluminum nitride, boron nitride carbon, boron carbide, graphite, carbon fiber, carbon nanotube , At least one of alumina, cordierite, zinc oxide, zirconia, and titanium oxide. A hardened product, which is a hardened product of the composition as described in any one of claims 1 to 8. A layered body is a layered body of a layer of a cured product of the composition as described in any one of claims 1 to 8 and a metal, metal compound, or semiconductor layer. An electronic machine, including: Electronic device with a heating element, and The hardened product as described in item 9 of the patent application or the laminate as described in item 10 of the patent application.

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