WO2019159368A1 - Composition de résine époxy, produit durci de résine époxy, film thermoconducteur et procédé pour la production de produit durci de résine époxy - Google Patents

Composition de résine époxy, produit durci de résine époxy, film thermoconducteur et procédé pour la production de produit durci de résine époxy Download PDF

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Publication number
WO2019159368A1
WO2019159368A1 PCT/JP2018/005788 JP2018005788W WO2019159368A1 WO 2019159368 A1 WO2019159368 A1 WO 2019159368A1 JP 2018005788 W JP2018005788 W JP 2018005788W WO 2019159368 A1 WO2019159368 A1 WO 2019159368A1
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Prior art keywords
epoxy resin
resin composition
liquid crystal
crystal structure
epoxy
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PCT/JP2018/005788
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English (en)
Japanese (ja)
Inventor
竹澤　由高
慎吾 田中
房郎 北條
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日立化成株式会社
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Priority to PCT/JP2018/005788 priority Critical patent/WO2019159368A1/fr
Publication of WO2019159368A1 publication Critical patent/WO2019159368A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/02—Polycondensates containing more than one epoxy group per molecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
    • C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
    • C08G59/40—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the curing agents used
    • C08G59/62—Alcohols or phenols
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins

Definitions

  • the present invention relates to an epoxy resin composition, an epoxy resin cured product, a heat conductive film, and a method for producing an epoxy resin cured product.
  • the amount of heat generated per unit volume tends to increase with the increase in energy density due to downsizing and higher performance of electronic devices. For this reason, high heat conductivity is calculated
  • the epoxy resin composition containing an epoxy resin is widely used for the insulating material from the viewpoint of high withstand voltage and easy molding.
  • the present invention provides an epoxy resin composition, an epoxy resin cured product, a thermally conductive film, and a method for producing an epoxy resin cured product that are excellent in thin film formability and thermal conductivity in a cured state. This is the issue.
  • a reaction-induced epoxy resin composition that includes an epoxy compound and a curing agent and is capable of forming a smectic liquid crystal structure, and does not contain a filler or the filler content is a non-volatile content of the epoxy resin composition.
  • the epoxy resin composition which is 20 mass% or less of the whole.
  • ⁇ 2> The epoxy resin composition according to ⁇ 1>, wherein the smectic liquid crystal structure forms a domain, and an average value of the diameter of the domain is 20 ⁇ m or more.
  • ⁇ 3> The epoxy resin composition according to ⁇ 1> or ⁇ 2>, wherein the smectic liquid crystal structure forms a domain, and the domain includes a spherulite.
  • ⁇ 4> The epoxy resin composition according to any one of ⁇ 1> to ⁇ 3>, wherein the smectic liquid crystal structure is formed via a nematic liquid crystal structure.
  • ⁇ 5> The epoxy resin composition according to any one of ⁇ 1> to ⁇ 4>, wherein the smectic liquid crystal structure can be formed at any curing temperature selected from the range of 130 ° C. to 160 ° C.
  • ⁇ 6> The epoxy resin composition according to any one of ⁇ 1> to ⁇ 5>, wherein a smectic liquid crystal structure can be formed within 3 minutes at a curing temperature of 160 ° C.
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • the filler includes at least one selected from the group consisting of silica particles, alumina particles, magnesium oxide particles, aluminum nitride particles, and boron nitride particles.
  • ⁇ 12> A cured epoxy resin, which is a cured product of the epoxy resin composition according to any one of ⁇ 1> to ⁇ 11>.
  • the cured epoxy resin according to ⁇ 12> having a periodic structure of a smectic liquid crystal structure, wherein the periodic length of the periodic structure is 1.0 nm to 4.0 nm.
  • ⁇ 14> A heat conductive film which is a film-like product of the cured epoxy resin according to ⁇ 12> or ⁇ 13>.
  • ⁇ 15> including a step of heat-treating the epoxy resin composition according to any one of ⁇ 1> to ⁇ 11>, wherein the heat treatment is performed at a temperature X (° C.) satisfying the following formula: Production method.
  • an epoxy resin composition an epoxy resin cured product, a thermally conductive film, and a method for producing an epoxy resin cured product that are excellent in thin film formability and thermal conductivity in a cured state.
  • the content of each component in the composition is the sum of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. It means the content rate of.
  • the particle diameter of each component in the composition is a mixture of the plurality of types of particles present in the composition unless there is a specific indication when there are a plurality of types of particles corresponding to each component in the composition. Means the value of.
  • the average thickness (also referred to as the average value of the thickness) is a value given as an arithmetic average value obtained by measuring the thickness of five randomly selected objects. The thickness can be measured using a micrometer or the like.
  • the epoxy resin composition of the present embodiment is a reaction-induced epoxy resin composition that includes an epoxy compound and a curing agent and can form a smectic liquid crystal structure, and does not contain a filler or the filler content is It is 20 mass% or less of the whole non volatile matter of an epoxy resin composition.
  • the epoxy resin composition of the present embodiment (hereinafter also simply referred to as an epoxy resin composition) does not contain a filler, or its content is 20% by mass or less of the entire nonvolatile content of the epoxy resin composition. The deterioration of the thin film formation property by containing is suppressed.
  • the epoxy resin composition is a reaction-induced type, it is considered that excellent fluidity before curing at a curing temperature is achieved and good thin film formability is achieved.
  • the epoxy resin composition of the present embodiment can form a smectic liquid crystal structure, it is considered that good thermal conductivity after curing is achieved.
  • the “reaction-inducing epoxy resin composition” is an isotropic structure (isotropic phase) in which the liquid crystal structure is not formed before the curing reaction starts, but the liquid crystal structure is developed with the progress of the curing reaction. It means an epoxy resin composition having the property of forming.
  • the epoxy resin composition that is not reaction-induced include a resin composition in which a liquid crystal structure is already formed before the curing reaction starts and the curing reaction proceeds in the state of the liquid crystal structure.
  • the epoxy resin composition has higher fluidity in the isotropic structure state than in the liquid crystal structure state. For this reason, reaction-induced epoxy resin compositions tend to have higher fluidity before curing at the curing temperature than non-reaction-induced epoxy resin compositions. Moreover, since the reaction-induced epoxy resin composition also forms a liquid crystal structure after curing in the same manner as the non-reaction-induced epoxy resin composition, high thermal conductivity can be obtained.
  • the epoxy resin composition is reaction-induced depends on the molecular structure of the epoxy compound and the molecular structure of the curing agent.
  • the epoxy resin composition of the present embodiment can form a smectic liquid crystal structure by a reaction between an epoxy compound and a curing agent.
  • An epoxy compound having a mesogenic structure is an example of an epoxy compound that can react with a curing agent to form a liquid crystal structure such as a smectic liquid crystal structure (hereinafter also referred to as a liquid crystalline epoxy compound).
  • the “epoxy compound having a mesogen structure” means a compound having an epoxy group and a mesogen structure.
  • mesogen structure examples include a biphenyl structure, a terphenyl structure, a terphenyl analog structure, an anthracene structure, a structure in which two or more of these mesogen structures are connected by an azomethine group or an ester group, a phenylbenzoate structure, a cyclohexylbenzoate structure, and the like. It is done.
  • the “resin matrix” means a portion corresponding to a reaction product of an epoxy compound and a cured product in a cured product of an epoxy resin composition (hereinafter also referred to as an epoxy resin cured product).
  • a higher order structure (periodic structure) formed in a resin matrix means a state in which molecules are aligned in a resin matrix (for example, a crystal structure or a liquid crystal structure is present in the resin matrix). Existing state).
  • the presence of such a crystal structure or liquid crystal structure can be directly confirmed by, for example, observation with a polarizing microscope under crossed Nicols or X-ray scattering.
  • the presence of the crystal structure or liquid crystal structure is indirectly measured by measuring the change in storage modulus of the resin with respect to temperature by utilizing the property that the change in the storage modulus of the resin with respect to temperature is reduced when the crystal structure or liquid crystal structure is present. Can be confirmed.
  • Examples of highly ordered higher order structures derived from mesogenic structures include nematic liquid crystal structures and smectic liquid crystal structures.
  • the nematic liquid crystal structure is a liquid crystal structure in which the molecular long axis is oriented in a uniform direction and has only alignment order.
  • the smectic liquid crystal structure is a liquid crystal structure having a one-dimensional positional order in addition to the alignment order and having a layer structure with a constant period. Further, the direction of the period of the layer structure is uniform within the same periodic structure of the smectic liquid crystal structure. That is, the order of the molecules is higher in the smectic liquid crystal structure than in the nematic liquid crystal structure.
  • a smectic liquid crystal structure when the epoxy compound reacts with the curing agent, a smectic liquid crystal structure is formed. Whether or not a smectic liquid crystal structure is formed by the reaction between the epoxy compound and the curing agent depends on the molecular structure of the epoxy compound, the molecular structure of the curing agent, the curing temperature, and the like. In the present embodiment, the entire periodic structure formed in the resin matrix may be a smectic liquid crystal structure or a part thereof may be a smectic liquid crystal structure.
  • the periodic structure formed in the resin matrix includes a smectic liquid crystal structure
  • X-ray diffraction measurement is performed using an X-ray analyzer (for example, manufactured by Rigaku Corporation) using a CuK ⁇ 1 line and a tube voltage of 40 kV, a tube current of 20 mA, and 2 ⁇ in the range of 0.5 ° to 30 °.
  • the ratio of the smectic liquid crystal structure in the entire periodic structure in the resin matrix is preferably 60% by volume or more, and more preferably 80% by volume or more.
  • the ratio of the smectic liquid crystal structure in the entire periodic structure can be easily measured by, for example, polishing the epoxy resin cured product to a predetermined thickness (for example, 50 ⁇ m) and observing with a polarizing microscope. Specifically, a cured epoxy resin having a smectic liquid crystal structure is polished to a thickness of 50 ⁇ m, and observed with a polarizing microscope (for example, product name: “OPTIPHOT2-POL” manufactured by Nikon Corporation) to produce a smectic liquid crystal.
  • a polarizing microscope for example, product name: “OPTIPHOT2-POL” manufactured by Nikon Corporation
  • the periodic structure of the smectic liquid crystal structure preferably has a period length (length of one period) of 1.0 nm or more, and more preferably 2.0 nm or more. When the period length is 1.0 nm or more, higher thermal conductivity can be exhibited.
  • the period length may be 4.0 nm, and is preferably 1.0 nm to 4.0 nm.
  • the periodic length of the periodic structure is obtained by performing X-ray diffraction using a cured epoxy resin product as a measurement sample under the above measurement conditions using a wide-angle X-ray diffractometer (for example, Rigaku Corporation, product name: “RINT2500HL”).
  • the diffraction angle thus obtained can be obtained by converting the following Bragg equation.
  • d is the length of one period
  • ⁇ is the diffraction angle
  • n is the reflection order
  • ⁇ is the X-ray wavelength (0.15406 nm).
  • the process in which the epoxy resin composition forms a smectic liquid crystal structure is not particularly limited. From the viewpoint of suppressing rapid volume shrinkage, it is preferable to form a smectic liquid crystal structure via a nematic liquid crystal structure. This is because when the transition from the isotropic structure to the smectic liquid crystal structure directly without passing through the nematic liquid crystal structure, the density change is large, and thus volume shrinkage tends to occur rapidly.
  • the smectic liquid crystal structure formed by the epoxy resin composition forms a domain
  • the average value of the domain diameter is preferably 20 ⁇ m or more, more preferably 40 ⁇ m or more. More preferably, it is 60 ⁇ m or more. From the viewpoint of isotropic property, the average value of the domain diameters is preferably 100 ⁇ m or less.
  • the “domain” corresponds to a portion in which a periodic structure is formed in one direction in the resin matrix, and the periodic structure is in a direction different from the portion where the periodic structure is not formed or the periodic structure of the domain. It means an island-like region surrounded by the formed part.
  • the diameter of the domain and its average value can be measured in a pseudo manner as the diameter of the cross section of the domain appearing in the observed cross section of the cured epoxy resin and its average value.
  • the diameter of the cross section of the domain is measured, for example, by polarizing microscope observation of the cured epoxy resin as described above.
  • the average value of the diameter of the cross section of the domain is measured for 10 randomly selected domains among the domains appearing in the observed cross section of the epoxy resin cured product, and the arithmetic average value is calculated as the domain of the smectic liquid crystal structure.
  • the diameter of a domain means the maximum diameter of a domain when the shape of the domain is not a perfect circle (ellipse, polygon, etc.).
  • the maximum diameter is the length of the longest line segment connecting the two arbitrary points located on the contour line of the domain appearing on the observation cross section of the cured epoxy resin.
  • the diameter of the domain can be controlled by, for example, the curing conditions of the epoxy resin composition.
  • the lower the curing temperature of the epoxy resin composition the slower the growth rate of the domains, with the result that the domain diameter tends to increase.
  • the longer the curing time of the epoxy resin composition the more the domain grows and the diameter tends to increase.
  • the curing temperature of the epoxy resin composition is preferably 160 ° C. or lower, more preferably 150 ° C. or lower, and further preferably 140 ° C. or lower. Further, the curing time of the epoxy resin composition is preferably 30 seconds or longer, and more preferably 1 minute or longer.
  • the curing temperature of the epoxy resin composition is preferably not too low. Accordingly, the curing temperature is preferably 130 ° C. or higher. Moreover, from the viewpoint of shortening the curing time of the epoxy resin composition, the curing time is preferably within 5 minutes, and more preferably within 3 minutes.
  • the epoxy resin composition is capable of forming a smectic liquid crystal structure at any curing temperature selected from the range of 130 ° C to 160 ° C. If a curing temperature range of 130 ° C. to 160 ° C. is passed, a smectic liquid crystal structure can be formed even if the curing temperature is not constant. For example, a smectic liquid crystal structure can be formed even in the process of raising the temperature from 30 ° C. to 180 ° C. at 5 ° C./min. In one embodiment, the epoxy resin composition is capable of forming a smectic liquid crystal structure within 3 minutes at a curing temperature of 160 ° C.
  • the smectic liquid crystal structure formed by the epoxy resin composition is in a domain state and preferably contains spherulites.
  • the spherulite means a domain whose three-dimensional shape is a sphere, an ellipsoid, or a disk. Whether the domain of the smectic liquid crystal structure contains spherulites can be determined, for example, by determining whether the shape of the domain appearing in the observed cross section of the cured epoxy resin is circular, elliptical, or the like.
  • each domain is grown without being deformed by an adjacent domain.
  • the method of making the epoxy resin composition before hardening contain a solvent is mentioned.
  • the domains collide with each other in the process of growing the domain of the smectic liquid crystal structure with hardening.
  • the individual domains tend not to be spherulites but to have a polygonal cross section.
  • the epoxy resin composition before curing contains a solvent and is cured while volatilizing the solvent, the epoxy resin composition is diluted with the solvent, so that the interval between the nuclei forming the smectic liquid crystal structure is widened.
  • the domains of the smectic liquid crystal structure do not collide with each other and the individual domains tend to be spherulites.
  • epoxy compound is not particularly limited as long as it can form a smectic liquid crystal structure by reacting with a curing agent, and may be one type or two or more types.
  • the epoxy compound preferably includes a compound represented by the following general formula (I) as an epoxy compound having a mesogenic structure. 1 type or 2 types or more may be sufficient as the compound represented by general formula (I).
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • R 1 to R 4 are each independently preferably a hydrogen atom or an alkyl group having 1 to 2 carbon atoms, more preferably a hydrogen atom or a methyl group, and even more preferably a hydrogen atom.
  • 2 to 4 of R 1 to R 4 are hydrogen atoms, more preferably 3 or 4 are hydrogen atoms, and more preferably that all 4 are hydrogen atoms.
  • any of R 1 to R 4 is an alkyl group having 1 to 3 carbon atoms
  • at least one of R 1 and R 4 is preferably an alkyl group having 1 to 3 carbon atoms.
  • At least a part of the epoxy compound may be in a prepolymer state obtained by reacting with a curing agent (prepolymerizing agent) described later.
  • a curing agent prepolymerizing agent
  • an epoxy compound having a mesogen structure in the molecule including the compound represented by the general formula (I) is easily crystallized, and its solubility in a solvent is often lower than that of other epoxy resin compounds.
  • crystallization is suppressed and the moldability of the epoxy resin composition tends to be improved.
  • the prepolymerizing agent may be the same as or different from the curing agent described later.
  • the prepolymerizing agent is preferably a compound (divalent phenol compound) having two hydroxyl groups as substituents on one benzene ring.
  • the dihydric phenol compound include catechol, resorcinol, hydroquinone, and derivatives thereof.
  • the derivative of the divalent phenol compound include compounds in which an alkyl group having 1 to 8 carbon atoms is substituted on the benzene ring.
  • dihydric phenol compounds it is preferable to use at least one selected from the group consisting of resorcinol and hydroquinone from the viewpoint of improving the thermal conductivity of the cured product, and it is more preferable to use hydroquinone. Since hydroquinone has a structure in which two hydroxyl groups are substituted so as to have a para-position, a prepolymer obtained by reacting with an epoxy compound tends to have a linear structure. For this reason, it is considered that the stacking property of molecules is high and higher-order structures are more easily formed.
  • the prepolymerizing agent used for prepolymerization may be one kind or two or more kinds.
  • the blending ratio of the epoxy compound and the prepolymerizing agent is not particularly limited, and can be selected according to a desired molecular weight, a ratio to the whole epoxy compound, and the like.
  • the mixing ratio of the epoxy compound and the prepolymerizing agent is preferably the equivalent ratio of the epoxy group in the epoxy compound to the hydroxyl group in the prepolymerizing agent (epoxy group / hydroxyl group).
  • the blending ratio is preferably in the range of ⁇ 100 / 25, more preferably 100/10 to 100/15.
  • the content of the epoxy compound is preferably 5% by volume to 40% by volume and preferably 10% by volume to 35% by volume in the total nonvolatile content of the epoxy resin composition from the viewpoint of moldability and adhesiveness. More preferably, it is 15 volume% to 35 volume%, further preferably 15 volume% to 30 volume%.
  • the volume-based content of the epoxy compound with respect to the total nonvolatile content of the epoxy resin composition is a value determined by the following formula.
  • Content (% by volume) of epoxy compound with respect to the total nonvolatile content ⁇ (Bw / Bd) / ((Aw / Ad) + (Bw / Bd) + (Cw / Cd) + (Dw / Dd)) ⁇ ⁇ 100
  • each variable is as follows.
  • Aw Mass composition ratio of filler (% by mass) Bw: mass composition ratio of epoxy compound (mass%) Cw: mass composition ratio (% by mass) of curing agent Dw: mass composition ratio (% by mass) of other optional components (excluding solvent) Ad: Specific gravity of filler Bd: Specific gravity of epoxy compound Cd: Specific gravity of curing agent Dd: Specific gravity of other optional components (excluding solvent)
  • the epoxy compound contained in the epoxy resin composition may be a combination of a liquid crystal epoxy compound and another epoxy compound other than the liquid crystal epoxy compound.
  • Other epoxy compounds include glycidyl ethers of phenolic compounds such as bisphenol A, bisphenol F, bisphenol S, phenol novolak, cresol novolak, resorcinol novolak; glycidyl ethers of alcohol compounds such as butanediol, polyethylene glycol, and polypropylene glycol; phthalic acid Glycidyl esters of carboxylic acid compounds such as isophthalic acid and tetrahydrophthalic acid; glycidyl type (including methyl glycidyl type) epoxy compounds such as those in which active hydrogen bonded to a nitrogen atom such as aniline or isocyanuric acid is substituted with a glycidyl group; Vinylcyclohexene epoxide obtained by epoxidation of olefin bond in the molecule, 3,4-
  • the content of other epoxy compounds is not particularly limited, and is preferably 0.3 or less, more preferably 0.2 or less when the liquid crystalline epoxy compound is 1 on a mass basis, 0 More preferably, it is 1 or less.
  • the epoxy resin composition contains a curing agent.
  • the curing agent is not particularly limited as long as it is a compound capable of causing a curing reaction with the epoxy compound.
  • Specific examples of the curing agent include amine curing agents, acid anhydride curing agents, phenol curing agents, polymercaptan curing agents, polyaminoamide curing agents, isocyanate curing agents, and blocked isocyanate curing agents. Only one type or two or more types of curing agents may be used.
  • the curing agent is preferably an amine curing agent or a phenol curing agent, more preferably a phenol curing agent, and a phenol curing agent containing a phenol novolac resin. Is more preferable.
  • low molecular phenol compounds and phenol resins obtained by novolacizing them can be used.
  • Low molecular phenol compounds include monofunctional phenol compounds such as phenol, o-cresol, m-cresol, and p-cresol, bifunctional phenol compounds such as catechol, resorcinol, hydroquinone, 1,2,3-trihydroxybenzene, 1 Trifunctional phenol compounds such as 1,2,4-trihydroxybenzene and 1,3,5-trihydroxybenzene can be used.
  • a phenol novolac resin obtained by connecting these low molecular phenol compounds with a methylene chain or the like to form a novolac can be used as a curing agent.
  • the phenol novolac resin used as the curing agent may contain a phenol compound as a monomer.
  • the monomer content ratio in the phenol novolac resin (hereinafter also referred to as “monomer content ratio”) is not particularly limited. From the viewpoint of thermal conductivity and moldability, the monomer content is preferably 5% by mass to 80% by mass, more preferably 15% by mass to 60% by mass, and 20% by mass to 50% by mass. More preferably it is.
  • the monomer content is 80% by mass or less, the amount of monomer that does not contribute to crosslinking during the curing reaction is suppressed, and the amount of the high-molecular-weight polymer that is crosslinked increases, so that a higher-density higher-order structure is formed, There is a tendency for conductivity to improve. Further, when the monomer content ratio is 5% by mass or more, it is easy to flow at the time of molding. Therefore, when the epoxy resin composition contains an inorganic filler, the adhesion with the filler is further improved and more excellent. Thermal conductivity and heat resistance tend to be achieved.
  • the number of equivalents of the functional group of the curing agent is preferably 0.005 to 5 equivalents, more preferably 0.01 to 3 equivalents with respect to 1 equivalent of the epoxy group in the epoxy compound.
  • the amount is preferably 0.5 equivalent to 1.5 equivalent. It exists in the tendency which can improve the hardening rate of an epoxy compound more as the equivalent number of the functional group of a hardening
  • curing agent is 0.005 equivalent or more with respect to 1 equivalent of an epoxy group. Moreover, it exists in the tendency which can control hardening reaction more appropriately that the equivalent number of the functional group of a hardening
  • the chemical equivalent in this specification represents the equivalent number of the hydroxyl group of the phenol curing agent with respect to 1 equivalent of an epoxy group, for example, when a phenol curing agent is used as a curing agent, and an amine curing agent is used as the curing agent. When used, it represents the number of equivalents of active hydrogen in the amine curing agent relative to 1 equivalent of epoxy group.
  • a curing accelerator may be used in combination as necessary.
  • the epoxy resin composition can be further sufficiently cured.
  • the kind in particular of hardening accelerator is not restrict
  • the curing accelerator include imidazole compounds, phosphine compounds, and borate salt compounds.
  • the epoxy resin composition may contain a filler.
  • ceramic particles can be used from the viewpoints of thermal conductivity and insulation. Examples of the ceramic particles include alumina particles, silica particles, magnesium oxide particles, boron nitride particles, aluminum nitride particles, and silicon nitride particles.
  • the filler preferably includes at least one selected from the group consisting of alumina particles, boron nitride particles, aluminum nitride particles, and magnesium oxide particles, and more preferably includes alumina particles.
  • the alumina particles preferably include alumina particles with high crystallinity, and more preferably include ⁇ -alumina particles.
  • a periodic structure of a smectic liquid crystal structure is formed in a direction perpendicular to the surface of the alumina particles from the viewpoint of thermal conductivity. Whether or not the periodic structure of the smectic liquid crystal structure is formed in the direction perpendicular to the surface of the alumina particles can be confirmed by, for example, observation of the cured epoxy resin as described above with a polarizing microscope.
  • the volume average particle diameter of the filler is preferably 0.01 ⁇ m to 1 mm from the viewpoint of thermal conductivity, and more preferably 0.10 ⁇ m to 100 ⁇ m from the viewpoint of filling properties.
  • the volume average particle diameter of the filler is measured using a laser diffraction method.
  • the measurement by the laser diffraction method can be performed using a laser diffraction scattering particle size distribution measuring device (for example, LS230 manufactured by Beckman Coulter, Inc.).
  • a laser diffraction scattering particle size distribution measuring device for example, LS230 manufactured by Beckman Coulter, Inc.
  • the particle diameter (D50) at which the cumulative volume from the small diameter side is 50% is defined as the volume average particle diameter of the filler.
  • the volume average particle diameter of the filler contained in the epoxy resin composition is measured using a laser diffraction / scattering particle size distribution analyzer after extracting the filler from the epoxy resin composition.
  • the extraction of the filler and the measurement of the volume average particle diameter can be performed by, for example, sufficiently dispersing the components other than the filler of the epoxy resin composition using an organic solvent, nitric acid, aqua regia, etc. with an ultrasonic disperser or the like.
  • a dispersion can be prepared by using the dispersion.
  • the extraction of the filler contained in the cured epoxy resin or the heat conductive film and the measurement of the volume average particle diameter can be performed in the same manner.
  • the content is 20% by mass or less of the entire nonvolatile content of the epoxy resin composition, preferably 15% by mass or less, and more preferably 10% by mass or less. preferable.
  • the epoxy resin composition contains a filler in an amount of a certain ratio or less, hardness, flexibility, fluidity, etc. can be easily adjusted, and the growth of a smectic liquid crystal structure is promoted by using the filler as a nucleus. The effect can be expected.
  • the filler content is 20% by mass or less of the entire nonvolatile content of the epoxy resin composition
  • the thin film formability of the epoxy resin composition is favorably maintained.
  • cures in the state which contacted the other member and the epoxy resin composition it exists in the tendency for the adhesiveness to another member to be fully acquired.
  • the domains in the smectic liquid crystal structure formed by the curing reaction are less likely to collide with the filler and tend to grow sufficiently to obtain high thermal conductivity.
  • the epoxy resin composition may further contain other components such as a solvent, a coupling agent, a dispersant, an elastomer, and a release agent. From the viewpoint of forming spherulite domains, the epoxy resin composition preferably contains a solvent.
  • the type of solvent is not particularly limited, and acetone, isobutyl alcohol, isopropyl alcohol, isopentyl alcohol, diethyl ether, ethylene glycol monoethyl ether, xylene, cresol, chlorobenzene, isobutyl acetate, isopropyl acetate, isopentyl acetate, ethyl acetate, methyl acetate , Cyclohexanol, cyclohexanone, 1,4-dioxane, dichloromethane, styrene, tetrachloroethylene, tetrahydrofuran, toluene, n-hexane, 1-butanol, 2-butanol, methanol, methyl isobutyl ketone, methyl ethyl ketone, methyl cyclohexanol, methyl cyclohexanone, chloroform , Carbon tetrachloride
  • the epoxy resin composition of the present embodiment has a high orientation of the epoxy compound and is excellent in thermal conductivity when used as a cured product. Therefore, the epoxy resin composition of the present embodiment is suitably used for a member (for example, a heat dissipation material) of a heat-generating electronic component (for example, an IC (Integrated Circuit) chip or a printed wiring board) of various electric and electronic devices. be able to.
  • a member for example, a heat dissipation material
  • a heat-generating electronic component for example, an IC (Integrated Circuit) chip or a printed wiring board
  • the manufacturing method of the cured epoxy resin of the present embodiment includes a step of heat-treating the epoxy resin composition of the present embodiment, and the heat treatment is performed at a temperature X (° C.) that satisfies the following formula. (B + 5 °C) ⁇ X ⁇ (A-5 °C)
  • A is the upper limit (° C.) of the temperature at which the epoxy resin composition can form a smectic liquid crystal structure
  • B is the lower limit (° C.) of the temperature at which the epoxy resin composition can form a smectic liquid crystal structure. It is. A and B satisfy the relationship B ⁇ A-10.
  • the temperature X of the heat treatment can be set according to the type and composition ratio of components contained in the epoxy resin composition. For example, it is preferably selected from the range of 100 ° C. to 200 ° C., more preferably selected from the range of 120 ° C. to 180 ° C.
  • the temperature X of the heat treatment may be constant from the start to the end of the heat treatment or may change. When X changes, it is preferable to satisfy the above conditions in the initial curing stage. Moreover, it is preferable that X satisfies the above-mentioned conditions at 20% or more of the total heat treatment time.
  • the time for the heat treatment is not particularly limited, and is preferably selected from a range of 5 minutes to 60 minutes, for example, and more preferably selected from a range of 10 minutes to 30 minutes.
  • the epoxy resin cured product obtained after the heat treatment may be further subjected to another heat treatment (hereinafter also referred to as “post-curing treatment”).
  • post-curing treatment By performing post-curing treatment on the cured epoxy resin, the crosslinking density tends to increase.
  • the post-curing treatment may be performed only once or twice or more.
  • the temperature of the post-curing treatment is not particularly limited, and is preferably selected from the range of 140 ° C. to 240 ° C., for example, and more preferably selected from the range of 160 ° C. to 220 ° C.
  • the temperature of the post-curing treatment may be constant from the start to the end of the heat treatment or may vary.
  • the time for the post-curing treatment is not particularly limited, and is preferably selected from a range of, for example, 10 minutes to 600 minutes, and more preferably selected from a range of 60 minutes to 300 minutes.
  • the heating device used for post-curing is not particularly limited, and a commonly used heating device can be used.
  • the epoxy resin composition may be heat-treated in a film state.
  • the heat conductive film of this embodiment which is a film-form material of an epoxy resin hardened
  • the cured epoxy resin of the present embodiment is a cured product of the epoxy resin composition of the present embodiment.
  • the heat conductive film of this embodiment is a film-like product of the cured epoxy resin of this embodiment.
  • the cured epoxy resin and the heat conductive film of the present embodiment are obtained by curing the epoxy resin composition of the present embodiment, the thin film formability is excellent and the heat conductivity is excellent.
  • a periodic structure having a smectic liquid crystal structure is formed.
  • the periodic length of the periodic structure of the smectic liquid crystal structure is preferably 2.0 nm to 4.0 nm, and more preferably 2.0 nm to 3.0 nm.
  • the heat conductive film is preferably prepared by performing a heat treatment in a state where the epoxy resin composition is formed into a film shape.
  • the average thickness of the heat conductive film is not particularly limited, and can be selected from a range of 0.01 mm to 3 mm, for example.
  • phenol novolak resin solution (hereinafter also referred to as curing agent 1).
  • the number average molecular weight of the obtained phenol novolak resin was 484, and the number of structural units n was 3.9 on average.
  • the monomer content ratio was 40% by mass. From 1 H-NMR measurement, it was found that an average of 2.1 hydroxyl groups were contained per structural unit of phenol novolac resin (corresponding to 1 molecule of phenol compound). The hydroxyl equivalent was 62 g / eq.
  • Epoxy compound 2, curing agent 1, and triphenylphosphine as a curing accelerator were mixed to prepare an epoxy resin composition.
  • curing agent 1 was adjusted so that ratio of the equivalent number of the hydroxyl group of the hardening
  • the compounding amount of the curing accelerator was set to 0.8% by mass with respect to the total mass of the epoxy compound 2 and the curing agent.
  • the state of the phase change accompanying the curing reaction during the heat treatment was examined by taking out the epoxy resin composition a plurality of times during the heat treatment and observing with a polarizing microscope. As a result, the structure changed in the order of isotropic structure (Iso), nematic liquid crystal structure (N), and smectic liquid crystal structure (Sm).
  • Iso isotropic structure
  • N nematic liquid crystal structure
  • Sm smectic liquid crystal structure
  • the measured diffraction angle 2 ⁇ was 3.2 °, and it was confirmed that a periodic structure of a smectic liquid crystal structure was formed. Moreover, the period length obtained by converting the measured diffraction angle by the Bragg equation was 2.7 (nm).
  • thermal conductivity The produced thermal conductive film was cut into a 1 cm square and used as a test piece for measuring thermal diffusivity.
  • the thermal diffusivity of the test piece was measured using a flash method apparatus (“NanoFlash LFA447” manufactured by NETZSCH). By multiplying the measurement result by the density measured by the Archimedes method and the specific heat measured by the DSC method, the thermal conductivity in the thickness direction of the heat conductive film was obtained and found to be 0.8 W / (m ⁇ K). It was.
  • Example 2 (Examples 2 and 3)
  • alumina particles manufactured by Nippon Steel & Sumikin Materials Co., Ltd., Micron Company, trade name: “AX3-32”, volume average particle size: 4 ⁇ m, the same in the following Examples and Comparative Examples) were used as epoxy resin compositions.
  • An epoxy resin composition was prepared in the same manner as in Example 1 except that the content was 5% by mass and 10% by mass with respect to the whole nonvolatile content, and a heat conductive film was produced.
  • the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • Example 4 In Example 1, an epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy compound 1 was used instead of the epoxy compound 2, and a heat conductive film was produced. In the same manner as in Example 1, the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • the blending amount of the epoxy compound 1 and the curing agent 1 was adjusted so that the ratio of the number of equivalents of the hydroxyl group of the curing agent 1 to the number of equivalents of the epoxy group of the epoxy compound 1 (epoxy group: hydroxyl group) was 1: 1.
  • the blending amount of the curing accelerator was set to 0.8% by mass with respect to the total mass of the epoxy compound 1 and the curing agent 1.
  • Example 4 the epoxy resin composition was prepared in the same manner as in Example 4 except that the alumina particles were blended so that the content of the epoxy resin composition was 5% by mass and 10% by mass, respectively, with respect to the entire nonvolatile content.
  • Example 1 To prepare a heat conductive film.
  • the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • Example 7 In Example 1, instead of the epoxy compound 2, an epoxy compound having a mesogenic structure (1- (3-methyl-4-oxiranimethoxyphenyl) -4- (oxiranylmethoxyphenyl) -1-cyclohexene) (hereinafter referred to as “epoxy compound 2”)
  • epoxy compound 2 an epoxy compound having a mesogenic structure (1- (3-methyl-4-oxiranimethoxyphenyl) -4- (oxiranylmethoxyphenyl) -1-cyclohexene)
  • epoxy compound 2 an epoxy compound having a mesogenic structure (1- (3-methyl-4-oxiranimethoxyphenyl) -4- (oxiranylmethoxyphenyl) -1-cyclohexene)
  • the compounding amount of the epoxy compound 3 and the curing agent 1 was adjusted such that the ratio of the number of equivalents of the hydroxyl group of the curing agent 1 to the number of equivalents of the epoxy group of the epoxy compound 3 (epoxy group: hydroxyl group) was 1: 1.
  • the blending amount of the curing accelerator was set to 0.8% by mass with respect to the total mass of the epoxy compound 3 and the curing agent 1.
  • Example 7 the epoxy resin composition was the same as Example 7 except that the alumina particles were blended so that the content of the epoxy resin composition with respect to the entire nonvolatile content was 5% by mass and 10% by mass, respectively.
  • Example 7 To prepare a heat conductive film.
  • the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • Example 10 In Example 7, instead of curing agent 1, 1,5-diaminonaphthalene (hereinafter also referred to as curing agent 2) was used, and in the same manner as in Example 7, except that the curing accelerator was omitted.
  • An epoxy resin composition was prepared to produce a heat conductive film.
  • the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • the blending amount of the epoxy compound 3 and the curing agent 2 is adjusted so that the ratio of the number of equivalents of the amino group of the curing agent 2 to the number of equivalents of the epoxy group of the epoxy compound 3 (epoxy group: amino group) is 1: 1. did.
  • Example 10 the epoxy resin composition was the same as Example 10 except that the alumina particles were blended so that the content of the epoxy resin composition with respect to the entire nonvolatile content was 5 mass% and 10 mass%, respectively.
  • Example 10 To prepare a heat conductive film.
  • the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • Example 13 In Example 1, 5 g of methyl ethyl ketone (MEK) was further added as a solvent to prepare an epoxy resin composition. The prepared epoxy resin composition was stirred for 30 minutes at room temperature (25 ° C.) using a mix roller. Thereafter, it was formed into a film at room temperature. Next, heat treatment was performed at 140 ° C. for 30 minutes to produce a heat conductive film. In the same manner as in Example 1, the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • MEK methyl ethyl ketone
  • Example 13 the epoxy resin composition was prepared in the same manner as in Example 13 except that the alumina particles were blended so that the content of the epoxy resin composition with respect to the entire nonvolatile content was 5 mass% and 10 mass%, respectively.
  • Example 13 To prepare a heat conductive film.
  • the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • Example 1 In Example 1, in place of the epoxy compound 1, a bisphenol A type epoxy compound (trade name: “jER828”, hereinafter also referred to as “epoxy compound 4” manufactured by Mitsubishi Chemical Corporation), which is an epoxy compound having no mesogen structure, is used. Except having used, it carried out similarly to Example 1, and prepared the epoxy resin composition, and produced the heat conductive film. In the same manner as in Example 1, the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • jER828 bisphenol A type epoxy compound manufactured by Mitsubishi Chemical Corporation
  • the compounding amount of the epoxy compound 4 and the curing agent 1 was adjusted so that the ratio of the number of equivalents of the hydroxyl group of the curing agent 1 to the number of equivalents of the epoxy group of the epoxy compound 4 (epoxy group: hydroxyl group) was 1: 1.
  • the blending amount of the curing accelerator was set to 0.8% by mass with respect to the total mass of the epoxy compound 4 and the curing agent 1.
  • Comparative Examples 2 and 3 the epoxy resin composition was prepared in the same manner as in Comparative Example 1 except that the alumina particles were blended so that the content of the epoxy resin composition with respect to the entire nonvolatile content was 5 mass% and 10 mass%, respectively.
  • a heat conductive film To prepare a heat conductive film.
  • the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • Example 10 an epoxy resin composition was prepared in the same manner as in Example 1 except that the epoxy compound 4 was used instead of the epoxy compound 3, and a heat conductive film was produced. In the same manner as in Example 1, the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • the compounding amount of the epoxy compound 4 and the curing agent 2 is adjusted so that the ratio of the number of equivalents of the amino group of the curing agent 2 to the number of equivalents of the epoxy group of the epoxy compound 4 (epoxy group: amino group) is 1: 1. did.
  • Comparative Examples 5 and 6 the epoxy resin composition was the same as Comparative Example 4 except that the alumina particles were blended so that the content of the epoxy resin composition with respect to the entire nonvolatile content was 5 mass% and 10 mass%, respectively.
  • a heat conductive film To prepare a heat conductive film. In the same manner as in Example 1, the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • Example 7 an epoxy resin composition was prepared in the same manner as in Example 13 except that the epoxy compound 4 was used instead of the epoxy compound 2, and a heat conductive film was produced. Then, in the same manner as in Example 1, the periodic length, domain diameter, and thermal conductivity of the periodic structure were obtained. The results are shown in Table 1.
  • the compounding amount of the epoxy compound 4 and the curing agent 1 was adjusted so that the ratio of the number of equivalents of the hydroxyl group of the curing agent 1 to the number of equivalents of the epoxy group of the epoxy compound 4 (epoxy group: hydroxyl group) was 1: 1.
  • the blending amount of the curing accelerator was set to 0.8% by mass with respect to the total mass of the epoxy compound 4 and the curing agent 1.
  • Comparative Examples 8 and 9 In Comparative Example 7, the epoxy resin composition was the same as Comparative Example 7 except that the alumina particles were blended so that the content of the epoxy resin composition with respect to the entire nonvolatile content was 5% by mass and 10% by mass, respectively.
  • Example 10 (Comparative Example 10)
  • an epoxy resin composition was prepared in the same manner as in Example 1 except that the alumina particles were blended so that the content of the epoxy resin composition with respect to the entire nonvolatile content was 50% by mass.
  • a conductive film was prepared.
  • the state of phase change, the period length of the periodic structure, the domain diameter, and the thermal conductivity were obtained. The results are shown in Table 1.
  • the thermal conductivity films produced in Comparative Examples 1 to 9 had lower thermal conductivity than the thermal conduction films produced in Examples. This is because the smectic liquid crystal domain is formed in the heat conduction film produced in the example, whereas the smectic liquid crystal structure domain is not formed in the heat conduction film produced in the comparative example. It is done.
  • the heat conductive film produced in Comparative Example 10 in which the content of alumina particles exceeded 20 mass% had smectic liquid crystal structure domains formed, but the domain diameter was smaller than those in Examples 1-15. This is presumably because the rate at which the domain growth collides with the alumina particles and stops is larger than in the example. Moreover, a heat conductive film having an average thickness of 50 ⁇ m could not be formed.

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Abstract

L'invention concerne une composition de résine époxy qui est une composition de résine époxy de type à induction de réaction contenant un composé époxy et un agent durcisseur et pouvant former une structure à cristaux liquides smectiques, qui ne contient pas de charge ou qui a une teneur en charge inférieure ou égale à 20 % en masse de la totalité de la fraction non volatile de la composition de résine époxy.
PCT/JP2018/005788 2018-02-19 2018-02-19 Composition de résine époxy, produit durci de résine époxy, film thermoconducteur et procédé pour la production de produit durci de résine époxy WO2019159368A1 (fr)

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011074366A (ja) * 2009-09-03 2011-04-14 Sumitomo Chemical Co Ltd ジエポキシ化合物、該化合物を含む組成物及び該組成物を硬化して得られる硬化物
JP2014055251A (ja) * 2012-09-13 2014-03-27 Mitsubishi Chemicals Corp 高熱伝導性樹脂組成物
WO2017175775A1 (fr) * 2016-04-05 2017-10-12 日立化成株式会社 Composition de résine, matériau de barrière contre l'hydrogène gazeux, produit durci, matériau composite et structure
WO2017221810A1 (fr) * 2016-06-22 2017-12-28 日立化成株式会社 Matériau barrière au gaz, composition de résine, matière barrière au gaz, produit durci, et matériau composite
WO2017221811A1 (fr) * 2016-06-22 2017-12-28 日立化成株式会社 Composition de résine époxy, produit durci, et matériau composite
JP2018062604A (ja) * 2016-10-14 2018-04-19 日立化成株式会社 エポキシ樹脂組成物、エポキシ樹脂硬化物、熱伝導フィルム、及びエポキシ樹脂硬化物の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011074366A (ja) * 2009-09-03 2011-04-14 Sumitomo Chemical Co Ltd ジエポキシ化合物、該化合物を含む組成物及び該組成物を硬化して得られる硬化物
JP2014055251A (ja) * 2012-09-13 2014-03-27 Mitsubishi Chemicals Corp 高熱伝導性樹脂組成物
WO2017175775A1 (fr) * 2016-04-05 2017-10-12 日立化成株式会社 Composition de résine, matériau de barrière contre l'hydrogène gazeux, produit durci, matériau composite et structure
WO2017221810A1 (fr) * 2016-06-22 2017-12-28 日立化成株式会社 Matériau barrière au gaz, composition de résine, matière barrière au gaz, produit durci, et matériau composite
WO2017221811A1 (fr) * 2016-06-22 2017-12-28 日立化成株式会社 Composition de résine époxy, produit durci, et matériau composite
JP2018062604A (ja) * 2016-10-14 2018-04-19 日立化成株式会社 エポキシ樹脂組成物、エポキシ樹脂硬化物、熱伝導フィルム、及びエポキシ樹脂硬化物の製造方法

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