WO2017209209A1 - Procédé de production pour stratifié - Google Patents

Procédé de production pour stratifié Download PDF

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Publication number
WO2017209209A1
WO2017209209A1 PCT/JP2017/020342 JP2017020342W WO2017209209A1 WO 2017209209 A1 WO2017209209 A1 WO 2017209209A1 JP 2017020342 W JP2017020342 W JP 2017020342W WO 2017209209 A1 WO2017209209 A1 WO 2017209209A1
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WIPO (PCT)
Prior art keywords
resin layer
epoxy
resin composition
group
resin
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Application number
PCT/JP2017/020342
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English (en)
Japanese (ja)
Inventor
智雄 西山
一也 木口
竹澤　由高
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日立化成株式会社
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Publication of WO2017209209A1 publication Critical patent/WO2017209209A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • C08G59/20—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 epoxy compounds used
    • C08G59/22—Di-epoxy compounds
    • C08G59/24—Di-epoxy compounds carbocyclic

Definitions

  • the present invention relates to a method for manufacturing a laminate.
  • a laminate having a structure in which a resin layer for insulation or the like is disposed between a pair of members is used for various applications as a part of an electronic device and an electric device.
  • Such a laminate is manufactured by cutting (separating) into a desired shape with a resin layer formed on one member, and then placing the other member on the resin layer. .
  • the resin layer and the member are cut in the singulation process after the resin layer is formed on one member, and the resin layer is damaged. It has been found that there is a possibility that a substance derived from this member may be mixed, a protrusion called a burr at the end of the cut surface of the member may be formed.
  • This invention makes it a subject to provide the novel manufacturing method of the laminated body which has a pair of member and the resin layer arrange
  • ⁇ 1> a resin layer forming step of forming a resin layer on the separated first member, and a member arranging step of arranging the separated second member on the resin layer.
  • the resin layer is formed by applying a resin composition to the first member, and the resin composition has a thixotropic index at a temperature when applying the resin composition to the first member.
  • the manufacturing method of the laminated body as described in ⁇ 1> which is 3 or more.
  • ⁇ 3> The method for producing a laminate according to ⁇ 1> or ⁇ 2>, wherein the resin layer includes an epoxy resin.
  • ⁇ 4> Any one of ⁇ 1> to ⁇ 3>, wherein the resin layer is formed using an epoxy resin composition containing two or more epoxy monomers having a mesogenic skeleton and a curing agent.
  • the manufacturing method of the laminated body as described in any one of. ⁇ 5> The method for producing a laminate according to ⁇ 4>, wherein the two or more epoxy monomers having a mesogenic skeleton include a compound represented by the following general formula (I).
  • R 1 to R 4 each independently represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms.
  • a novel method for producing a laminate having a pair of members and a resin layer disposed between the pair of members is provided.
  • the present invention is not limited to the following embodiments.
  • the components including element steps and the like are not essential unless otherwise specified.
  • the term “process” includes a process that is independent of other processes and includes the process if the purpose of the process is achieved even if it cannot be clearly distinguished from the other processes. It is.
  • numerical values indicated by using “to” include numerical values described before and after “to” as the minimum value and the maximum value, respectively.
  • the upper limit value or the lower limit value described in one numerical range may be replaced with the upper limit value or the lower limit value of another numerical range. Good. Further, in the numerical ranges described in this specification, the upper limit value or the lower limit value of the numerical range may be replaced with the values shown in the examples.
  • 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 term “layer” or “film” refers to a part of the region in addition to the case where the layer or the film is formed when the region where the layer or film exists is observed. It is also included when it is formed only.
  • laminate indicates that layers are stacked, and two or more layers may be combined, or two or more layers may be detachable.
  • the “number of structural units” indicates an integer value for a single molecule, but a rational number that is an average value as an aggregate of a plurality of types of molecules.
  • B stage refer to the provisions of JIS K6900: 1994.
  • surface roughness refer to the definition of (Rzjis) in JIS B 0601-2001.
  • the manufacturing method of the laminated body of this embodiment arrange
  • the first member and the second member are “separated” means that the size and shape of each member before forming the resin layer is the size of each member in the finally obtained laminate. It means that it becomes the shape and shape.
  • FIG. 1 shows an example of the steps of a method for manufacturing a laminate using a first member that is not separated.
  • the first member 1 for forming the resin layer is prepared (FIG. 1A), and the resin layer 2 is formed thereon (FIG. 1B).
  • the resin layer 2 contains a volatile component such as a solvent
  • the volatile component is removed (FIG. 1C)
  • the resin layer 2 is sandwiched between the pair of hot plates 3 and 4 and heated (FIG. 1D).
  • the first member 1 in a state where the resin layer 2 is formed is cut (divided) into a predetermined size (FIG. 1 (e)).
  • the 2nd member 5 is arrange
  • FIG. 2 shows an example of a process of a laminate manufacturing method (corresponding to the laminate manufacturing method of the present embodiment) using the separated first member.
  • the first member 1 for forming the resin layer is prepared (FIG. 1A) and cut (divided) into a predetermined size (FIG. 1B).
  • the resin layer 2 is formed on the first member 1 (FIG. 1C).
  • the resin layer 2 contains a volatile component such as a solvent
  • the volatile component is removed (FIG. 1 (d)), and the resin layer 2 is sandwiched between a pair of hot plates 3 and 4 and heated (FIG. 1 (e)).
  • the 2nd member 5 is arrange
  • a laminated body is manufactured without passing through the process of cutting a resin layer and a member. Therefore, it is possible to avoid various problems associated with the cutting of the resin layer and the member. Moreover, since a cutting process is not passed from the formation of the resin layer to obtaining the laminate, it is advantageous in terms of productivity.
  • the first member 1 when the first member 1 is cut in a state where the resin layer 2 is formed on the first member 1, a burr 10 is generated along the cut surface of the first member 1.
  • the burrs 10 may interfere with the arrangement of the laminated body in the press device in parallel when performing press bonding or the like in the next process, and the adhesion between each member and the resin layer may be impaired.
  • the crack 11 arises in the resin layer 2, and when a high voltage is applied to a laminated body, the crack 11 may be a starting point and may lead to a dielectric breakdown from a partial discharge.
  • the cutting waste 12 of the first member 1 and the cutting waste 13 of the resin layer 2 are generated to prevent the resin layer 2 from entering the surface irregularities of the first member 1, thereby reducing the adhesiveness of the resin layer 2 and insulating properties. There is a possibility of worsening. If the cutting waste 12 of the first member 1 is a conductive substance such as metal, it may become a conductive foreign substance and adversely affect the insulation of the resin layer 2.
  • the laminate manufactured by the manufacturing method of the present embodiment is not particularly limited as long as at least the first member, the resin layer, and the second member are arranged in this order.
  • a resin layer 2 is formed on each of the first member 1 and the second member 2, and a laminated body is manufactured by arranging the resin layer 2 of the first member 1 and the resin layer 2 of the second member 5 to face each other. May be.
  • a resin layer is formed on the first member.
  • the method for forming the resin layer is not particularly limited, and methods such as coating, printing, and transfer can be applied depending on the application. From the viewpoint of improving the adhesion of the resin layer to the first member, it is preferable to form the resin layer using a liquid resin composition.
  • the resin layer is formed using a liquid resin composition, the followability of the resin composition to the unevenness of the surface of the first member is improved, and the adhesion of the resin layer to the first member tends to be increased.
  • the “liquid resin composition” means a resin composition that is liquid at least when applied to the first member.
  • the liquid level is not particularly limited, and can be selected according to the surface state of the first member, the method of applying the resin composition, and the like.
  • the viscosity when applying the resin composition to the first member is preferably 10 Pa ⁇ s or less.
  • the viscosity of the resin composition is a value measured at 5 min ⁇ 1 (rpm) using (Toki Sangyo Co., Ltd., TV-33) at the temperature at which the resin composition is applied to the first member.
  • the composition is not particularly limited, and the resin layer alone may contain a component that adjusts the viscosity such as a solvent.
  • the resin composition contains a solvent, the solvent may be removed by drying or the like after the resin composition is applied on the first member.
  • the resin layer From the viewpoint of forming the resin layer at a predetermined position of the singulated first member, it is preferable to form the resin layer by applying a resin composition having excellent shape retention to the first member.
  • a resin composition having a thixotropic index of 1 or more at the temperature at which the resin composition is applied to the first member From the viewpoint of achieving both good coatability and shape retention, it is more preferable to use a resin composition having a thixotropic index of 1 to 10 at the temperature when the resin composition is applied to the first member. .
  • the thixotropic index of the resin composition is 5 min ⁇ 1 using a E-type viscometer (Toki Sangyo Co., Ltd., TV-33) at the temperature at which the resin composition is applied to the first member.
  • the ratio of viscosity B (Pa ⁇ s) measured at 0.5 min ⁇ 1 (rpm) to viscosity A (Pa ⁇ s) measured at rpm) (viscosity B / viscosity A).
  • the resin layer forming step preferably includes a step of heating the resin layer.
  • a step of heating the resin layer volatile components such as a solvent contained in the resin layer are efficiently removed.
  • the resin component in the resin layer reacts to increase the viscosity, and the followability to the second member is reduced to some extent.
  • the second member having a small surface roughness is used as the resin layer. Therefore, good adhesion can be ensured.
  • the method of heating the resin layer is not particularly limited, but a method of bringing the resin layer into a B-stage state is preferable.
  • the method and conditions for bringing the resin layer into the B stage state are not particularly limited. From the viewpoint of forming a resin layer having a smooth surface and reduced thickness unevenness, a method of heating while pressing the first member and the resin layer formed thereon with a pair of hot plates is preferable.
  • the second member is placed on the resin layer formed on the first member.
  • the method for arranging the second member is not particularly limited.
  • the resin layer After disposing the second member on the resin layer formed on the first member, the resin layer is cured to obtain a laminate.
  • the method for curing the resin layer is not particularly limited.
  • the second member may be sandwiched between a pair of hot plates in a state where the second member is disposed on the resin layer and heated while being pressed.
  • the manufacturing method of the laminated body of this embodiment may satisfy
  • the surface roughness (Rz) of the surface in contact with the resin layer of the first member is larger than the surface roughness (Rz) of the surface in contact with the resin layer of the second member.
  • the surface roughness (Rz) of the surface in contact with the resin layer of the second member is 30 ⁇ m or less.
  • the manufacturing method of the laminated body of the present embodiment satisfies the condition (2), even if the followability to the surface shape of the second member of the resin layer formed on the first member is reduced, the second member Adequate adhesion is obtained when the surface roughness (Rz) of the surface in contact with the resin layer is 30 ⁇ m or less.
  • the material of the first member and the second member is not particularly limited, and examples thereof include metals, semiconductors, glasses, resins, and composites thereof.
  • the shape in particular of a 1st member and a 2nd member is not restrict
  • the material and shape of the first member and the second member may be the same or different.
  • size of the 1st and 2nd member of the state separated into pieces is not restrict
  • the area may be in the range of 1 cm 2 to 200 cm 2 .
  • the first member and the second member may be subjected to a surface roughening treatment.
  • a surface roughening treatment In general, as the surface roughness of the surface where the member is in contact with the resin layer is larger, the anchor effect that is manifested by the resin layer entering into the irregularities on the surface of the member increases, and the adhesive strength tends to increase. As a result, it can be expected to improve the shear strength for evaluating the adhesive force mainly applied in the planar direction of the resin layer, and the peel strength for evaluating the adhesive force mainly applied in the vertical direction of the resin layer.
  • the member subjected to the surface roughening treatment may be obtained using a material having a rough surface or may be obtained by roughening a material having a smooth surface.
  • the surface roughening treatment method is not particularly limited, and may be performed by a physical method or a chemical method. Physical methods include file processing, sandblasting, laser irradiation, and the like. Examples of the chemical treatment include magnesium treatment, CZ treatment, blackening treatment, etching treatment and the like when the material is copper. When the material is aluminum, alumite treatment is exemplified.
  • the method of surface treatment is not limited to these, and physical treatment or chemical treatment is performed alone, physical treatment and chemical treatment are combined, or two or more chemical treatments are combined. Or two or more physical processes may be combined.
  • the surface which contacts the resin layer of the first member and the second member may be provided with a surface treatment agent.
  • Surface treatment agents include solid or liquid thermosetting resin monomer coating and thermoplastic resin solvent coating, silanol coupling agent, titanate coupling agent, aluminosilicate agent, leveling for the purpose of improving the wettability of the resin. And surface protecting agents such as agents.
  • the type of resin contained in the resin layer is not particularly limited. Examples thereof include thermosetting resins such as epoxy resins, phenol resins, urea resins, melamine resins, urethane resins, silicone resins, and unsaturated polyester resins.
  • the resin contained in the resin layer may be one type or two or more types. From the viewpoint of electrical insulation and adhesiveness, the resin layer preferably contains an epoxy resin.
  • the resin layer may contain a component other than the resin such as a filler as necessary.
  • the thickness of the resin layer is not particularly limited. From the viewpoint of sufficiently obtaining the effects (insulating properties, etc.) obtained by providing the resin layer, the larger the thickness, the better. From the viewpoint of manufacturing cost, thermal conductivity, etc., the smaller the thickness, the better. For example, it may be in the range of 80 ⁇ m to 300 ⁇ m. In this specification, the thickness of the resin layer can be measured by a known method, and the arithmetic average value of the values measured at five points is used.
  • the use of the laminate manufactured by the manufacturing method of the present embodiment is not particularly limited.
  • a semiconductor device can be given.
  • semiconductor devices it is suitably used for components with particularly high heat generation density.
  • Epoxy monomer The epoxy monomer contained in the epoxy resin composition may be one type alone or two or more types. Moreover, what the epoxy monomer was in the state of the oligomer or the prepolymer may be included.
  • the type of epoxy monomer is not particularly limited, and can be selected according to the use of the laminate.
  • an epoxy monomer having a mesogenic skeleton and having two glycidyl groups in one molecule (hereinafter also referred to as a specific epoxy monomer) may be used.
  • a resin layer formed using an epoxy resin composition containing a specific epoxy monomer tends to exhibit high thermal conductivity.
  • the “mesogen skeleton” indicates a molecular structure that may exhibit liquid crystallinity. Specific examples include a biphenyl skeleton, a phenylbenzoate skeleton, an azobenzene skeleton, a stilbene skeleton, and derivatives thereof.
  • An epoxy resin composition containing an epoxy monomer having a mesogenic skeleton tends to form a higher-order structure at the time of curing and tends to achieve higher thermal conductivity when a cured product is produced.
  • Specific epoxy monomers include, for example, biphenyl type epoxy monomers and tricyclic type epoxy monomers.
  • the specific epoxy monomer contained in the epoxy resin composition may be one kind alone or two or more kinds. Moreover, what the specific epoxy monomer was in the state of the oligomer or the prepolymer may be included.
  • Biphenyl type epoxy monomers include 4,4'-bis (2,3-epoxypropoxy) biphenyl, 4,4'-bis (2,3-epoxypropoxy) -3,3 ', 5,5'-tetramethyl An epoxy monomer obtained by reacting biphenyl, epichlorohydrin and 4,4′-biphenol or 4,4 ′-(3,3 ′, 5,5′-tetramethyl) biphenol, ⁇ -hydroxyphenyl- ⁇ -hydropoly ( Biphenyldimethylene-hydroxyphenylene) and the like.
  • Biphenyl type epoxy resins are named according to product names such as “YX4000”, “YL6121H” (Mitsubishi Chemical Corporation), “NC-3000”, “NC-3100” (Nippon Kayaku Co., Ltd.). The thing marketed is mentioned.
  • Examples of the tricyclic epoxy monomer include epoxy monomers having a terphenyl skeleton, 1- (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -1-cyclohexene, 1- Examples include (3-methyl-4-oxiranylmethoxyphenyl) -4- (4-oxiranylmethoxyphenyl) -benzene, compounds represented by the following general formula (I), and the like.
  • the specific epoxy monomer is preferably capable of forming a higher order structure and capable of forming a smectic structure when used alone as an epoxy monomer and cured. Is more preferable.
  • examples of such an epoxy monomer include compounds represented by the following general formula (I).
  • the epoxy resin composition contains a compound represented by the following general formula (I)
  • higher thermal conductivity can be achieved.
  • 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 or 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 preferably hydrogen atoms, more preferably 3 or 4 are hydrogen atoms, and all 4 are further hydrogen atoms. preferable.
  • 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.
  • the higher order structure is a state in which the constituent elements are arranged microscopically, and corresponds to, for example, a crystal phase and a liquid crystal phase. Whether or not such a higher-order structure exists can be easily determined by observation with a polarizing microscope. That is, when an interference pattern due to depolarization is observed in the observation in the crossed Nicol state, it can be determined that a higher order structure exists.
  • the higher order structure usually exists in an island shape in the resin, and forms a domain structure. Each island forming the domain structure is called a higher-order structure.
  • the structural units constituting the higher order structure are generally bonded by a covalent bond.
  • High-order structures with high regularity derived from the mesogenic skeleton include nematic structures and smectic structures.
  • the nematic 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 structure is a liquid crystal structure having a one-dimensional positional order in addition to the orientation order and having a layer structure with a constant period.
  • the direction of the period of the layer structure is uniform inside the structure having the same period of the smectic structure. That is, the order of molecules is higher in the smectic structure than in the nematic structure.
  • the smectic structure has a higher thermal conductivity than the nematic structure. That is, the order of the molecule is higher in the smectic structure than in the nematic structure, and the thermal conductivity of the cured product is higher in the case of showing the smectic structure. Since the epoxy resin composition containing the compound represented by the general formula (I) can react with a curing agent to form a smectic structure, it is considered that high thermal conductivity can be exhibited.
  • Whether or not a smectic structure can be formed using the epoxy resin composition can be determined by the following method.
  • 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 °.
  • a diffraction peak exists in the range of 2 ⁇ of 1 ° to 10 °, it is determined that the periodic structure includes a smectic structure. Note that in the case of a highly ordered high-order structure derived from a mesogenic structure, a diffraction peak appears in the range of 2 ⁇ of 1 ° to 30 °.
  • the epoxy resin composition contains two or more types of specific epoxy monomers and a curing agent, and the two or more types of specific epoxy monomers are compatible with each other, and react with the curing agent to form a smectic structure.
  • An epoxy resin composition that can be formed (hereinafter, also referred to as “specific epoxy resin composition”) may be used.
  • the specific epoxy resin composition has a low melting point and excellent thermal conductivity after curing.
  • two or more types of epoxy monomers mean two or more types of epoxy monomers having different molecular structures. However, epoxy monomers having a stereoisomer (optical isomer, geometric isomer, etc.) relationship do not fall under “two or more epoxy monomers” and are regarded as the same type of epoxy monomer.
  • the specific epoxy resin composition has a low melting point and excellent thermal conductivity after curing is not clear, but two or more specific epoxy monomers are compatible with each other to form a smectic structure. It is considered that the melting point of the previous specific epoxy resin composition can be lowered and high thermal conductivity can be exhibited after curing.
  • the specific epoxy resin composition contains two or more specific epoxy monomers, and the specific epoxy monomers are compatible with each other.
  • the melting point of a mixture of two or more types of specific epoxy monomers compatible with each other (hereinafter also referred to as “epoxy monomer mixture”) is the specific epoxy having the highest melting point among the specific epoxy monomers constituting the epoxy monomer mixture. There is a phenomenon that the melting point of the monomer becomes lower. Therefore, it becomes possible to exhibit the low melting point of the specific epoxy resin composition.
  • the thermal conductivity when the specific epoxy resin composition is semi-cured or cured is higher than the thermal conductivity when the specific epoxy monomer alone constituting the epoxy monomer mixture is semi-cured or cured. It becomes possible to do.
  • the epoxy monomer mixture includes three or more types of specific epoxy monomers, it is sufficient that the epoxy monomer mixture composed of all the specific epoxy monomers constituting the epoxy monomer mixture is compatible as a whole. Any two selected specific epoxy monomers may not be compatible with each other.
  • compatible means phase separation derived from a specific epoxy monomer when the specific epoxy resin composition is semi-cured or cured after the epoxy monomer mixture is melted and naturally cooled. Means that no condition is observed. Moreover, even if each specific epoxy monomer is phase-separated in the epoxy monomer mixture before making a semi-cured product or a cured product, when a phase-separated state is not observed when making a semi-cured product or a cured product, It is determined that the specific epoxy monomers contained in the monomer mixture are compatible with each other.
  • Whether or not the specific epoxy monomers are compatible with each other can be determined by the presence or absence of a phase separation state when the specific epoxy resin composition is made into a semi-cured product or a cured product. For example, it can be judged by observing a semi-cured product or a cured product of a specific epoxy resin composition at a curing temperature described later using an optical microscope. More specifically, the determination can be made by the following method. The epoxy monomer mixture is melted by heating above the temperature at which the epoxy monomer mixture transitions to the isotropic phase, and then the molten epoxy monomer mixture is allowed to cool naturally.
  • the curing temperature can be appropriately selected according to the specific epoxy resin composition.
  • the curing temperature is preferably 100 ° C. or higher, more preferably 100 ° C. to 250 ° C., and still more preferably 120 ° C. to 210 ° C.
  • the melting point of the epoxy monomer mixture composed of the specific epoxy monomers in a compatible combination is lower than the melting point of the specific epoxy monomer having the highest melting point among the specific epoxy monomers constituting the epoxy monomer mixture.
  • the melting point refers to the temperature at which an epoxy monomer undergoes a phase transition from a liquid crystal phase to an isotropic phase in an epoxy monomer having a liquid crystal phase.
  • an epoxy monomer having no liquid crystal phase it indicates the temperature at which the state of the substance changes from a solid (crystalline phase) to a liquid (isotropic phase).
  • the liquid crystal phase is one of the phases located between the crystalline state (crystalline phase) and the liquid state (isotropic phase).
  • the presence or absence of a liquid crystal phase can be determined by a method of observing a change in the state of a substance in the process of raising the temperature from room temperature (for example, 25 ° C.) using a polarizing microscope. In the observation in the crossed Nicols state, interference fringes due to depolarization are seen in the crystal phase and the liquid crystal phase, and the isotropic phase appears in the dark field. The transition from the crystal phase to the liquid crystal phase can be confirmed by the presence or absence of fluidity. In other words, the expression of the liquid crystal phase means that the liquid crystal phase has a fluidity and has a temperature region where interference fringes due to depolarization are observed.
  • the specific epoxy monomer or the epoxy monomer mixture has fluidity and has a temperature region where interference fringes due to depolarization are observed, the specific epoxy monomer Alternatively, it is determined that the epoxy monomer mixture has a liquid crystal phase.
  • the temperature range is preferably 10 ° C. or higher, more preferably 20 ° C. or higher, and further preferably 40 ° C. or higher.
  • the temperature region is 10 ° C. or higher, high thermal conductivity tends to be achieved. Furthermore, the wider the temperature region, the higher the thermal conductivity, which is preferable.
  • the melting point of the specific epoxy monomer or epoxy monomer mixture can be determined by using a differential scanning calorimeter (DSC) in a temperature range from 25 ° C. to 350 ° C. under a temperature rising rate of 10 ° C./min. It is measured as a temperature at which an energy change (endothermic reaction) occurs with a phase transition.
  • DSC differential scanning calorimeter
  • the two or more types of specific epoxy monomers contained in the specific epoxy resin composition are compatible with each other, and are not particularly limited as long as they can form a smectic structure by reacting with a curing agent described later. It can be selected from epoxy monomers having a skeleton.
  • the specific epoxy monomer can be selected from those exemplified above.
  • the specific epoxy resin composition is different from the compound represented by the general formula (I) and the compound represented by the general formula (I) as two or more kinds of specific epoxy monomers, and is represented by the general formula (I). It is preferable to contain a specific epoxy monomer that is compatible with the compound (hereinafter referred to as “specific epoxy monomer different from the compound represented by the general formula (I)”).
  • the epoxy resin composition contains a compound represented by the general formula (I) and a specific epoxy monomer different from the compound represented by the general formula (I), thereby effectively reducing the melting point and heat conductivity. It is possible to achieve both improvements.
  • the content of the specific epoxy monomer in the epoxy monomer mixture is not particularly limited as long as it can form a smectic structure by reaction between the epoxy monomer mixture and a curing agent described later, and can be selected as appropriate. From the viewpoint of lowering the melting point, the content of the specific epoxy monomer is preferably 5% by mass or more, more preferably 10% by mass to 90% by mass, more preferably 100% by mass with respect to the total mass of the epoxy monomer mixture. % Is more preferable.
  • the total content of the specific epoxy monomer in the epoxy resin composition is not particularly limited. From the viewpoint of thermosetting and thermal conductivity, the total content of the specific epoxy monomer is preferably 3% by mass to 10% by mass with respect to the total mass of the epoxy resin composition, and 3% by mass to 8% by mass. It is more preferable that
  • the epoxy resin composition contains a curing agent.
  • the curing agent is not particularly limited as long as it is a compound capable of curing reaction with a specific epoxy monomer, and a commonly used curing agent can be appropriately selected and used.
  • Specific examples of the curing agent include acid anhydride curing agents, amine curing agents, phenol curing agents, polyaddition curing agents such as mercaptan curing agents, and catalytic curing agents such as imidazole. These curing agents may be used alone or in combination of two or more.
  • the amine-based curing agent those usually used as curing agents for epoxy monomers can be used without particular limitation, and commercially available ones may be used.
  • the amine curing agent is preferably a polyfunctional curing agent having two or more functional groups, and from the viewpoint of thermal conductivity, is a polyfunctional curing agent having a rigid skeleton. It is more preferable.
  • bifunctional amine curing agent examples include 4,4′-diaminodiphenylmethane, 4,4′-diaminodiphenyl ether, 4,4′-diaminodiphenyl sulfone, 4,4′-diamino-3,3.
  • Examples include '-dimethoxybiphenyl, 4,4'-diaminophenyl benzoate, 1,5-diaminonaphthalene, 1,3-diaminonaphthalene, 1,4-diaminonaphthalene, 1,8-diaminonaphthalene and the like.
  • thermo conductivity it is preferably at least one selected from the group consisting of 4,4′-diaminodiphenylmethane, 1,5-diaminonaphthalene and 4,4′-diaminodiphenylsulfone, More preferred is 5-diaminonaphthalene.
  • phenol and a novolac phenol resin can be used.
  • the phenol curing agent include monofunctional compounds such as phenol, o-cresol, m-cresol, and p-cresol; bifunctional compounds such as catechol, resorcinol, and hydroquinone; 1,2,3-trihydroxybenzene, 1, And trifunctional compounds such as 2,4-trihydroxybenzene and 1,3,5-trihydroxybenzene.
  • a phenol novolak resin obtained by connecting these phenol curing agents with a methylene chain or the like to form a novolak can be used.
  • the phenol novolak resin include resins obtained by novolacizing one phenol compound such as cresol novolak resin, catechol novolak resin, resorcinol novolak resin, hydroquinone novolak resin; catechol resorcinol novolak resin, resorcinol hydroquinone novolak resin, etc. Examples thereof include resins obtained by novolacizing two or more phenol compounds.
  • the phenol novolak resin When a phenol novolak resin is used as the phenolic curing agent, the phenol novolak resin has a structural unit represented by at least one selected from the group consisting of the following general formulas (II-1) and (II-2) It is preferable to include a compound.
  • R 21 and R 24 each independently represents an alkyl group, an aryl group or an aralkyl group.
  • R 22 , R 23 , R 25 and R 26 each independently represent a hydrogen atom, an alkyl group, an aryl group or an aralkyl group.
  • m21 and m22 each independently represents an integer of 0-2.
  • n21 and n22 each independently represents an integer of 1 to 7.
  • the alkyl group may be linear, branched or cyclic.
  • the aryl group may have a structure containing a hetero atom in the aromatic ring. In this case, a heteroaryl group in which the total number of heteroatoms and carbon is 6 to 12 is preferable.
  • the alkylene group in the aralkyl group may be any of a chain, a branched chain, and a cyclic group.
  • the aryl group in the aralkyl group may have a structure containing a hetero atom in the aromatic ring. In this case, a heteroaryl group in which the total number of heteroatoms and carbon is 6 to 12 is preferable.
  • R 21 and R 24 each independently represents an alkyl group, an aromatic group (aryl group), or an aralkyl group. These alkyl group, aromatic group and aralkyl group may further have a substituent if possible. Examples of the substituent include an alkyl group (except when R 21 and R 24 are alkyl groups), an aromatic group, a halogen atom, and a hydroxyl group.
  • m21 and m22 each independently represents an integer of 0 to 2, and when m21 or m22 is 2, two R 21 or R 24 may be the same or different.
  • m21 and m22 are each independently preferably 0 or 1, and more preferably 0.
  • n21 and n22 are the numbers of structural units represented by the above general formulas (II-1) and (II-2) contained in the phenol novolac resin, and each independently represents an integer of 1 to 7.
  • R 22 , R 23 , R 25 and R 26 each independently represent a hydrogen atom, an alkyl group, an aryl group, or an aralkyl group.
  • the alkyl group, aryl group and aralkyl group represented by R 22 , R 23 , R 25 and R 26 may further have a substituent, if possible.
  • the substituent include an alkyl group (provided that R 22 , R 23 , R 25 and R 26 are alkyl groups), an aryl group, a halogen atom, a hydroxyl group and the like.
  • R 22 , R 23 , R 25 and R 26 are each independently a hydrogen atom, an alkyl group, from the viewpoint of storage stability and thermal conductivity, Alternatively, it is preferably an aryl group, more preferably a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or an aryl group having 6 to 12 carbon atoms, and further preferably a hydrogen atom. Furthermore, from the viewpoint of heat resistance, at least one of R 22 and R 23 is preferably an aryl group, more preferably an aryl group having 6 to 12 carbon atoms.
  • R 25 and R 26 is preferably an aryl group, and more preferably an aryl group having 6 to 12 carbon atoms.
  • the aryl group may have a structure containing a hetero atom in the aromatic ring. In this case, a heteroaryl group in which the total number of heteroatoms and carbon is 6 to 12 is preferable.
  • the phenolic curing agent may contain one type of compound having the structural unit represented by the above general formula (II-1) or general formula (II-2) alone, or may contain two or more types. Preferably, it contains at least one compound having a structural unit derived from resorcinol represented by the general formula (II-1).
  • the compound having the structural unit represented by the general formula (II-1) may further include at least one partial structure derived from a phenol compound other than resorcinol.
  • examples of the partial structure derived from a phenol compound other than resorcinol include phenol, cresol, catechol, hydroquinone, 1,2,3-trihydroxybenzene, 1,2,4-trimethyl. Examples thereof include partial structures derived from hydroxybenzene and 1,3,5-trihydroxybenzene. The partial structures derived from these may be contained singly or in combination of two or more.
  • the compound having the structural unit represented by the general formula (II-2) may include at least one partial structure derived from a phenol compound other than catechol.
  • examples of the partial structure derived from a phenol compound other than catechol include, for example, phenol, cresol, resorcinol, hydroquinone, 1,2,3-trihydroxybenzene, 1,2,4-trimethyl. Examples thereof include partial structures derived from hydroxybenzene and 1,3,5-trihydroxybenzene. The partial structures derived from these may be contained singly or in combination of two or more.
  • the partial structure derived from the phenol compound means a monovalent or divalent group constituted by removing one or two hydrogen atoms from the benzene ring portion of the phenol compound.
  • the position where the hydrogen atom is removed is not particularly limited.
  • the content of the partial structure derived from resorcinol is not particularly limited. From the viewpoint of the elastic modulus, the content of the partial structure derived from resorcinol is preferably 55% by mass or more based on the total mass of the compound having the structural unit represented by the general formula (II-1), and the glass transition temperature From the viewpoint of (Tg) and the linear expansion coefficient, it is more preferably 80% by mass or more, and from the viewpoint of thermal conductivity, it is further preferably 90% by mass or more.
  • the phenol novolac resin more preferably includes a novolac resin having a partial structure represented by at least one selected from the group consisting of the following general formulas (III-1) to (III-4).
  • n31 to n34 each independently represent a positive integer and represent the number of each structural unit contained.
  • Ar 31 to Ar 34 each independently represent a group represented by the following general formula (III-a) or a group represented by the following general formula (III-b).
  • R 31 and R 34 each independently represent a hydrogen atom or a hydroxyl group.
  • R 32 and R 33 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • a curing agent having a partial structure represented by at least one of general formula (III-1) to general formula (III-4) is produced as a by-product by a production method described later in which a divalent phenol compound is novolakized. It can be generated.
  • the partial structures represented by the general formulas (III-1) to (III-4) may be included as the main chain skeleton of the compound, or may be included as a part of the side chain. Furthermore, each structural unit constituting the partial structure represented by any one of the above general formulas (III-1) to (III-4) may be included randomly or regularly. It may be contained in a block shape. In the above general formulas (III-1) to (III-4), the hydroxyl substitution position is not particularly limited as long as it is on the aromatic ring.
  • a plurality of Ar 31 to Ar 34 may all be the same atomic group or include two or more atomic groups. Also good. Ar 31 to Ar 34 each independently represents a group represented by any one of the above general formulas (III-a) and (III-b).
  • R 31 and R 34 are each independently a hydrogen atom or a hydroxyl group, but are preferably a hydroxyl group from the viewpoint of thermal conductivity. Further, the substitution positions of R 31 and R 34 are not particularly limited.
  • R 32 and R 33 in the above general formula (III-a) and general formula (III-b) each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms.
  • the alkyl group having 1 to 8 carbon atoms in R 32 and R 33 include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, and an n-pentyl group. , N-hexyl group, n-heptyl group, and n-octyl group.
  • the substitution positions of R 32 and R 33 in general formula (III-a) and general formula (III-b) are not particularly limited.
  • Ar 31 to Ar 34 in the general formula (III-a) and the general formula (III-b) are groups derived from dihydroxybenzene (in the general formula (III-a), from the viewpoint of achieving higher thermal conductivity.
  • One type is preferable.
  • group derived from dihydroxybenzene means a divalent group formed by removing two hydrogen atoms from the aromatic ring portion of dihydroxybenzene, and the position at which the hydrogen atom is removed is not particularly limited. Further, the “group derived from dihydroxynaphthalene” has the same meaning.
  • Ar 31 to Ar 34 are more preferably each independently a group derived from dihydroxybenzene, and 1,2-dihydroxybenzene (catechol) More preferably, it is at least one selected from the group consisting of a group derived from the above and a group derived from 1,3-dihydroxybenzene (resorcinol).
  • Ar 31 to Ar 34 preferably include at least a group derived from resorcinol from the viewpoint of particularly improving thermal conductivity.
  • the structural unit represented by n31 to n34 preferably contains a group derived from resorcinol.
  • the compound having a partial structure represented by at least one selected from the group consisting of general formula (III-1) to general formula (III-4) includes a structural unit derived from resorcinol, it is derived from resorcinol
  • the content of the structural unit containing the group is, in terms of elastic modulus, in the whole compound having the structure represented by at least one of the above general formulas (III-1) to (III-4) It is preferably 55% by mass or more, more preferably 80% by mass or more from the viewpoint of Tg and linear expansion coefficient, and further preferably 90% by mass or more from the viewpoint of thermal conductivity.
  • the total value of mx and nx is preferably 20 or less, more preferably 15 or less, and still more preferably 10 or less from the viewpoint of fluidity.
  • the lower limit of the total value of m and n is not particularly limited.
  • Mx and nx represent the number of structural units and indicate how much the corresponding structural unit is added in the molecule. Therefore, an integer value is shown for a single molecule. Note that mx and nx in (mx / nx) and (mx + nx) indicate rational numbers that are average values in the case of an assembly of a plurality of types of molecules.
  • the phenol novolak resin having a partial structure represented by at least one selected from the group consisting of the above general formulas (III-1) to (III-4) is particularly substituted or unsubstituted in Ar 31 to Ar 34
  • a curing agent having a low melting point can be obtained as compared with a novolak phenol resin or the like.
  • Whether or not the phenol novolac resin has a partial structure represented by any one of the general formulas (III-1) to (III-4) is determined by field desorption ionization mass spectrometry (FD-MS). The determination can be made based on whether or not the fragment component includes a component corresponding to the partial structure represented by any of the general formulas (II-1) to (II-4).
  • FD-MS field desorption ionization mass spectrometry
  • the molecular weight of the phenol novolac resin having a partial structure represented by at least one selected from the group consisting of general formula (III-1) to general formula (III-4) is not particularly limited.
  • the number average molecular weight (Mn) is preferably 2000 or less, more preferably 1500 or less, and even more preferably 350 to 1500.
  • the weight average molecular weight (Mw) is preferably 2000 or less, more preferably 1500 or less, and further preferably 400 to 1500.
  • Mn and Mw are measured by a usual method using GPC (gel permeation chromatography).
  • the hydroxyl equivalent of the phenol novolac resin having a partial structure represented by at least one selected from the group consisting of general formula (III-1) to general formula (III-4) is not particularly limited.
  • the hydroxyl group equivalent is preferably 50 g / eq to 150 g / eq on average, more preferably 50 g / eq to 120 g / eq, and 55 g / eq to 120 g / eq. More preferably, it is eq.
  • a hydroxyl equivalent means the value measured based on JISK0070: 1992.
  • the phenol novolac resin may contain a monomer that is a phenol compound constituting the phenol novolac resin.
  • the content of the monomer that is a phenol compound constituting the phenol novolac resin (hereinafter also referred to as “monomer content”) is not particularly limited. From the viewpoint of thermal conductivity and moldability, the monomer content in the phenol novolac resin is preferably 5% by mass to 80% by mass, more preferably 15% by mass to 60% by mass, and 20% by mass. More preferably, it is ⁇ 50 mass%.
  • the monomer content is 80% by mass or less, the amount of monomers that do not contribute to crosslinking decreases during the curing reaction, and the high molecular weight material that contributes to crosslinking occupies a large amount. It is formed and the thermal conductivity is improved.
  • the monomer content is 5% by mass or more, it is easy to flow during molding, so that the adhesion with the inorganic filler contained as necessary is further improved, and more excellent thermal conductivity and heat resistance. Tend to be achieved.
  • the content of the curing agent in the epoxy resin composition is not particularly limited.
  • the ratio of the number of active hydrogen equivalents of the amine curing agent (amine equivalent number) to the number of epoxy groups equivalent of the epoxy monomer (amine equivalent number / epoxy equivalent number) Is preferably 0.5 to 2.0, more preferably 0.8 to 1.2.
  • the curing agent is a phenolic curing agent
  • the number of equivalents of epoxy groups is preferably 0.5 to 2.0, and more preferably 0.8 to 1.2.
  • the epoxy resin composition may contain a curing accelerator.
  • a curing agent and a curing accelerator in combination, it can be further sufficiently cured.
  • the kind and content of the curing accelerator are not particularly limited, and an appropriate one can be selected from the viewpoint of reaction rate, reaction temperature, and storage property.
  • Specific examples include imidazole compounds, tertiary amine compounds, organic phosphine compounds, complexes of organic phosphine compounds and organic boron compounds, and the like.
  • it is preferably at least one selected from the group consisting of an organic phosphine compound and a complex of an organic phosphine compound and an organic boron compound.
  • organic phosphine compound examples include triphenylphosphine, diphenyl (p-tolyl) phosphine, tris (alkylphenyl) phosphine, tris (alkoxyphenyl) phosphine, tris (alkylalkoxyphenyl) phosphine, and tris (dialkylphenyl).
  • Phosphine tris (trialkylphenyl) phosphine, tris (tetraalkylphenyl) phosphine, tris (dialkoxyphenyl) phosphine, tris (trialkoxyphenyl) phosphine, tris (tetraalkoxyphenyl) phosphine, trialkylphosphine, dialkylarylphosphine And alkyldiarylphosphine.
  • an organic phosphine compound and an organic boron compound include tetraphenylphosphonium / tetraphenylborate, tetraphenylphosphonium / tetra-p-tolylborate, tetrabutylphosphonium / tetraphenylborate, and tetraphenylphosphonium.
  • One of these curing accelerators may be used alone, or two or more thereof may be used in combination.
  • the mixing ratio should be determined without any particular restrictions depending on the characteristics (for example, how much flexibility is required) required for the semi-cured epoxy resin composition. Can do.
  • the content of the curing accelerator in the epoxy resin composition is not particularly limited.
  • the content of the curing accelerator is preferably 0.5% by mass to 1.5% by mass of the total mass of the epoxy monomer and the curing agent, and 0.5% by mass to 1% by mass. More preferably, the content is 0.6% by mass to 1% by mass.
  • the epoxy resin composition may include an inorganic filler. By including the inorganic filler, the epoxy resin composition can achieve high thermal conductivity.
  • the inorganic filler may be non-conductive or conductive. Use of a non-conductive inorganic filler tends to suppress a decrease in insulation. Moreover, it exists in the tendency for thermal conductivity to improve more by using a conductive inorganic filler.
  • non-conductive inorganic filler examples include aluminum oxide (alumina), magnesium oxide, aluminum nitride, boron nitride, silicon nitride, silica (silicon oxide), silicon oxide, aluminum hydroxide, and barium sulfate.
  • conductive inorganic filler examples include gold, silver, nickel, and copper.
  • the inorganic filler is preferably at least one selected from the group consisting of aluminum oxide (alumina), boron nitride, magnesium oxide, aluminum nitride, and silica (silicon oxide). More preferably, it is at least one selected from the group consisting of boron nitride and aluminum oxide (alumina).
  • These inorganic fillers may be used alone or in combination of two or more.
  • the inorganic filler having a small particle diameter is packed in the voids of the inorganic filler having a large particle diameter, thereby filling the inorganic filler more densely than using only the inorganic filler having a single particle diameter. It becomes possible to exhibit higher thermal conductivity.
  • aluminum oxide when aluminum oxide is used as the inorganic filler, aluminum oxide having a volume average particle diameter of 16 ⁇ m to 20 ⁇ m is oxidized in the inorganic filler by 60 volume% to 75 volume% and volume average particle diameter of 2 ⁇ m to 4 ⁇ m.
  • the volume average particle diameter (D50) of the inorganic filler can be measured using a laser diffraction method.
  • the inorganic filler in the epoxy resin composition is extracted and measured using a laser diffraction / scattering particle size distribution analyzer (for example, trade name: LS230, manufactured by Beckman Coulter, Inc.).
  • LS230 laser diffraction / scattering particle size distribution analyzer
  • the inorganic filler component is extracted from the epoxy resin composition and sufficiently dispersed with an ultrasonic disperser, etc., and the weight cumulative particle size distribution curve of this dispersion liquid Measure.
  • the volume average particle diameter (D50) refers to the particle diameter at which accumulation is 50% from the small diameter side in the volume cumulative distribution curve obtained from the above measurement.
  • the content of the inorganic filler is preferably more than 50% by volume, more than 70% by volume, and 90% by volume when the total volume of the epoxy resin composition is 100% by volume. The following is more preferable.
  • the content of the inorganic filler exceeds 50% by volume, higher thermal conductivity can be achieved.
  • the content of the inorganic filler is 90% by volume or less, the flexibility of the epoxy resin composition and the insulating property tend to be suppressed.
  • the epoxy resin composition may contain at least one silane coupling agent.
  • the silane coupling agent has a role of forming a covalent bond between the surface of the inorganic filler and the surrounding resin (equivalent to a binder agent), an improvement in thermal conductivity, and prevents moisture penetration. It can be thought that it plays a role of improving sex.
  • the type of silane coupling agent is not particularly limited, and a commercially available product may be used.
  • the terminal is an epoxy group, an amino group, a mercapto group. It is preferable to use a silane coupling agent having a ureido group and a hydroxyl group.
  • silane coupling agent examples include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropylmethyldimethoxysilane.
  • silane coupling agent oligomers manufactured by Hitachi Chemical Techno Service Co., Ltd. represented by trade name: SC-6000KS2. These silane coupling agents may be used alone or in combination of two or more.
  • the epoxy resin composition may contain other components in addition to the above components, if necessary.
  • examples of other components include a solvent, an elastomer, a dispersant, and an anti-settling agent.
  • the solvent is not particularly limited as long as it does not inhibit the curing reaction of the epoxy resin composition, and a commonly used organic solvent can be appropriately selected and used.
  • First member A an aluminum plate having a surface roughness (Rz) of 18 ⁇ m on the surface in contact with the resin layer (size: 40 mm ⁇ 40 mm ⁇ 3 mm)
  • Second member A copper plate having a surface roughness (Rz) of 3 ⁇ m on the surface in contact with the resin layer (size: 40 mm ⁇ 40 mm ⁇ 3 mm)
  • First member B an aluminum plate having a surface roughness (Rz) of 18 ⁇ m on the surface in contact with the resin layer (size: 160 mm ⁇ 160 mm ⁇ 3 mm)
  • Second member B copper plate having a surface roughness (Rz) of 3 ⁇ m on the surface in contact with the resin layer (size: 160 mm ⁇ 160 mm ⁇ 3 mm)
  • the formation of the resin layer in the laminate for evaluation in Examples and Comparative Examples was performed using an epoxy resin composition.
  • the material used for preparation of an epoxy resin composition and its abbreviation are shown below.
  • Mn and Mw weight average molecular weight were measured as follows. Mn and Mw were measured using a high performance liquid chromatography (manufactured by Hitachi, Ltd., trade name: L6000) and a data analyzer (manufactured by Shimadzu Corporation, trade name: C-R4A). As analytical GPC columns, G2000HXL and G3000HXL (trade names) manufactured by Tosoh Corporation were used. The sample concentration was 0.2% by mass, tetrahydrofuran was used as the mobile phase, and the measurement was performed at a flow rate of 1.0 mL / min. A calibration curve was prepared using a polystyrene standard sample, and Mn and Mw were calculated using polystyrene conversion values.
  • the hydroxyl equivalent was measured as follows.
  • the hydroxyl equivalent was measured by acetyl chloride-potassium hydroxide titration method.
  • the determination of the titration end point was performed by potentiometric titration instead of the coloring method using an indicator because the solution color was dark.
  • the hydroxyl group of the measurement resin is acetylated in a pyridine solution, the excess reagent is decomposed with water, and the resulting acetic acid is titrated with a potassium hydroxide / methanol solution.
  • the obtained CRN is a mixture of compounds having a partial structure represented by at least one of the general formulas (III-1) to (III-4), and Ar is represented by the general formula (III-a )
  • R 31 is a hydroxyl group
  • R 32 and R 33 are hydrogen atoms, a group derived from 1,2-dihydroxybenzene (catechol) and a group derived from 1,3-dihydroxybenzene (resorcinol)
  • TPP Triphenylphosphine [Wako Pure Chemical Industries, Ltd., trade name]
  • KBM-573 3-phenylaminopropyltrimethoxysilane [silane coupling agent, manufactured by Shin-Etsu Chemical Co., Ltd., trade name]
  • the density of boron nitride (HP-40) is 2.20 g / cm 3
  • the density of alumina (AA-3 and AA-04) is 3.98 g / cm 3
  • epoxy monomers (monomer A and monomer B) and curing agent When the density of the mixture with (CRN) was 1.20 g / cm 3 and the ratio of the inorganic filler to the total volume of the total solid content of the epoxy resin composition was calculated, it was 72% by volume.
  • the first member A is prepared such that the epoxy resin composition is dried using a dispenser (trade name: SHOTMASTER300DS-S, manufactured by Musashi Engineering Co., Ltd.) so that the resin layer has a size of 40 mm ⁇ 40 mm and a thickness of 400 ⁇ m. It was applied on the surface in contact with the resin layer. Thereafter, it was allowed to stand at room temperature (20 ° C. to 30 ° C.) for 5 minutes using an oven (trade name: SPHH-201 manufactured by ESPEC), and further dried at 130 ° C. for 5 minutes to form a resin layer.
  • a dispenser trade name: SHOTMASTER300DS-S, manufactured by Musashi Engineering Co., Ltd.
  • Example 2 to 4 Epoxy resin compositions of Examples 2 to 4 were prepared in the same manner as in Example 1 except that the amount of the solvent (CHN) was changed. Subsequently, the laminated body for evaluation was produced like Example 1 except having used each epoxy resin composition.
  • Example 5 In the same manner as in Example 1, a resin layer was formed on the surface of the first member A in contact with the resin layer using the epoxy resin composition used in Example 1, and a B stage was obtained. Similarly, a resin layer was formed on the surface of the second member A in contact with the resin layer using the epoxy resin composition used in Example 1, and a B-stage state was obtained. Next, in a state where the resin layer of the first member A and the resin layer of the second member A are stacked so as to face each other, vacuum thermocompression bonding (press temperature: 180 ° C., degree of vacuum: 1 kPa, press pressure: 15 MPa, pressurization time: 6 minutes). Thereafter, heating was performed at 150 ° C. for 2 hours and 210 ° C. for 4 hours under atmospheric pressure conditions, followed by cooling to prepare a laminate for evaluation.
  • Example 1 Using the epoxy resin composition used in Example 1 with a dispenser (trade name: SHOTMASTER300DS-S, manufactured by Musashi Engineering Co., Ltd.), the size of the resin layer after drying is 160 mm ⁇ 160 mm and the thickness is 400 ⁇ m. The first member B was coated on the surface in contact with the resin layer. Thereafter, the resin layer was formed by drying at room temperature (20 ° C. to 30 ° C.) for 5 minutes and further at 130 ° C. for 5 minutes.
  • a dispenser trade name: SHOTMASTER300DS-S, manufactured by Musashi Engineering Co., Ltd.
  • Example 2 the epoxy resin composition used in Example 1 was first dried so as to have a size of 160 mm ⁇ 160 mm and a thickness of 200 ⁇ m after drying using a dispenser (trade name: SHOTMASTER300DS-S manufactured by Musashi Engineering Co., Ltd.). It applied on the surface which contacts the resin layer of member B. Thereafter, the resin layer was formed by drying at room temperature (20 ° C. to 30 ° C.) for 5 minutes and further at 130 ° C. for 5 minutes. Similarly, a resin layer was also formed on the surface of the second member B in contact with the resin layer.
  • a dispenser trade name: SHOTMASTER300DS-S manufactured by Musashi Engineering Co., Ltd.
  • the 1st member B and the 2nd member B in which the resin layer was formed were cut
  • the resin layer of the first member B and the resin layer of the second member B are overlapped so as to face each other, and in this state, vacuum thermocompression bonding (press temperature: 180 ° C., vacuum degree: 1 kPa, press pressure: 15 MPa, pressurization time: 6 minutes). Thereafter, heating was performed at 150 ° C. for 2 hours and 210 ° C. for 4 hours under atmospheric pressure conditions, followed by cooling to prepare a laminate for evaluation.

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Abstract

Procédé de production de stratifié comprenant : une étape de formation de couche de résine dans laquelle une couche de résine est formée sur un premier élément séparé en pièces individuelles ; et une étape d'agencement de l'élément dans laquelle un second élément séparé en pièces individuelles est disposé sur la couche de résine.
PCT/JP2017/020342 2016-06-02 2017-05-31 Procédé de production pour stratifié WO2017209209A1 (fr)

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Citations (3)

* Cited by examiner, † Cited by third party
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JP2013234313A (ja) * 2011-11-02 2013-11-21 Hitachi Chemical Co Ltd エポキシ樹脂組成物、その半硬化体および硬化体、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板、およびパワー半導体装置
JP2015002321A (ja) * 2013-06-18 2015-01-05 株式会社デンソー パッケージ構造体
JP2016065146A (ja) * 2014-09-25 2016-04-28 京セラケミカル株式会社 熱硬化性樹脂組成物、半導体装置及び電気・電子部品

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JP2013234313A (ja) * 2011-11-02 2013-11-21 Hitachi Chemical Co Ltd エポキシ樹脂組成物、その半硬化体および硬化体、並びにそれを用いた樹脂シート、プリプレグ、積層板、金属基板、プリント配線板、およびパワー半導体装置
JP2015002321A (ja) * 2013-06-18 2015-01-05 株式会社デンソー パッケージ構造体
JP2016065146A (ja) * 2014-09-25 2016-04-28 京セラケミカル株式会社 熱硬化性樹脂組成物、半導体装置及び電気・電子部品

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