Manufacturing method of molded product

Abstract

The present invention provides a method for producing a molded article that has excellent airtightness and excellent adhesion between a thermoplastic resin composition and a member that is formed of a metal or a ceramic, the method being considerably suppressed in flowing out of a pre-gelled epoxy resin composition due to the temperature and pressure during insert molding. A method for producing a molded article, the method comprising: (1) a step in which an epoxy resin composition is applied to the surface of an insert member that is formed of a metal or a ceramic, thereby forming an epoxy resin composition layer; (2) a step in which the insert member obtained in the step (1) is heated, thereby pre-gelling the epoxy resin composition; and (3) a step in which the insert member obtained in the step (2) is arranged within a mold and a thermoplastic resin composition is insert molded on the epoxy resin composition layer, so that the epoxy resin composition is cured. With respect to this method for producing a molded article, the epoxy resin composition contains 1 to 80 parts by mass of a pre-gelling agent relative to 100 parts by mass of an epoxy resin.

Description

[Technical field]

[0001] The present invention relates to a method for producing a molded article. [Background technology]

[0002] Conventionally, when manufacturing a molded product in which a metal or ceramic member and a thermoplastic resin are integrally molded, various efforts have been made to improve the adhesion between the metal or ceramic member and the thermoplastic resin to prevent gaps from occurring between the two, which would reduce airtightness and liquidtightness, since the metal or ceramic member and the thermoplastic resin are not directly bonded to each other.

[0003] For example, Patent Document 1 describes that a pregelled epoxy resin adhesive layer is formed in advance on the front surface of a metal or ceramic member that comes into contact with the thermoplastic resin, and then the thermoplastic resin is molded integrally with the member while the epoxy resin adhesive is cured, thereby obtaining a molded product that has excellent adhesion between the thermoplastic resin and the member and excellent stress relaxation properties at the interface between the two. However, in the method described in Patent Document 1, the pregelled epoxy resin adhesive flows out due to the temperature and pressure during insert molding, which can impair the adhesion and airtightness between the member and the thermoplastic resin, resulting in insufficient product reliability. Thus, there is still room for improvement in the adhesion and airtightness between the member and the thermoplastic resin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2012-245665 A Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide a method for producing a molded article in which outflow of a pregelled epoxy resin composition due to the temperature and pressure during insert molding is significantly suppressed and which has excellent adhesiveness and airtightness between a metal or ceramic member and a thermoplastic resin composition. [Means for solving the problem]

[0006] Means for Solving the Problems The present inventors have conducted extensive research to solve the above problems and have found that by using an epoxy resin composition containing a specific amount of a pregelling agent as an epoxy resin composition, outflow of the pregelled epoxy resin composition due to temperature and pressure during insert molding can be significantly suppressed, and a molded product having excellent adhesion and airtightness between a metal or ceramic member and a thermoplastic resin composition and high product reliability can be produced, thereby completing the present invention.

[0007] That is, the present invention provides (1) a step of applying an epoxy resin composition to a surface of an insert member made of a metal or ceramic to form an epoxy resin composition layer; (2) a step of heating the insert member obtained in step (1) to pregel the epoxy resin composition; (3) A step of placing the insert member obtained in the step (2) in a mold, insert-molding a thermoplastic resin composition onto the epoxy resin composition layer, and curing the epoxy resin composition. A method for producing a molded article comprising the steps of: The epoxy resin composition comprises 1 to 80 parts by mass of a pregelling agent based on 100 parts by mass of an epoxy resin, and relates to a method for producing a molded product.

[0008] The thermoplastic resin composition includes a crystalline thermoplastic resin, The epoxy resin composition is applied to a copper plate in a thickness of 100 μm, and pre-gelled by heating at 100° C. for 4 minutes. When the crystalline thermoplastic resin is injection-molded under the conditions of a cylinder temperature of the melting point of the crystalline thermoplastic resin + 50° C., a mold temperature of 150° C., and a holding pressure of 70 MPa, the flow width is 0 to 8 mm, or The thermoplastic resin composition includes an amorphous thermoplastic resin, The epoxy resin composition is applied to a copper plate in a thickness of 100 μm, and pre-gelled by heating at 100° C. for 4 minutes. When the amorphous thermoplastic resin is injection-molded under the conditions of a cylinder temperature of 120° C. (glass transition temperature of the amorphous thermoplastic resin) or higher, a mold temperature of 100° C., and a holding pressure of 70 MPa, the flow width is preferably 0 to 8 mm.

[0009] The epoxy resin composition has a tensile shear adhesive strength of 200 N / cm at 125°C measured in accordance with JIS K6850-1999 using a test piece made of the material of the insert member and a test piece made of the thermoplastic resin composition. 2 More preferably, it is equal to or greater than this.

[0010] The particle size of the pregelling agent at 25° C. is preferably 1 to 100 μm.

[0011] The epoxy resin composition preferably contains a silane coupling agent.

[0012] The epoxy resin composition preferably contains a thixotropy-imparting agent.

[0013] The epoxy resin composition preferably contains an amine-based curing agent and a dicyandiamide-based curing agent.

[0014] The thermoplastic resin is preferably at least one selected from the group consisting of polyphenylene sulfide, polybutylene terephthalate, liquid crystal polymer, polyamide, cyclic olefin polymer, polycarbonate, and polyethylene terephthalate.

[0015] The present invention also relates to a molded article produced by the method for producing a molded article of the present invention.

[0016] A bus bar or a metal terminal is preferred. Effect of the Invention

[0017] According to the method for producing a molded article of the present invention, by using an epoxy resin composition containing a specific amount of a pregelling agent as the epoxy resin composition, outflow of the pregelled epoxy resin composition due to the temperature and pressure during insert molding is significantly suppressed, and a molded article having excellent adhesiveness and airtightness between a metal or ceramic member and the thermoplastic resin composition and high product reliability can be produced. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0018] <<Method of manufacturing molded products>> The method for producing the molded product of the present invention comprises the steps of: (1) a step of applying an epoxy resin composition to a surface of an insert member made of a metal or ceramic to form an epoxy resin composition layer; (2) a step of heating the insert member obtained in step (1) to pregel the epoxy resin composition; (3) A step of placing the insert member obtained in the step (2) in a mold, insert-molding a thermoplastic resin composition onto the epoxy resin composition layer, and curing the epoxy resin composition. A method for producing a molded article comprising the steps of: The epoxy resin composition comprises 1 to 80 parts by mass of a pregelling agent based on 100 parts by mass of an epoxy resin, and relates to a method for producing a molded product.

[0019] <Process (1)> In step (1), an epoxy resin composition is applied to the surface of an insert member made of metal or ceramic to form an epoxy resin composition layer.

[0020] (Insert material) The material of the insert member is metal or ceramic. The metal is not particularly limited, but examples thereof include copper, silver, aluminum, etc. The ceramic is not particularly limited, but examples thereof include fine ceramics, etc. The insert member may be made of a single material or may be made of a combination of two or more materials. The shape of the insert member is not particularly limited as long as it can be placed in the mold, and a shape according to the molded product to be manufactured can be adopted.

[0021] (Epoxy resin composition) The epoxy resin contained in the epoxy resin composition is not particularly limited, and examples thereof include bifunctional epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol AD ​​type epoxy resins, naphthalene type epoxy resins, glycidylamine type epoxy resins, alicyclic epoxy resins, polyether modified epoxy resins, silicone modified epoxy resins, and glycidyl ester type epoxy resins, and multifunctional epoxy resins such as phenol novolac type epoxy resins, biphenyl type epoxy resins, naphthalene type epoxy resins, dicyclopentadiene type epoxy resins, xylylene type epoxy resins, cresol novolac type epoxy resins, and tetrakisphenolethane type epoxy resins. These may be used alone or in combination of two or more.

[0022] When epoxy resins are used in combination, from the viewpoint of improving heat resistance, for example, two or more selected from bisphenol A type epoxy resin, bisphenol F type epoxy resin, and glycidylamine type epoxy resin can be used in combination. When bisphenol A type epoxy resin and bisphenol F type epoxy resin are used in combination, the content ratio (mass ratio) of bisphenol A type epoxy resin to bisphenol F type epoxy resin is preferably 5:95 to 95:5, more preferably 20:80 to 80:20. In addition, the content ratio (mass ratio) of bisphenol A type epoxy resin and / or bisphenol F type epoxy resin to glycidylamine type epoxy resin is preferably 1:99 to 90:10, more preferably 10:90 to 80:20.

[0023] The epoxy equivalent of the epoxy resin is not particularly limited, but is preferably 50 to 1000 g / eq, and more preferably 100 to 300 g / eq. If the epoxy equivalent is less than 50 g / eq, the heat resistance and moisture resistance may decrease, and if it exceeds 1000 g / eq, the viscosity may become too high, which may decrease the handleability during application.

[0024] The content of the epoxy resin in the epoxy resin composition is preferably 10 to 90% by mass, and more preferably 10 to 60% by mass. If it is less than 10% by mass, the heat resistance and the like may decrease, and if it exceeds 90% by mass, the contents of other components described below decrease relatively, and the epoxy resin composition may become inferior in fluidity (viscosity), adhesiveness, and the like.

[0025] Since the epoxy resin composition contains 1 to 80 parts by mass of a pregelling agent per 100 parts by mass of epoxy resin, the particles of the pregelling agent expand by heating in step (2), and the fluidity of the epoxy resin composition is reduced (the viscosity is increased), making it possible to maintain the shape of the epoxy resin composition (pregelation), and the flow-out of the epoxy resin composition due to the temperature and pressure during insert molding is suppressed, and after pregelation under specific conditions, the flow width when heated and pressurized can be made within a specific range. The pregelling agent is not particularly limited, but examples thereof include (meth)acrylic resins and acrylonitrile resins. These may be used alone or in combination of two or more. As the pregelling agent, epoxy group-containing polymethyl methacrylate is preferred.

[0026] The particle size of the pregelling agent at 25°C is not particularly limited, but is preferably 1 to 100 μm, more preferably 1 to 50 μm. If the particle size is less than 1 μm, the pregelling effect may not be sufficiently obtained, and if it exceeds 100 μm, it may be difficult to adjust the thickness of the epoxy resin composition layer. Here, the particle size can be measured by a laser particle size distribution meter.

[0027] The number average molecular weight of the pregelling agent is not particularly limited, but from the viewpoint of the pregelling effect, it is preferably 10,000 to 10,000,000, and more preferably 100,000 to 5,000,000. If the number average molecular weight is less than 10,000, the pregelling effect may not be sufficiently obtained, and if it exceeds 10,000,000, the viscosity may increase excessively.

[0028] The content of the pregelling agent is not particularly limited as long as it is 1 to 80 parts by mass relative to 100 parts by mass of the epoxy resin, but is preferably 1 to 60 parts by mass. If the content of the pregelling agent is less than 1 part by mass, the effect of reducing the fluidity of the epoxy resin composition may not be sufficiently obtained, and if it exceeds 80 parts by mass, the adhesiveness may decrease.

[0029] The epoxy resin composition may optionally contain other components such as a curing agent, a curing accelerator, a silane coupling agent, a thixotropy imparting agent, a filler, a thermoplastic resin, a solvent, a reactive diluent, etc. These optional components may be used alone or in combination of two or more kinds.

[0030] The curing agent is not particularly limited, but examples thereof include diaminodiphenylmethane, imidazole, 2-methylimidazole, 2-phenylimidazole-isocyanuric acid adduct, amine-based curing agents, dicyandiamide-based curing agents, phenol-based curing agents such as triphenylphosphine and tetraphenylphosphonium-tetraphenylborate, acid anhydrides such as tetrahydrophthalic anhydride, diazabicycloundecene, N-8-benzyl-1,8-diazabicyclo(5,4,0)-undecene-7·chloride, and 1,8-diazabicyclo(5,4,0)-undecene-7·phenol salt. These may be used alone or in combination of two or more. Among these, amine-based curing agents and dicyandiamide-based curing agents are preferred from the viewpoints of adhesion and curing properties.

[0031] The average particle size of the curing agent is not particularly limited, but is preferably 0.1 to 100 μm, and more preferably 1 to 50 μm. If the average particle size of the curing agent is less than 0.1 μm, the viscosity may increase significantly, and if it exceeds 100 μm, the coating thickness may be limited.

[0032] The content of the curing agent is not particularly limited, but is preferably 1 to 50 parts by mass, more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the epoxy resin. If the content of the curing agent is less than 1 part by mass, the curability may be significantly reduced, and if it exceeds 50 parts by mass, the heat resistance may be reduced. In addition, when an amine-based curing agent and a dicyandiamide-based curing agent are contained, the content ratio (mass ratio) of these is preferably 1:5 to 5:1, more preferably 1:1 to 1:3.

[0033] From the viewpoint of adhesion to metal, the epoxy resin composition preferably contains a silane coupling agent. The silane coupling agent is not particularly limited, but examples thereof include epoxy silane, mercapto silane, etc. These may be used alone or in combination of two or more kinds.

[0034] The content of the silane coupling agent is not particularly limited, but is preferably 0.1 to 10 parts by mass, more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the epoxy resin. If the content of the silane coupling agent is less than 0.1 part by mass, a sufficient effect of improving adhesion may not be obtained, and if it exceeds 10 parts by mass, the reactivity may decrease.

[0035] The epoxy resin composition preferably contains a thixotropy imparting agent from the viewpoint of suppressing outflow of the epoxy resin composition due to the temperature and pressure during insert molding. The thixotropy imparting agent is not particularly limited, but examples thereof include finely powdered silica having a primary particle size of 100 nm or less, bentonite, etc. These may be used alone or in combination of two or more kinds.

[0036] The content of the thixotropy-imparting agent is not particularly limited, but is preferably 0.1 to 10 parts by mass, and more preferably 0.1 to 5 parts by mass, relative to 100 parts by mass of the epoxy resin. If the content of the thixotropy-imparting agent is less than 0.1 part by mass, the effect of suppressing outflow may not be sufficient, and if it exceeds 10 parts by mass, the viscosity may increase excessively.

[0037] The filler is not particularly limited, but examples thereof include silica, alumina, calcium carbonate, talc, mica, wollastonite, aluminum hydroxide, magnesium hydroxide, ferrite, boron nitride, aluminum nitride, silicon carbide, silicon nitride, kaolin, magnesium oxide, zirconium oxide, titanium oxide, etc. These may be used alone or in combination of two or more.

[0038] The particle size of the filler is not particularly limited, but is preferably 0.2 to 150 μm, and more preferably 1 to 50 μm.

[0039] The content of the filler is not particularly limited, but is preferably 10 to 1000 parts by mass, more preferably 20 to 500 parts by mass, and even more preferably 30 to 300 parts by mass, relative to 100 parts by mass of the epoxy resin. If the content of the filler is less than 10 parts by mass, the effect of the filler may not be sufficiently obtained, and if it exceeds 1000 parts by mass, the viscosity may increase excessively.

[0040] The thermoplastic resin optionally contained in the epoxy resin composition is not particularly limited, but examples thereof include acrylic resin, polyamide resin, polyacetal resin, polyvinyl butyral resin, polyethersulfone, polyimide resin, polyetherimide resin, polyester resin, amorphous polyester, polyether resin (e.g., phenoxy resin (polyhydroxypolyether)), polyamideimide resin, polycarbodiimide, polycaprolactone, polyphenylene ether, etc. In addition, examples thereof include thermoplastic elastomers such as styrene-butadiene copolymer, polyamide block copolymer, polyester elastomer, polyurethane elastomer, silicone elastomer, etc. These may be used alone or in combination of two or more.

[0041] The solvent is not particularly limited, but examples thereof include ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, cyclohexanone, cyclopentanone, dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, ethyl acetate, propylene glycol monoethyl ether acetate, isophorone, ethylene glycol monomethyl ether acetate, methyl isobutyl ketone, butyl acetate, dimethylformamide, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, etc. These may be used alone or in combination of two or more.

[0042] The reactive diluent is not particularly limited, but examples thereof include limonene dioxide, para-tertiary butyl phenyl glycidyl ether, etc. These may be used alone or in combination of two or more kinds.

[0043] The content of the reactive diluent is not particularly limited, but is preferably 0.1 to 50 parts by mass, and more preferably 1 to 30 parts by mass, relative to 100 parts by mass of the epoxy resin. If the content of the reactive diluent exceeds 50 parts by mass, the glass transition point may be significantly decreased.

[0044] When the thermoplastic resin composition used in the insert molding in step (3) contains a crystalline thermoplastic resin, the epoxy resin composition is applied to a copper plate with a thickness of 100 μm, heated at 100 ° C for 4 minutes to pregelate, and then injection-molded with the crystalline thermoplastic resin under the conditions of a cylinder temperature of the melting point of the crystalline thermoplastic resin + 50 ° C, a mold temperature of 150 ° C, and a holding pressure of 70 MPa. When the thermoplastic resin composition contains an amorphous thermoplastic resin, the epoxy resin composition is applied to a copper plate with a thickness of 100 μm, heated at 100 ° C for 4 minutes to pregelate, and then injection-molded with the crystalline thermoplastic resin under the conditions of a cylinder temperature of the glass transition temperature of the amorphous thermoplastic resin + 120 ° C, a mold temperature of 100 ° C, and a holding pressure of 70 MPa. The above-mentioned flow width is preferably 1 to 7 mm in any case, and more preferably 2 to 5 mm. If the flow width is within the above range, the epoxy resin composition is sufficiently spread at the interface between the thermoplastic resin composition and the insert member, which is preferable in that it is easy to ensure airtightness. On the other hand, if the flow width exceeds 8 mm, the airtightness may decrease, or the epoxy resin composition may cover the insert member, resulting in a loss of electrical conductivity. Here, the flow width of the epoxy resin composition can be measured by the method described in the examples. Here, it is preferable to use a copper plate made of C1100 copper.

[0045] Here, when the thermoplastic resin composition contains an alloy material containing a crystalline thermoplastic resin and an amorphous thermoplastic resin as the thermoplastic resin, the above-mentioned flow width measurement conditions can be set based on the thermoplastic resin with the larger volume ratio, and when the volume ratios of the crystalline thermoplastic resin and the amorphous thermoplastic resin are equivalent, the conditions can be set based on the thermoplastic resin with the higher melting point of the crystalline thermoplastic resin or the higher glass transition temperature of the amorphous thermoplastic resin.

[0046] The epoxy resin composition has a tensile shear adhesive strength of 100 N / cm at 125°C measured in accordance with JIS K6850-1999 using a test piece made of the material of the insert member and a test piece made of the thermoplastic resin composition. 2 More than 200N / cm is preferable. 2More preferably, the tensile shear adhesive strength is 100N / cm 2 If it is less than this, the adhesion to the insert member or the thermoplastic resin composition will be insufficient, and the product reliability may be poor.

[0047] In step (1), the epoxy resin composition can be applied to the surface of the insert member by a conventional method such as applying it using a dispenser. The thickness of the epoxy resin composition layer is not particularly limited, but is preferably 5 to 1000 μm, more preferably 50 to 300 μm. If the thickness is less than 5 μm, the adhesion may be insufficient, and if it exceeds 1000 μm, the pregelled epoxy resin composition may flow out significantly due to the temperature and pressure during insert molding.

[0048] <Process (2)> In step (2), the insert member obtained in step (1) is heated to pregel the epoxy resin composition. The heating temperature is not particularly limited, but is preferably 60 to 150° C., and more preferably 80 to 120° C. The heating time is not particularly limited, but is preferably 0.5 to 10 minutes, and more preferably 1 to 5 minutes.

[0049] In this specification, pregelation means that the fluidity (viscosity) of the epoxy resin composition is reduced to such an extent that the epoxy resin composition can retain its shape at room temperature (25°C), regardless of whether or not the epoxy resin reacts. Whether or not the epoxy resin composition has pregelated can be confirmed by the presence or absence of tackiness on the surface.

[0050] <Process (3)> In step (3), the insert member obtained in step (2) is placed in a mold, and a thermoplastic resin composition is insert-molded onto the epoxy resin composition layer, and the epoxy resin composition is cured. Here, "on the epoxy resin composition layer" means a state in which at least a part of the epoxy resin composition layer is covered.

[0051] (Thermoplastic resin composition) The thermoplastic resin contained in the thermoplastic resin composition may be a crystalline thermoplastic resin, an amorphous thermoplastic resin, or an alloy material containing a crystalline thermoplastic resin and an amorphous thermoplastic resin. The crystalline thermoplastic resin is not particularly limited, but examples thereof include polyphenylene sulfide, polybutylene terephthalate, liquid crystal polymer, polyamide, polyethylene terephthalate, polyacetal, etc. The amorphous thermoplastic resin is not particularly limited, but examples thereof include polyhydroxy polyether, polyether sulfone, cyclic olefin polymer, polycarbonate, etc. These may be used alone or in combination of two or more. Among these, at least one selected from the group consisting of polyphenylene sulfide, polybutylene terephthalate, liquid crystal polymer, polyamide, cyclic olefin polymer, polycarbonate, and polyethylene terephthalate is preferable, and polyphenylene sulfide is more preferable.

[0052] The thermoplastic resin composition may optionally contain other components such as a filler, a crystal nucleating agent, an impact modifier, an antioxidant, a lubricant, a release agent, a colorant, a compatibilizer, etc. These optional components may be used alone or in combination of two or more kinds.

[0053] The molding conditions in the insert molding can be appropriately set depending on the type of thermoplastic resin, etc. In general, the molding resin temperature is 150 to 400° C., preferably 200 to 400° C., and more preferably 250 to 400° C. The molding cycle time is 1 second to 5 minutes, preferably 1 second to 4 minutes, and more preferably 1 second to 3 minutes.

[0054] In step (3), when insert molding is performed, the thermoplastic resin composition heated to the above-mentioned molding resin temperature is injected into a mold and brought into contact with the epoxy resin composition layer to cure the epoxy resin composition. Therefore, it is preferable to set the above-mentioned molding conditions more specifically, taking into consideration not only the conditions necessary for insert molding of the thermoplastic resin composition, but also the conditions necessary for curing the epoxy resin composition. For example, when polyphenylene sulfide is used as the thermoplastic resin and an epoxy resin composition containing an amine-based curing agent is used, the molding resin temperature is preferably 290 to 350°C, and the molding cycle time is preferably 5 seconds to 3 minutes. When polybutylene terephthalate is used as the thermoplastic resin and an epoxy resin composition containing an amine-based curing agent is used, the molding resin temperature is preferably 220 to 300°C, and the molding cycle time is preferably 5 seconds to 3 minutes. When a liquid crystal polymer is used as the thermoplastic resin and an epoxy resin composition containing an amine-based curing agent is used, the molding resin temperature is preferably 290 to 400°C, and the molding cycle time is preferably 1 second to 3 minutes.

[0055] In order to inject the thermoplastic resin composition into the mold, for example, an injection molding machine can be used. When using an injection molding machine, the molding conditions are preferably a mold temperature of 60 to 180°C, an injection temperature of the thermoplastic resin composition of 180 to 400°C, and a molding cycle time of 1 second to 3 minutes. More specifically, for example, when polyphenylene sulfide is used as the thermoplastic resin and an epoxy resin composition containing an amine-based curing agent is used, the molding temperature is preferably 150°C, a resin injection temperature of 330°C, and a molding cycle time of 40 seconds. When polybutylene terephthalate is used as the thermoplastic resin and an epoxy resin composition containing an amine-based curing agent is used, the molding temperature is preferably 80°C, a resin injection temperature of 260°C, and a molding cycle time of 90 seconds. When a liquid crystal polymer is used as the thermoplastic resin and an epoxy resin composition containing an amine-based curing agent is used, the molding temperature is preferably 80°C, a resin injection temperature of 350°C, and a molding cycle time of 90 seconds.

[0056] The molded product obtained by the molded product manufacturing method of the present invention has excellent adhesiveness and airtightness between a metal or ceramic member and a thermoplastic resin composition, and therefore has high product reliability and can be suitably used for applications requiring high airtightness, such as vehicle-mounted applications. Examples of the molded product include, but are not limited to, bus bars and metal terminals. Among these, bus bars are preferred from the viewpoint of their applicability to vehicle-mounted conductive parts. EXAMPLES

[0057] The present invention will be described below with reference to examples, but the present invention is not limited to the following examples. In the following, "parts" and "%" mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0058] (Materials used) Epoxy resin Bisphenol A / F epoxy resin (content ratio (mass ratio) of bisphenol A epoxy resin to bisphenol F epoxy resin: 50:50, epoxy equivalent: 156-170g / eq) Polysulfide modified epoxy resin (epoxy equivalent: 280g / eq) Aromatic glycidyl ether type epoxy resin (epoxy equivalent: 400g / eq) Glycidylamine type epoxy resin (epoxy equivalent: 100-120g / eq) Pregelling agent Epoxy group-containing polymethyl methacrylate (particle size (25°C): 2 μm) Hardener Amine-based hardener (average particle size: 6 μm) Dicyandiamide hardener (average particle size: 4 μm) ·Silane coupling agent Epoxysilane Compounds Thixotropic agent Fine silica (average particle size: 12 nm) Filler Silica (fused silica, average particle size: 7 μm) Alumina (average particle size: 12 μm) ·Reactive diluents Limonene dioxide Insert material Tough pitch copper (C1100) terminal (Standard Test Piece Co., Ltd., 34.5 x 2.5 x 1.2 mm) ·Thermoplastic resin Polyphenylene sulfide (manufactured by Polyplastics Co., Ltd., DURAFIDE (registered trademark) 6150T73, melting point 280°C)

[0059] (Synthesis Example 1, Comparative Synthesis Examples 1-2) An epoxy resin composition was obtained by mixing the components in the mass ratio (solid content ratio) shown in Table 1. The tensile shear adhesive strength of the obtained epoxy resin composition was evaluated by the following method. The results are shown in Table 1.

[0060] (Tensile shear adhesive strength) A copper plate (C1100) was used as the test piece made of the material of the insert member, and a molded product of polyphenylene sulfide (DURAFIDE (registered trademark) 6150T73, manufactured by Polyplastics Co., Ltd.) was used as the thermoplastic resin test piece, and the tensile shear adhesive strength was measured at 25°C and 125°C in accordance with JIS K6850-1999 and evaluated according to the following criteria. The reason for evaluating the tensile shear adhesive strength under conditions of 25°C (normal temperature) and 125°C (high temperature) was to confirm whether the desired adhesive strength could be maintained during the process of curing the epoxy resin composition. ◎: Tensile shear adhesive strength: 200N / cm 2 End ○: Tensile shear adhesive strength: 100N / cm 2 More than 200N / cm 2 less than ×: Tensile shear adhesive strength: 100N / cm 2 less than

[0061] [Table 1]

[0062] (Examples 1 to 3, Comparative Examples 1 to 3) An epoxy resin composition was obtained by mixing the components in the mass ratio (solid content ratio) shown in Table 2. The flow width of the obtained epoxy resin composition was evaluated by the following method. The results are shown in Table 2.

[0063] The epoxy resin compositions obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were applied to the outer circumference of a tough pitch copper (C1100) terminal (manufactured by Standard Test Piece Co., Ltd., 34.5 x 2.5 x 1.2 mm) at a central 10 mm in the longitudinal direction using a dispenser to form an epoxy resin composition layer having a thickness of about 100 μm. The layer was then heated at 100° C. for 4 minutes. In Examples 1 to 3 and Comparative Examples 1 to 3, it was confirmed by surface tackiness that the epoxy resin composition had been pregelled. The obtained insert member was placed in a mold, and a thermoplastic resin (polyphenylene sulfide) was insert molded at the molding resin temperature shown in Table 2 with a molding cycle time of 40 seconds, while simultaneously curing the epoxy resin composition to obtain a molded product. The obtained molded product was subjected to a He leak test by the following method. The results are shown in Table 2.

[0064] (flow width) An epoxy resin composition was applied to a thickness of 100 μm on the outer circumference of a copper (C1100) plate having a length of 34 mm, a width of 2.3 mm, and a thickness of 1.2 mm, using a dispenser, and pre-gelled by heating at 100° C. for 4 minutes. Thereafter, a cavity having inner dimensions of length 12 mm, width 5.3 mm, and thickness 4.2 mm was provided on the outer circumference of the copper plate having a length of 12 mm on the outer circumference of the copper plate having a length of 12 mm on the inner circumference, so that the thickness of the thermoplastic resin composition in contact with each surface of the copper plate was 1.5 mm. Under the conditions of a cylinder temperature of 330° C., a mold temperature of 150° C., an injection speed of 22 mm, a holding pressure of 70 MPa, and a holding pressure time of 20 seconds, a thermoplastic resin was injected from one end of the applied portion of the epoxy resin composition to the other end, and injection molding was performed. The flow width of the epoxy resin composition that flowed out onto the copper plate protruding from the end of the thermoplastic resin composition at 11 mm was measured and evaluated according to the following criteria. ○: Flow width: 0mm or more and less than 8mm ×: Flow width: less than 0 mm or 8 mm or more

[0065] Here, the epoxy resin composition was applied to a central 10 mm area of ​​the copper plate, and the thermoplastic resin composition was molded to cover the epoxy resin composition to a central 12 mm area of ​​the copper plate. Therefore, when the epoxy resin composition has not flowed at all, the end of the epoxy resin composition is located 1 mm inward from the end of the thermoplastic resin composition. For convenience, however, the state in which the epoxy resin composition has flowed out to the exact position of the end of the thermoplastic resin composition was defined as a flow width of 0 mm, and the state in which the epoxy resin composition has not flowed outward from the end of the thermoplastic resin composition was defined as a flow width of less than 0 mm.

[0066] (He leak test (vacuum method)) A structure with an upper chamber, a lower chamber, and an intermediate portion was prepared as a structure for a leak test. The molded products obtained in Examples 1 to 3 and Comparative Examples 1 to 3 were set in an airtight state in the intermediate portion of the structure. Soapy water was placed in the upper chamber, and pressurized air was introduced into the lower chamber. The pressure of the pressurized air was 500 kPa in total, consisting of 400 kPa He pressurization and 100 kPa vacuum pressure. The amount of He leakage was measured using a leak tester (Cosmo Instruments, G-Fine) and evaluated according to the following criteria. ○:1.0×10 -10 Pa·m 3 / s or less ×:1.0×10 -10 Pa·m 3 / s or more

[0067] [Table 2]

[0068] The molded bodies obtained in Examples 1 to 3 had no helium leakage and were excellent in airtightness.

Claims

1. (1) A step of applying an epoxy resin composition to a surface of an insert member made of a metal or ceramic to form an epoxy resin composition layer; (2) a step of heating the insert member obtained in the step (1) to pre-gel the epoxy resin composition; (3) A step of placing the insert member obtained in the step (2) in a mold, insert-molding a thermoplastic resin composition onto the epoxy resin composition layer, and curing the epoxy resin composition. Including, The epoxy resin composition contains 1 to 80 parts by mass of a pregelling agent having a particle size of 1 to 100 μm at 25° C. per 100 parts by mass of epoxy resin.

2. The thermoplastic resin composition includes a crystalline thermoplastic resin, The epoxy resin composition is applied to a copper plate in a thickness of 100 μm, and pre-gelled by heating at 100° C. for 4 minutes. When the crystalline thermoplastic resin is injection-molded under the conditions of a cylinder temperature of the melting point of the crystalline thermoplastic resin + 50° C., a mold temperature of 150° C., and a holding pressure of 70 MPa, the flow width is 0 to 8 mm, or The thermoplastic resin composition includes an amorphous thermoplastic resin, The method for producing a molded product according to claim 1, wherein the epoxy resin composition is applied to a copper plate in a thickness of 100 μm, and pre-gelled by heating at 100° C. for 4 minutes. The method then performs injection molding of the amorphous thermoplastic resin under conditions of a cylinder temperature of the glass transition temperature of the amorphous thermoplastic resin + 120° C., a mold temperature of 100° C., and a holding pressure of 70 MPa, resulting in a flow width of 0 to 8 mm.

3. The epoxy resin composition has a tensile shear adhesive strength of 200 N / cm at 125°C measured in accordance with JIS K6850-1999 using a test piece made of the material of the insert member and a test piece made of the thermoplastic resin composition. ２ The method for producing a molded article according to claim 1 or 2, wherein the molded article is a molded product.

4. 3. The method for producing a molded article according to claim 1, wherein the pregelling agent is an epoxy group-containing polymethyl methacrylate.

5. The method for producing a molded article according to claim 1 or 2, wherein the epoxy resin composition contains a silane coupling agent.

6. The method for producing a molded article according to claim 1 or 2, wherein the epoxy resin composition contains a thixotropy imparting agent.

7. The method for producing a molded article according to claim 1 or 2, wherein the epoxy resin composition contains an amine-based curing agent and a dicyandiamide-based curing agent.

8. 3. The method for producing a molded article according to claim 1 or 2, wherein the thermoplastic resin is at least one selected from the group consisting of polyphenylene sulfide, polybutylene terephthalate, liquid crystal polymer, polyamide, cyclic olefin polymer, polycarbonate and polyethylene terephthalate.

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