JP2012245665A - Molding method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an integrated molding method of a composite molded product of a thermoplastic resin and a dissimilar material by which excellent adhesion between the thermoplastic resin and a member comprising a metal or a ceramic is obtained and excellent stress relaxation in the boundary between the resin and the member is also obtained.SOLUTION: In the integral molding of the thermoplastic resin and the member comprising the metal or the ceramic, an epoxy resin adhesive layer which is obtained using an amine-based curing agent and is rendered into a B-stage or pregelled, is formed beforehand at a thickness of 5-500 μm on the whole surface of the member in contact with the thermoplastic resin and after that, the thermoplastic resin and the member are integrally molded under a condition of 60-180°C mold temperature, 250-400°C thermoplastic resin injection temperature and 1 sec to 3 min molding cycle time and the adhesive is cured at the molding temperature and within the molding cycle time.

Description

  The present invention relates to a method for molding a composite molded body of a thermoplastic resin and a dissimilar material that has excellent adhesion between a thermoplastic resin and a member made of metal or ceramics and also has excellent stress relaxation at the resin-member interface.

  As an example of use of a composite molded body of a thermoplastic resin and a dissimilar material in which a thermoplastic resin is integrally molded with a member such as a metal, there is a lithium ion battery that is attracting attention as an in-vehicle power source for driving an automobile.

  As a lithium ion battery, a positive electrode and a negative electrode, in which a solid electrode mainly composed of an electrode active material capable of receiving lithium ions is formed on the surface of a current collecting member such as a metal foil, are integrated with a metal electrode terminal. What sealed the battery container with the nonaqueous electrolyte solution by the plastic resin lid body is known.

  However, in a composite molded body of a thermoplastic resin and a member made of a material that is not bonded to a thermoplastic resin, such as metal or ceramics, a gap is formed between the resin and the member, resulting in airtightness, liquid-tightness. There was a problem that the performance decreased. For this reason, in lithium ion batteries, a sealing structure is known in which the sealing property between the inside and outside of the battery can be maintained by bonding a resin insulating sealing member to the battery lid and the electrode terminal. Since this structure additionally installs a sealing member on the lid, there is a problem that the arrangement is difficult depending on the battery structure.

  On the other hand, Patent Document 1 discloses a molded part provided with a seal structure that closes a gap generated between a resin and an insert member. Patent Document 2 discloses that a metal member on which a coating layer made of a triazine thiol or a silane coupling agent is formed and a resin insulating sealing member are firmly bonded and integrally molded.

  However, in the former technique, there is a possibility that the sealing performance is easily deteriorated due to the breakage of the seal structure, and in the latter technique, the surface-treated metal and the resin are firmly bonded to each other. Below, there is a problem that the thermal stress due to the thermal shrinkage difference between the metal and the resin is not sufficiently relaxed, and the resin member may be broken.

  On the other hand, Patent Document 3 discloses insert molding a metal member subjected to surface treatment with a triazine dithiol compound or a silane coupling agent and a low elastic modulus thermoplastic resin. However, the low elastic modulus thermoplastic resin has a problem that it is inferior in mechanical properties.

JP 2008-47437 A JP 2002-237436 A JP 2008-27823 A

  In order to solve such a problem, the present invention provides a thermoplastic resin and a dissimilar material that are excellent in adhesion between a thermoplastic resin and a member made of metal or ceramics and also excellent in stress relaxation at the resin-member interface. An object of the present invention is to provide a method for molding a composite molded article.

The present invention is a molding method in which a thermoplastic resin and a member made of metal or ceramics are integrally molded, and an epoxy resin adhesive layer formed into a B-stage or pregel is formed on the entire surface of the member in contact with the thermoplastic resin. After forming in advance, the thermoplastic resin is molded integrally with the member and the epoxy resin adhesive is cured.
In one aspect of the present invention, a thermoplastic resin and an insert member made of metal or ceramics are insert-molded.
In a further aspect of the present invention, a step of forming an epoxy resin adhesive layer that is B-staged or pregelled on an insert member made of metal or ceramics,
Placing the insert member in which a B-staged or pre-gelled adhesive layer is formed in a mold; and
A step of injecting a thermoplastic resin into the mold and molding the thermoplastic resin integrally with the member and curing the epoxy resin adhesive.
In another aspect of the present invention, a thermoplastic resin and an outsert member made of metal or ceramics are outsert-molded.
In another aspect of the present invention, an adhesive layer is formed by attaching a B-staged epoxy resin film to a member made of metal or ceramics.
In a further aspect of the present invention, the epoxy resin adhesive uses an amine-based curing agent.
In a further aspect of the invention, the B-staged or pregelled adhesive layer thickness is 5 to 500 μm.
In a further embodiment of the present invention, the thermoplastic resin is polyphenylene sulfide, polybutylene terephthalate, liquid crystal polymer, polyamide, polyhydroxy polyether, polyether sulfone or polyethylene terephthalate.
The present invention is also a molding method for molding a thermoplastic resin into a battery lid together with an electrode terminal member,
Forming a B-staged or pregelled epoxy resin adhesive layer on the entire surface of the member in contact with the thermoplastic resin;
A step of placing the member on which the B-staged or pregelled adhesive layer is formed in the mold, and injecting a thermoplastic resin into the mold to be molded integrally with the member and curing the epoxy resin adhesive And a step of forming the battery lid.
In another aspect, the battery lid is a lithium ion secondary battery lid.

  With the above-described configuration, according to the molding method of the present invention, the adhesiveness between the thermoplastic resin and the member made of metal or ceramics is good, and even if a high mechanical strength thermoplastic resin is used, the adhesive layer can be heated. The thermal stress generated at the boundary between the plastic resin and the member can be sufficiently relaxed, and the heat cycle resistance is good. Furthermore, according to the molding method of the present invention, insert molding and outsert molding can be easily performed using an epoxy resin adhesive, and in this case, a conventional molding process can be applied. Moreover, the above-mentioned adhesion performance can be exhibited with the completion of the manufacturing process of the molded product.

  Therefore, according to the molding method of the present invention, the air-tightness and liquid-tightness of an integrally molded product of various thermoplastic resins and members made of metal or ceramics, including a lid of a lithium ion battery, are improved, and A product having excellent heat stress performance can be manufactured using a conventional molding method.

The cross-sectional conceptual diagram of the composite molded product in an Example. Sectional conceptual diagram of the composite molded product in the comparative example. The conceptual diagram of the apparatus of a leak test.

  In the molding method of the present invention, a B-staged or pregelled epoxy resin adhesive layer is formed in advance on the entire surface of a member made of metal or ceramic in contact with the thermoplastic resin, and then the thermoplastic resin is integrated with the member. Mold.

  As a molding method for molding the thermoplastic resin integrally with the above member, a conventionally known integral molding method can be applied. For example, an insert member made of metal or ceramic is surrounded by a molten thermoplastic resin in a mold. Then, it may be solidified to produce a molded product in which the insert member and the thermoplastic resin are integrated, or may be an insert molding method, or a part of the surface of the outsert member made of metal or ceramic is melt thermoplastic. An outsert molding method may be used in which a resin is molded with a mold and solidified to produce a molded product in which an outsert member and a thermoplastic resin are integrated.

  In the present invention, first, when the thermoplastic resin is molded integrally with a member made of metal or ceramic, an epoxy resin adhesive layer that has been B-staged or pregelled on the entire surface of the member in contact with the thermoplastic resin is preliminarily formed. Form. By forming an adhesive layer on the entire surface of the member made of metal or ceramics in contact with the thermoplastic resin, the entire surface of the molded body in contact with the member and the thermoplastic resin has good adhesion, even if partly Even if an adhesion defect occurs at the interface, air tightness and liquid tightness are not impaired. In addition, since the epoxy resin layer is present in the entire interface between the member and the thermoplastic resin in the molded body, the stress can be sufficiently relieved over the entire surface.

  Examples of the epoxy resin adhesive include an epoxy resin and a curing agent, and if necessary, an additive component such as a curing accelerator, a thermoplastic resin, a solvent, or a filler. It is also possible to cure the epoxy resin by self-polymerization in the presence of a curing accelerator without adding a curing agent. The epoxy resin is not particularly limited. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AD type epoxy resin, naphthalene type epoxy resin, glycidylamine type epoxy resin, alicyclic epoxy resin And bifunctional epoxy resins such as polyether-modified epoxy resins, silicone-modified epoxy resins, and glycidyl ester type epoxy resins. Also, polyfunctional epoxy resins such as phenol novolac type epoxy resin, biphenyl type epoxy resin, naphthalene type epoxy resin, dicyclopentadiene type epoxy resin, xylylene type epoxy resin, cresol novolac type epoxy resin, tetrakisphenol ethane type epoxy resin, By using together about 5 to 95% by weight of the total amount of the epoxy resin, the heat resistance can be improved.

  The curing agent is not particularly limited, and examples thereof include acid anhydrides, amine compounds, and phenol compounds. Of these, amine-based curing agents (for example, diaminodiphenylmethane) are preferable, and imidazole-based curing agents (for example, 2-methylimidazole) are more preferable.

  The blending amount of the curing agent is preferably 1 to 100 parts by weight, more preferably 5 to 80 parts by weight, and further preferably 10 to 50 parts by weight per 100 parts by weight of the epoxy resin.

  The curing accelerator is not particularly limited, and examples thereof include imidazole, derivatives thereof (for example, 2-methylimidazole), salts thereof (for example, 2-phenylimidazole / isocyanuric acid adducts, etc.); Bicycloundecene, derivatives thereof (for example, N-8-benzyl-1,8-diazabicyclo (5,4,0) -undecene-7 · chloride, etc.), salts thereof (for example, 1,8-diazabicyclo (5,4 , 0) -undecene-7.phenol salt); organic phosphine compounds and derivatives thereof (for example, triphenylphosphine, etc.) and salts thereof (for example, tetraphenylphosphonium, tetraphenylborate, etc.).

  The amount of the curing accelerator is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, and even more preferably 1 to 8 parts by weight per 100 parts by weight of the epoxy resin.

  The thermoplastic resin blended in the epoxy resin adhesive is not particularly limited, and for example, acrylic resin, polyamide resin, polyacetal resin, polyvinyl butyral resin, polyethersulfone, polyimide resin, polyetherimide resin, Polyester resin, amorphous polyester, polyether resin (for example, phenoxy resin (polyhydroxypolyether) etc.), polyamideimide resin, polycarbodiimide, polycaprolactone, polyphenylene ether and the like can be mentioned. Moreover, thermoplastic elastomers, such as a styrene-butadiene copolymer, a polyamide block copolymer, a polyester elastomer, a polyurethane elastomer, and a silicone elastomer, may be used.

  The thermoplastic resin is used as necessary. When used, the blending amount is preferably 10 to 300 parts by weight, more preferably 20 to 200 parts by weight, and more preferably 30 to 100 parts per 100 parts by weight of the epoxy resin. Further preferred.

  The solvent is not particularly limited. For example, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, cyclohexanone, cyclopentanone, dimethylacetamide, N-methyl-2-pyrrolidone, methyl ethyl ketone, ethyl acetate, propylene glycol monoethyl Examples include ether acetate, isophorone, ethylene glycol monomethyl ether acetate, methyl isobutyl ketone, butyl acetate, dimethylformamide, ethylene glycol monobutyl ether, and ethylene glycol monobutyl ether acetate.

  The amount of the solvent is preferably 10 to 1000 parts by weight, more preferably 30 to 500 parts by weight, and still more preferably 50 to 300 parts by weight per 100 parts by weight of the epoxy resin.

  The filler is not particularly limited. For example, silica, alumina, calcium carbonate, talc, mica, wollastonite, aluminum hydroxide, magnesium hydroxide, ferrite, boron nitride, aluminum nitride, silicon carbide, nitriding Examples include silicon, kaolin, magnesium oxide, zirconium oxide, and titanium oxide.

  The blending amount of the filler is preferably 10 to 1000 parts by weight, more preferably 20 to 500 parts by weight, and even more preferably 30 to 300 parts per 100 parts by weight of the epoxy resin.

  Examples of a method for forming the B-staged or pregelled epoxy resin adhesive layer include a method in which a liquid epoxy resin composition is applied and then B-staged or pregelled by drying. The drying conditions include whether or not a curing accelerator is used, or depending on the solvent used, the type of curing agent, etc., but generally 60 to 150 ° C. and 0.5 to 10 minutes are preferable, 80-120 degreeC and 1-5 minutes are more preferable. The same applies to the case where an amine curing agent is used as the curing agent. The B-stage is based on JIS K 6800, which means that the epoxy resin and the curing agent can react with each other to maintain their own shape. Pregelation is the reaction between the epoxy resin and the curing agent. It is in a state where it can maintain its own shape without having to.

  As a method of forming the B-staged or pregelled epoxy resin adhesive layer, a method of pasting a film in which an epoxy resin adhesive is previously Bstaged or pregelated may be used.

  In the present invention, the thermoplastic resin is then molded integrally with the above-mentioned member in which an epoxy resin adhesive layer that has been B-staged or pre-gelled is formed in advance, and the adhesive is cured. At this time, the adhesive is cured by proceeding a curing reaction from the B-staged or pregelled state within the molding cycle time at the molding temperature.

  The thickness of the B-staged or pregelled epoxy resin adhesive layer is generally preferably 5 to 500 μm, more preferably 10 to 400 μm, and further preferably 20 to 300 μm. Further, this thickness can be set to a more preferable value depending on the size of the molded body and the size of the thermal stress. For example, in a medium-sized molded body such as a lithium ion battery component for automobiles, 10 to 400 μm is more preferable. 20 to 300 μm is more preferable, and in a compact molded body such as a semiconductor device, 5 to 150 μm is more preferable, and 10 to 100 μm is further preferable.

  The thermoplastic resin is not particularly limited, and examples thereof include polyphenylene sulfide, polybutylene terephthalate, liquid crystal polymer, polyamide, polyhydroxy polyether, polyether sulfone, and polyethylene terephthalate. The resin used may be in the form of powder, pellets, etc., and can take an appropriate form depending on the purpose and resin type.

  As an integral molding method of the member and the thermoplastic resin, for example, in the case of insert molding, a step of forming an epoxy resin adhesive layer on an insert member made of metal or ceramic, A step of staging or pregelling, a step of placing the insert member formed with a B-staged or pregelling adhesive layer in the mold, and injecting a thermoplastic resin into the mold to be integrated with the member Examples of the molding method include a step of molding and curing the epoxy resin adhesive. In the case of using a film in which an epoxy resin adhesive is previously B-staged or pre-gelled, the step of B-staging or pre-gelling the adhesive layer can be omitted. In order to inject the resin into the mold, for example, an injection molding apparatus can be used. Other molding methods, for example, outsert molding method, single-side molding method, and the like can be performed by appropriately applying the same method according to each molding method. Such a molding method is a method well known to those skilled in the art.

  As molding conditions, although depending on the type of thermoplastic resin, generally, the molding resin temperature is preferably 150 to 400 ° C., and the molding cycle time is preferably 1 second to 5 minutes. More preferably, the molding resin temperature is 200 to 400 ° C. and the molding cycle time is 1 second to 4 minutes, and further preferably the molding resin temperature is 250 to 400 ° C. and the molding cycle time is 1 second to 3 minutes. The molding conditions can be appropriately set in consideration of the conditions necessary for curing the epoxy resin adhesive and the conditions necessary for thermoplastic resin molding. Specifically, for example, when an epoxy resin adhesive using polyphenylene sulfide and an amine curing agent is used, the molding resin temperature is preferably 290 to 350 ° C., and the molding cycle time is 5 seconds to 3 minutes. When an epoxy resin adhesive using polybutylene terephthalate and an amine curing agent is used, the molding resin temperature is preferably 220 to 300 ° C., and the molding cycle time is 5 seconds to 3 minutes. . Moreover, when using the epoxy resin adhesive which mix | blended the amine type hardening | curing agent using a liquid crystal polymer, Preferably, the molding resin temperature is 320-400 degreeC, and a molding cycle time is 1 second-3 minutes.

  As the mold temperature and the resin injection temperature when using an injection molding apparatus, the mold temperature is 60 to 180 ° C., the thermoplastic resin injection temperature is 250 to 400 ° C., and the molding cycle time is preferably 1 second to 3 minutes. Can be implemented. Specifically, for example, when an epoxy resin adhesive using polyphenylene sulfide and an amine curing agent is used, for example, a mold temperature of 150 ° C., a resin injection temperature of 320 ° C., and a molding cycle time of 90 seconds. Is preferably implemented. In addition, when an epoxy resin adhesive using polybutylene terephthalate and an amine-based curing agent is used, for example, a mold temperature of 80 ° C., a resin injection temperature of 260 ° C., and a molding cycle time of 90 seconds are preferable. Is done. Further, when an epoxy resin adhesive using a liquid crystal polymer and an amine-based curing agent is used, for example, the mold temperature is 80 ° C., the resin injection temperature is 350 ° C., and the molding cycle time is 90 seconds. The

  As an advantageous application example of the present invention, for example, in a battery having a thermoplastic resin lid integrally molded with an electrode terminal, the entire interface between the electrode terminal and the resin lid is epoxy-coated using the method of the present invention. A battery having an electrode terminal thermoplastic resin monolithic cover bonded with a resin adhesive layer, preferably a lithium ion battery, and more preferably an automotive lithium ion battery.

The battery lid molding method is a molding method in which a thermoplastic resin is molded into a battery lid together with an electrode terminal member,
Forming an epoxy resin adhesive layer on the entire surface of the member in contact with the thermoplastic resin;
A step of B-stage or pre-gelling the adhesive layer;
A step of placing the member on which the B-staged or pregelled adhesive layer is formed in the mold, and injecting a thermoplastic resin into the mold to be molded integrally with the member and curing the epoxy resin adhesive The method of forming the battery lid including the step of causing the step to be applied can be applied. In the case of using a film in which an epoxy resin adhesive is previously B-staged or pre-gelled, the step of B-staging or pre-gelling the adhesive layer can be omitted.

  As another advantageous application example of the present invention, for example, outsert molding of a thermoplastic resin together with an outsert member made of metal or ceramics can be mentioned. For example, when outsert molding of a reflector such as an LED on a lead frame, conventionally, the metal surface of the lead frame is roughened, a thermoplastic resin is molded, and then the excessively roughened surface is re-plated. In this method, the metal surface of the lead frame was roughened, but when a thermoplastic resin was outsert molded on the roughened surface, the adhesion between the resin and the metal surface was insufficient. However, using the method of the present invention, after forming a B-staged or pre-gelled adhesive layer on the metal surface of the lead frame in advance, by performing outsert molding of the thermoplastic resin, no roughening treatment is required, An LED that does not require an extra step such as re-plating of an extra rough surface and that has a reflector having excellent adhesion and stress relaxation can be used.

  As another advantageous application example of the present invention, when a thermoplastic resin layer is provided on a metal surface, the adhesion strength between the metal and the thermoplastic resin has been conventionally increased by primer treatment. After forming a B-staged or pregelled adhesive layer on the metal surface in advance using the method of the present invention instead of the treatment, a thermoplastic resin was applied, and the metal that could not be handled by the primer-treated thin film- A metal-thermoplastic resin bonding structure in which a gap generated between the resins is filled to improve adhesion can be exemplified.

  EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to these examples.

Examples 1-4
As the epoxy resin adhesive, a bisphenol A type epoxy resin was used, an amine compound was used as a curing agent, a polyetherimide resin was blended as a thermoplastic resin component, and an alumina was used as a filler. This adhesive was indicated in the table.
Further, polyphenylene sulfide (PPS) (manufactured by Polyplastics Co., Ltd.) was used as a thermoplastic resin for molding.

Preparation of insert member As shown in Table 1, an epoxy resin adhesive is applied to the middle part of a copper or aluminum round bar terminal (diameter: 10 mm, length: 24 mm) for a width of approximately 6 mm that contacts the thermoplastic resin for molding. And dried at 120 ° C. for 2 minutes to form a bregel. The thickness of the pregelatinized adhesive layer is as shown in Table 1.
An epoxy resin adhesive is applied to a doughnut-shaped region having a width of about 6 mm that is in contact with the molding thermoplastic resin around the center hole of an aluminum seat plate (diameter 42 mm, thickness 3 mm, center 16 mm diameter hole). And pregelled by drying at 120 ° C. for 2 minutes. The thickness of the pregelatinized adhesive layer is as shown in Table 1.

Insert molding composite molding 1
As shown in Table 1, a stepped disk-shaped composite molded article having a round bar terminal insert member penetrating in the center was integrally molded using an injection molding apparatus. Molding conditions were a mold temperature of 150 ° C., a resin injection cylinder temperature of 320 ° C., and a molding cycle time of 90 seconds. A schematic diagram of a cross-sectional view of a molded product without a seat plate is shown in FIG.
Composite molded product 2
As shown in Table 1, a stepped disk-like composite molded article in which a seat plate insert member was arranged and a round bar terminal insert member was passed through the center hole thereof was integrally molded using an injection molding apparatus. Molding conditions were a mold temperature of 150 ° C., a resin injection cylinder temperature of 320 ° C., and a molding cycle time of 90 seconds. A schematic diagram of a cross-sectional view of a molded product with a seat plate is shown in 1-2 of FIG.

Comparative Examples 1-4
Preparation of insert member As shown in Table 1, a copper or aluminum round bar terminal (diameter 10 mm, length 24 mm) with no epoxy resin adhesive applied (Comparative Examples 1 and 2), epoxy resin adhesive applied Then, a cured adhesive layer was formed (Comparative Example 3), and as shown in Table 1, an epoxy resin adhesive was applied in the same manner as in the Examples to form a bregel (Comparative Example 4). It was.
An insert member made of a copper or aluminum seat plate (diameter 42 mm, thickness 3 mm, center 16 mm diameter hole) to which no epoxy resin adhesive was applied was used.

Insert molded composite molded product 1 '
A stepped disk-shaped composite molded product having a round bar terminal sart member penetrated in the center was integrally molded with a composite molded product 1 'using an injection molding apparatus. Molding conditions were a mold temperature of 150 ° C., a resin injection cylinder temperature of 320 ° C., and a molding cycle time of 90 seconds. A schematic diagram of a cross-sectional view of a molded article without a seat plate and without an adhesive layer is shown in FIG.
Composite molded product 2 '
A stepped disc-shaped composite molded article in which a seat plate insert member is arranged and a round bar terminal insert member is passed through the center hole thereof is integrally molded using an injection molding apparatus. Molding conditions were a mold temperature of 150 ° C., a resin injection cylinder temperature of 320 ° C., and a molding cycle time of 90 seconds. A schematic diagram of a cross-sectional view of a molded product provided with a pre-cured adhesive layer with a seat plate is shown in FIG.

Evaluation Method (1) Leak Test Using the composite molded articles prepared in Examples 1 to 4 and Comparative Examples 1 to 4, the structure shown in FIG. 3 is prepared, and pressure is applied to insert member-molding thermoplastic resin. Air leakage from the interface was observed. Soap water was placed in the upper chamber of the structure, and pressurized air was introduced into the lower chamber. The composite molded product was set in an airtight state in the middle part. The inside of the container was pressurized to 0.1 MPa and held for 1 minute, and air leakage was observed. If it did not leak, the pressure was increased to 0.2 MPa and held for 1 minute. The pressure was increased every 0.1 MPa, this was repeated, and the pressure was increased to a maximum of 0.6 MPa for evaluation. The maximum pressure at which no air leak occurred was taken as the leak judgment result. The results are shown in Table 1.
(2) Heat cycle test About Example 3, the heat cycle test was implemented. One cycle is −40 ° C., 30 minutes later, and then heated to 125 ° C. for 30 minutes. This was repeated for 300 cycles. Thereafter, a leak test was performed. The results are shown in Table 1.

  From these results, in the composite molded products molded by the molding methods of Examples 1 to 4, since air leakage did not occur, it was demonstrated that the airtightness of the interface between the insert member and the molded thermoplastic resin is high. It was done.

1. Round bar terminal2. 2. Adhesive layer 3. Thermoplastic resin 4. Thermoplastic resin Round bar terminal6. Adhesive layer 6 '. 6. Adhesive layer Seat plate 8. Round bar terminal9. Thermoplastic resin10. Round bar terminal 11. Thermoplastic resin12. Seat plate 13. Precured adhesive layer a. Soapy water b. Air

Claims (16)

  A molding method in which a thermoplastic resin and a member made of metal or ceramics are integrally molded, and after an epoxy resin adhesive layer that has been B-staged or pregelled is formed in advance on the entire surface of the member in contact with the thermoplastic resin A molding method in which the thermoplastic resin is molded integrally with the member and the epoxy resin adhesive is cured.   The molding method according to claim 1, wherein the thermoplastic resin and an insert member made of metal or ceramic are insert-molded. Forming a B-staged or pregelled epoxy resin adhesive layer on an insert member made of metal or ceramic;
Placing the insert member in which a B-staged or pre-gelled adhesive layer is formed in a mold; and
The molding method according to claim 2, further comprising a step of injecting a thermoplastic resin into the mold and molding the thermoplastic resin integrally with the member and curing the epoxy resin adhesive.   The molding method according to claim 3, wherein the mold temperature is 60 to 180 ° C, the thermoplastic resin injection temperature is 250 to 400 ° C, and the molding cycle time is 1 second to 3 minutes.   The molding method according to claim 1, wherein a thermoplastic resin and an outsert member made of metal or ceramics are outsert-molded.   The molding method according to claim 1, wherein the adhesive layer is formed by pasting a B-staged epoxy resin film on a member made of metal or ceramics.   The molding method according to claim 1, wherein the epoxy resin adhesive uses an amine curing agent.   The forming method according to any one of claims 1 to 7, wherein the B-staged or pregelled adhesive layer has a thickness of 5 to 500 µm.   The molding method according to claim 1, wherein the thermoplastic resin is polyphenylene sulfide, polybutylene terephthalate, liquid crystal polymer, polyamide, polyhydroxy polyether, polyether sulfone, or polyethylene terephthalate. A molding method for molding a thermoplastic resin together with an electrode terminal member into a battery lid,
Forming a B-staged or pregelled epoxy resin adhesive layer on the entire surface of the member in contact with the thermoplastic resin;
A step of placing the member formed with the B-staged or pre-gelled adhesive layer in the mold, and injecting a thermoplastic resin into the mold to form it integrally with the member and curing the epoxy resin adhesive Forming the battery lid.   The molding method according to claim 10, wherein the battery lid is a lithium ion secondary battery lid.   The molding method according to claim 10 or 11, wherein the adhesive layer is formed by attaching a B-staged epoxy resin film to a member made of metal or ceramics.   The molding method according to claim 10, wherein the epoxy resin adhesive uses an amine-based curing agent.   The forming method according to any one of claims 10 to 13, wherein the B-staged or pregelled adhesive layer has a thickness of 5 to 500 µm.   The molding method according to any one of claims 10 to 14, wherein the thermoplastic resin is polyphenylene sulfide, polybutylene terephthalate, liquid crystal polymer, polyamide, polyhydroxy polyether, polyether sulfone, or polyethylene terephthalate.   The molding method according to claim 10-15, wherein the mold temperature is 60 to 180 ° C, the thermoplastic resin injection temperature is 250 to 400 ° C, and the molding cycle time is 1 second to 3 minutes.

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