JP2006273955A - Method for adhesion of metal and adherend and preparation of electroformed mold - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for tightly bonding an epoxy adhesive to a metal by making a curing agent used for epoxy adhesive, especially an amine based curing agent, hard to react with a coated film of a triazinethiol compound to keep molecular bonding of each triazinethiol compound. <P>SOLUTION: The invention relates to the method for adhesion of metal and an adherend comprising covering a surface of a metal with the triazinethiol compound, coating an epoxy compound having at least two epoxy groups in the molecule on the metal surface coated with the triazinethiol compound, heating the epoxy compound and then coating an epoxy adhesive mixed with the curing agent on the surface of the metal wherein the adherend is adhered to the surface of the metal through the epoxy adhesive. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method of adhering a metal and an adherend to a metal such as nickel, a nickel alloy and stainless steel and another adherend via an epoxy adhesive, and an electroforming mold using the adhesion method. The present invention relates to a method for manufacturing an electroforming mold.

In general, epoxy adhesives are suitable for bonding various materials such as metals, ceramics, plastics, etc., and since there is little gas generation or shrinkage during curing and high adhesive strength, automobiles, aircraft, electricity / electronics, civil engineering / architecture It is used in a wide range of fields.
As an example of this use, for example, in a method for producing an electroforming mold, a surface such as a surface of a mother mold shape transfer surface is obtained by electroplating a metal such as nickel on the surface of the mother mold, and on the opposite side of the metal mold. On the back side, apply an epoxy adhesive mixed with a curing agent, and then back up and adhere a back-up material such as a thermosetting resin, concrete, or low melting point alloy to the surface of this metal. The mother mold is removed to produce an electroformed mold.
The electroformed mold produced in this way is excellent in transferability and can be easily produced, and is therefore used as a precision mold for plastic molding and the like.

  By the way, when an adherend is bonded to a metal such as nickel or stainless steel using an epoxy adhesive, a high adhesive strength is not always obtained. In this case, the epoxy adhesive has a relatively low strength. The phenomenon of peeling from the metal surface occurs. Therefore, even in the above-mentioned electroforming mold, even if nickel plating and backup material are joined with an epoxy adhesive, nickel and epoxy adhesive have low adhesive strength. There is a problem that it may peel off.

  In order to solve this, for example, in the film of triazine thiol compound, a well-known technique of improving the adhesive strength with a polymer material such as plastic, rubber, adhesive, etc. is adopted, and the triazine thiol compound is preliminarily applied to the metal surface. It is conceivable that an epoxy adhesive mixed with a curing agent is applied to the surface of the metal, and then the adherend is adhered to the surface of the metal via the adhesive.

Conventionally, as a technique for forming a film of triazine thiol that improves the adhesive strength between a metal and a polymer material such as plastic, rubber, and adhesive, for example, a technique described in Japanese Patent Publication No. 8-856 is known. ing. This improves the adhesion strength between rubber, plastic and paint by immersing the metal with a triazine thiol compound solution.
A technique described in JP-A-2-298284 is also known. This improves the adhesion strength with rubber and plastic by electrochemically surface-treating a metal in an aqueous solution of a triazine thiol compound and forming a triazine thiol compound film on the metal surface.

Alternatively, a technique described in JP-A-11-58604 is known. In this technique, the adhesion strength of a metal to a thermoplastic resin is improved by dipping or electrochemically treating a metal with a solution of a triazine thiol compound.
Moreover, the technique described in Unexamined-Japanese-Patent No. 2004-87890 and Unexamined-Japanese-Patent No. 2004-266189 is also known. In these technologies, a film of triazine thiol derivative is formed on the insulating lead or lead frame of the package for electronic components, thereby improving the adhesive strength, adhesion and airtightness by the primary bond between the coating and the epoxy resin which is an insulating resin. I am letting.
As described above, it is known that the treatment of a metal with a triazine thiol compound or the formation of a film of a triazine thiol compound on a metal has an effect on the adhesion between the metal and the vulcanized rubber, or the metal and the thermoplastic or thermosetting plastic. It has been.

Japanese Patent Publication No. 8-856 JP-A-2-298284 JP-A-11-58604 Japanese Patent Laid-Open No. 2004-87890 JP 2004-266189 A

By the way, when an epoxy resin containing a curing agent or an epoxy adhesive mixed with a curing agent is directly applied to a metal treated with a triazine thiol compound, there is a problem in that an improvement in adhesive strength is not always observed. The reason why such high adhesive strength cannot be obtained is thought to be because the curing agent destroys the triazine thiol film. That is, curing agents used for epoxy adhesives, especially amine-based curing agents, are highly reactive to triazine thiol coatings, and react with the coatings to break molecular bonds between triazine thiols before reacting with epoxy groups. it seems to do.
Therefore, in particular, in an electroformed mold made by adhering electroformed nickel and a backup material, simply by treating with a triazine thiol compound, the strength becomes insufficient, and there is a possibility that the plastic mold cannot withstand the thermal shock of plastic molding. .

  The present invention has been made in view of the above problems, and the curing agent used in the epoxy adhesive, in particular, the amine curing agent is less likely to react with the coating of the triazine thiol compound. It is an object of the present invention to provide a method for bonding a metal and an adherend and a method for manufacturing an electroforming mold, which can protect a molecular bond and firmly bond an epoxy adhesive to the metal.

In order to achieve such an object, the adhesion method between the metal of the present invention and the adherend is made by coating a metal surface with a triazine thiol compound and then applying an epoxy adhesive mixed with a curing agent on the surface of the metal. In the method of adhering the metal and the adherend to the adherend via the epoxy adhesive on the surface of the metal,
Before applying the epoxy adhesive, an epoxy compound containing at least two epoxy groups in one molecule is applied to the surface of the metal coated with the triazine thiol compound, and then the epoxy compound is heated. It is configured to do. The epoxy adhesive is cured by room temperature or heating (secondary heating).

  The triazine thiol compound used in the present invention may be any compound having two or more thiol groups in one molecule, such as 1,3,5-triazine-2,4,6-trithiol or a sodium salt thereof. There are metal salts.

The epoxy compound containing an epoxy group used in the present invention is not particularly limited as long as it has two or more epoxy groups in one molecule. For example, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, heterocyclic epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, bromine epoxy resin, hydrogenated bisphenol A type epoxy resin, propylene glycol There are resins such as aliphatic epoxy resins such as glycidyl ether and pentaerythritol polyglycidyl ether, and urethane-modified epoxy resins.
Also, ethylene glycol diglycidyl ether, polyethylene diglycidyl ether, propylene glycol diglycidyl ether, polypropylene diglycidyl ether, butanediol diglycidyl ether, pentyl glycol diglycidyl ether, hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane Examples include compounds generally called reactive diluents such as triglycidyl ether. These resins and compounds may be used alone or in combination of two or more. Further, if necessary, a monoepoxy compound such as butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, glycidyl ether of an aliphatic alcohol or the like may be mixed for viscosity reduction. The epoxy compound may be diluted with a solvent that does not react with an epoxy group such as acetone or hexane.

  An epoxy adhesive mixed with a curing agent has an epoxy resin as a main component. As an epoxy resin, what mixed the 1 type, or 2 or more types of the epoxy resin used for the said primary heat processing is used, for example.

As a hardening | curing agent used for this invention, the general hardening | curing agent used for an epoxy resin is used. Such materials include amine-based curing agents and acid anhydride-based curing agents.
Examples of the amine curing agent include aliphatic amines such as diethylenetriamine, triethylenetetramine, and diethylaminopropylamine; mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, and N-aminoethyl. Alicyclic polyamines such as piperazine; Aliphatic polyamines containing aromatic rings such as metaxylenediamine; Polyethyleneimines having primary, secondary and tertiary amine nitrogens in one molecule; Metaphenylenediamine, Methylenedianiline Aromatic polyamines such as diaminodiphenylsulfone; polyamine compounds such as the above-mentioned aliphatic polyamines, aliphatic polyamines containing aromatic rings, and aromatic polyamines, known modification methods such as addition reaction with epoxy compounds, acrylonitrile, acrylic Modified polyamines produced by Michael addition reaction with esters, etc., Mannich reaction with methylol compounds, etc .; Imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2methylimidazole; Tertiary amines such as dimethylaminomethylphenol; tri-2-ethylhexylate of trisdimethylaminomethylphenol and the like. Moreover, the polyamide polyamine produced | generated mainly by the condensation reaction of a dimer acid and a polyamine is mentioned. Furthermore, general-purpose latent curing agents such as dicyandiamide, adipic acid dihydrazide, and isophthalic acid dihydrazide, and those that can be cured at 70 to 80 ° C., for example, JP-A-60-4524 and JP-A-62-26523. A latent curing agent disclosed in JP-A-1-254473 can also be used.

  Examples of the acid anhydride curing agent include dodecenyl succinic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like. These are used alone or as a mixture of two or more. If necessary, maleic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, polyazelineic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, etc. are used in combination. You can also. When an acid anhydride is used as a curing agent, a known curing accelerator such as an imidazole compound or benzyldimethylamine is usually used.

  When the epoxy compound coated on the surface of the metal coated with the triazine thiol compound is subjected to heat treatment (primary heating), as shown in FIG. 1, this epoxy compound reacts with the coating of the triazine thiol compound, and the triazine thiol The molecular bond between the compounds is protected. That is, by this primary heat treatment, the thiol group on the coating surface of the triazine thiol compound reacts with the epoxy group, and an epoxy compound layer is formed on the coating of the triazine thiol compound.

  In this state, an epoxy adhesive mixed with a curing agent is applied, and the adherend is bonded via the epoxy adhesive. In this case, since the molecular bonds between the triazine thiol compounds are protected by the preheated epoxy compound, the curing agent used for the epoxy adhesive, particularly the amine curing agent, reacts with the coating of the triazine thiol compound. In other words, the epoxy compound layer chemically bonded to the triazine thiol compound film prevents the curing agent contained in the epoxy adhesive from breaking the triazine thiol film by breaking the molecular bond between the triazine thiols. In this way, the epoxy adhesive is firmly bonded to the metal, and the adherend is securely bonded to the metal.

In this case, it is effective to perform the above heat treatment at 50 to 200 ° C. for 1 to 300 minutes, and preferably at 80 to 160 ° C. for 10 to 180 minutes.
By this primary heat treatment, the thiol group on the surface of the triazine thiol film reacts with the epoxy group, and an epoxy compound layer is reliably formed on the triazine thiol film. Note that the epoxy compound layer subjected to the primary heat treatment does not necessarily need to be cured.

  If necessary, the metal surface is electrochemically coated with the triazine thiol compound. In this case, it is effective to perform metal electrochemical treatment with a solution of a triazine thiol compound having at least two thiol groups. The electrochemical surface treatment method of the metal used in the present invention can be carried out according to the method described in JP-A-2-298284 or JP-A-2001-316872. That is, it is carried out by a three-electrode system in which two electrodes or a reference electrode is added, using a metal as an anode (working electrode) and platinum or stainless steel as a cathode (counter electrode) in an aqueous solution or organic solvent solution of a triazine thiol compound. Alternatively, a triazine thiol compound solution may be impregnated into cotton, felt, sponge, etc., and this may be sandwiched between a metal for electrochemical surface treatment and a counter electrode plate such as platinum, and voltage may be applied in the same manner as described above.

In addition, the manufacturing method of the electroforming mold of the present invention for achieving the above-mentioned object is to attach a metal to the surface of the mother die and mix a curing agent on the surface opposite to the metal mother die. An electroforming mold for producing an electroforming mold by applying an epoxy adhesive, adhering a backup material as an adherend to the surface of the metal via the epoxy adhesive, and then removing the mother mold In the manufacturing method of
Before applying the epoxy adhesive, the surface of the metal on which the surface of the matrix is opposite to the metal matrix attached by plating is coated with a triazine thiol compound and the surface of the metal coated with the triazine thiol compound. In addition, an epoxy compound containing at least two epoxy groups in one molecule is applied, and then the epoxy compound is heated.

As the epoxy adhesive mixed with the triazine thiol compound, the epoxy compound containing an epoxy group, and the curing agent used in the present invention, the same one as described above is used.
When the epoxy compound coated on the surface of the metal coated with the triazine thiol compound is subjected to heat treatment (primary heating), as shown in FIG. 1, this epoxy compound reacts with the coating of the triazine thiol compound, and the triazine thiol The molecular bond between the compounds is protected. That is, by this primary heat treatment, the thiol group on the coating surface of the triazine thiol compound reacts with the epoxy group, and an epoxy compound layer is formed on the coating of the triazine thiol compound.

In this state, an epoxy adhesive mixed with a curing agent is applied, and the adherend is bonded via the epoxy adhesive. In this case, since the molecular bonds between the triazine thiol compounds are protected by the preheated epoxy compound, the curing agent used for the epoxy adhesive, particularly the amine curing agent, reacts with the coating of the triazine thiol compound. In other words, the epoxy compound layer chemically bonded to the triazine thiol compound film prevents the curing agent contained in the epoxy adhesive from breaking the triazine thiol film by breaking the molecular bond between the triazine thiols. In this way, the epoxy adhesive is firmly bonded to the metal, and the adherend is securely bonded to the metal.
Therefore, even if a thermal shock during molding is applied to the electroformed mold, the adhesion strength of the metal to the epoxy adhesive is increased, so that the situation where the metal and the backup material are peeled off due to thermal shock is prevented. The durability is improved.

In this case, it is effective to perform the above heat treatment at 50 to 200 ° C. for 1 to 300 minutes, and preferably at 80 to 160 ° C. for 10 to 180 minutes.
By this primary heat treatment, the thiol group on the surface of the triazine thiol film reacts with the epoxy group, and an epoxy compound layer is reliably formed on the triazine thiol film. Note that the epoxy compound layer subjected to the primary heat treatment does not necessarily need to be cured.

  If necessary, the metal surface is electrochemically coated with the triazine thiol compound. In this case, it is effective to perform metal electrochemical treatment with a solution of a triazine thiol compound having at least two mercapto groups. The electrochemical surface treatment method of the metal used in the present invention can be carried out according to the method described in JP-A-2-298284 or JP-A-2001-316872. That is, it is carried out by a three-electrode system in which two electrodes or a reference electrode is added, using a metal as an anode (working electrode) and platinum or stainless steel as a cathode (counter electrode) in an aqueous solution or organic solvent solution of a triazine thiol compound. Alternatively, cotton, felt, sponge, or the like may be impregnated with a triazine thiol compound solution, and this may be sandwiched between a metal to be subjected to electrochemical surface treatment and a counter electrode plate such as platinum, and the voltage applied as described above.

  According to the method for adhering a metal and an adherend of the present invention, an epoxy compound containing at least two epoxy groups in one molecule is applied to the surface of a metal coated with a triazine thiol compound, and this is heated. Therefore, since this epoxy compound can react with the coating of the triazine thiol compound in advance to protect the molecular bond between the triazine thiol compounds, even if an epoxy adhesive mixed with a curing agent is applied in this state, epoxy adhesion The curing agent used for the agent, in particular the amine curing agent, becomes difficult to react with the coating film of the triazine thiol compound, and the situation where the triazine thiol film is destroyed can be prevented. Therefore, the epoxy adhesive is firmly bonded to the metal, and the adherend can be securely bonded to the metal.

  Further, according to the method for producing an electroforming mold of the present invention, as described above, the epoxy adhesive is firmly adhered to the metal, and the adherend can be securely adhered to the metal. Even if a thermal shock is applied to the mold during molding, the metal and the backup material can be prevented from peeling off, and the durability can be greatly improved.

Hereinafter, a method for bonding a metal and an adherend and a method for producing an electroforming mold according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.
First, a method for bonding a metal and an adherend according to an embodiment of the present invention will be described. As shown in FIG. 2, this bonding method follows the following steps.

(1) Coating of triazine thiol compound The surface of a metal is coated with a triazine thiol compound. The triazine thiol compound only needs to have two or more thiol groups in one molecule, and examples thereof include metal salts such as 1,3,5-triazine-2,4,6-trithiol or a sodium salt thereof. .
In an embodiment, the metal surface is electrochemically coated with a triazine thiol compound. Specifically, it is carried out by a three-electrode system in which two electrodes or a reference electrode is added in an aqueous solution or organic solvent solution of a triazine thiol compound with a metal as an anode (working electrode) and platinum or stainless steel as a cathode (counter electrode). Alternatively, a triazine thiol compound solution may be impregnated into cotton, felt, sponge, etc., and this may be sandwiched between a metal for electrochemical surface treatment and a counter electrode plate such as platinum, and voltage may be applied in the same manner as described above. The triazine thiol compound concentration is 0.001 to 10 wt / vol%, preferably 0.01 to 1 wt / vol%. Sodium carbonate or sodium hydroxide may be added to the triazine thiol compound solution as a supporting electrolyte. The printing voltage is 0.1 to 10 V, preferably 1 to 5 V, and the printing time is 10 seconds to 120 minutes, preferably 1 minute to 30 minutes. Thus, a triazine thiol film having a thickness of several tens to several hundreds of nanometers is formed on the surface of the metal subjected to the electrochemical surface treatment. A chemical bond of metal mercaptide is formed at the interface between the triazine thiol film and the metal, and a thiol group reactive with an epoxy group is present on the surface of the triazine thiol film.

(2) Application of epoxy compound An epoxy compound containing at least two epoxy groups in one molecule is applied to the surface of a metal coated with a triazine thiol compound.
Examples of the epoxy compound containing two or more epoxy groups in one molecule include bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin, complex Cyclic epoxy resins, glycidyl ester epoxy resins, glycidyl amine epoxy resins, bromine-containing epoxy resins, hydrogenated bisphenol A type epoxy resins, aliphatic epoxy resins such as propylene glycol glycidyl ether and pentaerythritol polyglycidyl ether, urethane modified There are resins such as epoxy resins. Also, ethylene glycol diglycidyl ether, polyethylene diglycidyl ether, propylene glycol diglycidyl ether, polypropylene diglycidyl ether, butanediol diglycidyl ether, pentyl glycol diglycidyl ether, hexanediol diglycidyl ether, glycerin triglycidyl ether, trimethylolpropane Examples include compounds generally called reactive diluents such as triglycidyl ether. These resins and compounds may be used alone or in combination of two or more. Further, if necessary, a monoepoxy compound such as butyl glycidyl ether, phenyl glycidyl ether, cresyl glycidyl ether, glycidyl ether of an aliphatic alcohol or the like may be mixed for viscosity reduction. The epoxy compound may be diluted with a solvent that does not react with an epoxy group such as acetone or hexane.

(3) Heat treatment The epoxy compound is heat treated. The heat treatment is performed at 50 to 200 ° C. for 1 to 300 minutes, preferably at 80 to 160 ° C. for 10 to 180 minutes.
The heating is performed by an appropriate method, for example, using a hot air dryer or an electric furnace.

  By this heat treatment, the epoxy compound reacts with the film of the triazine thiol compound to protect the molecular bond between the triazine thiol compounds. That is, by this primary heat treatment, the thiol group on the coating surface of the triazine thiol compound reacts with the epoxy group, and an epoxy compound layer is formed on the coating of the triazine thiol compound.

(4) Application of epoxy adhesive and adhesion of adherend material An epoxy adhesive mixed with a curing agent is applied to the surface of the metal, and the adherend is adhered to the surface of the metal via the epoxy adhesive.

  An epoxy adhesive mixed with a curing agent has an epoxy resin as a main component. As an epoxy resin, what mixed the 1 type, or 2 or more types of the epoxy resin used for the said primary heat processing is used, for example.

  As the curing agent, a general curing agent used for epoxy resins is used. Such materials include amine-based curing agents, acid anhydride-based curing agents, and the like. Examples of the amine curing agent include aliphatic amines such as diethylenetriamine, triethylenetetramine, and diethylaminopropylamine; mensendiamine, isophoronediamine, bis (4-amino-3-methylcyclohexyl) methane, and N-aminoethyl. Alicyclic polyamines such as piperazine; Aliphatic polyamines containing aromatic rings such as metaxylenediamine; Polyethyleneimines having primary, secondary and tertiary amine nitrogens in one molecule; Metaphenylenediamine, Methylenedianiline Aromatic polyamines such as diaminodiphenylsulfone; polyamine compounds such as the above-mentioned aliphatic polyamines, aliphatic polyamines containing aromatic rings, and aromatic polyamines, known modification methods such as addition reaction with epoxy compounds, acrylonitrile, acrylic Modified polyamines produced by Michael addition reaction with esters, etc., Mannich reaction with methylol compounds, etc .; Imidazole compounds such as 2-methylimidazole, 2-ethyl-4-methylimidazole, 1-cyanoethyl-2methylimidazole; Tertiary amines such as dimethylaminomethylphenol; tri-2-ethylhexylate of trisdimethylaminomethylphenol and the like. In addition, commercially-available versamide (manufactured by Henken Hakusui), tomide (manufactured by Fuji Kagaku Kogyo), sunmide (manufactured by Sanwa Chemical Co., Ltd.), racamide (manufactured by Dainippon Ink & Chemicals), etc. Polyamide polyamine known under the trade name of Further, general-purpose latent curing agents such as dicyandiamide, adipic acid dihydrazide, and isophthalic acid dihydrazide, and latent curing agents that can be cured at 70 to 80 ° C. can also be used.

  Examples of the acid anhydride curing agent include dodecenyl succinic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid anhydride, trialkyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like. These are used alone or as a mixture of two or more. If necessary, maleic anhydride, hexahydrophthalic anhydride, trimellitic anhydride, phthalic anhydride, tetrahydrophthalic anhydride, polyazelineic anhydride, pyromellitic anhydride, benzophenonetetracarboxylic anhydride, etc. are used in combination. You can also. When an acid anhydride is used as a curing agent, a known curing accelerator such as an imidazole compound or benzyldimethylamine is usually used.

(5) Curing of the epoxy adhesive The epoxy adhesive is cured at room temperature or by heating (secondary heating). The heating is performed by an appropriate method, for example, using a hot air dryer, an electric furnace, or the like.

  As a result, the molecular bonds between the triazine thiol compounds are protected by the preheated epoxy compound in advance, so that the curing agent used for the epoxy adhesive, particularly the amine curing agent, reacts with the coating of the triazine thiol compound. In other words, the epoxy compound layer chemically bonded to the triazine thiol compound film prevents the curing agent contained in the epoxy adhesive from breaking the triazine thiol film by breaking the molecular bond between the triazine thiols. As a result, the epoxy adhesive is firmly bonded to the metal, and the adherend is securely bonded to the metal.

  Next, a method for manufacturing an electroforming mold according to an embodiment of the present invention will be described. As shown in FIGS. 3 and 4, the method for manufacturing the electroforming mold follows the following steps. In addition, since the adhesion method of the metal which concerns on said embodiment and a to-be-adhered material is applied to the manufacturing method of this electroforming metal mold | die, description is abbreviate | omitted about the part which is common above.

(1) Creation of mother mold The mother mold is formed of, for example, a bakelite material.
(2) Formation of surface conductive layer A metal is applied to the surface of the mother die by, for example, a thickness of 0.01 mm or more using electroless plating or the like. In the embodiment, silver was applied by a silver mirror reaction.
(3) Electroforming (electro nickel plating)
The surface of the mother die is attached with nickel as a metal.

(4) Coating of triazine thiol compound The surface opposite to the metal matrix attached to the surface of the matrix by plating is coated with the triazine thiol compound in the same manner as described above.
(5) Application of epoxy compound An epoxy compound containing at least two epoxy groups in one molecule is applied to the surface of a metal coated with a triazine thiol compound in the same manner as described above.
(6) Heat treatment The epoxy compound is heat treated. The heat treatment is performed at 50 to 200 ° C. for 1 to 300 minutes, preferably at 80 to 160 ° C. for 10 to 180 minutes.
The heating is performed by an appropriate method, for example, using a hot air dryer or an electric furnace.

  By this heat treatment, the epoxy compound reacts with the film of the triazine thiol compound to protect the molecular bond between the triazine thiol compounds. That is, by this primary heat treatment, the thiol group on the coating surface of the triazine thiol compound reacts with the epoxy group, and an epoxy compound layer is formed on the coating of the triazine thiol compound.

(7) Application of epoxy adhesive An epoxy adhesive mixed with a curing agent is applied to the metal surface. The epoxy resin and the curing agent of the epoxy adhesive are the same as described above. In this case, glass fiber or chemical fiber may be laminated on the epoxy adhesive coating layer, or a woven fabric or nonwoven fabric impregnated with an epoxy adhesive may be used.
(8) Formwork installation Formwork is installed around the mother mold.

(9) Adhesion of backup material as adherend After that, an epoxy adhesive mixed with a curing agent is applied again, and then, for example, cement or concrete is poured into the mold as a backup material. In this case, when the backup material is cement or concrete, it may be poured immediately after application of an epoxy adhesive mixed with a curing agent. When the backup material is an epoxy resin or a composition containing an epoxy resin, it may be poured immediately after the primary heating.
Then, for example, curing is performed for several days to solidify the epoxy adhesive, and the backup material is attached to the metal.

  As a result, the molecular bonds between the triazine thiol compounds are protected by the preheated epoxy compound in advance, so that the curing agent used for the epoxy adhesive, particularly the amine curing agent, reacts with the coating of the triazine thiol compound. In other words, the epoxy compound layer chemically bonded to the triazine thiol compound film prevents the curing agent contained in the epoxy adhesive from breaking the triazine thiol film by breaking the molecular bond between the triazine thiols. As a result, the epoxy adhesive is firmly bonded to the metal, and the adherend is securely bonded to the metal.

(10) Demolding Demolding the mother mold. Thereby, an electroforming mold is completed.
In this electroformed mold, even when a thermal shock is applied during molding, the adhesion strength of the metal to the epoxy adhesive is increased, so that the situation where the metal and the backup material are separated due to thermal shock is prevented. The durability is improved.

  Next, examples will be described. Moreover, about these Examples, the T-type peeling test was done with the comparative example, and the peeling strength was measured and compared. First, each example and comparative example will be described. Specific compound names, processing conditions, etc., such as metal sheets and epoxy compounds relating to adhesion in each Example and Comparative Example, are shown in FIGS.

[Examples 1 to 12]
In Examples 1 to 12, as shown in FIGS. 5 to 8, a degreased and washed metal sheet (100 × 20 mm, thickness 0.1 mm) was used as an anode, and a platinum plate was used as a cathode. -Electrochemical surface treatment of a metal sheet was performed by applying a predetermined voltage for a predetermined time in a 0.2% aqueous solution of triazine-2,4,6-trithiol sodium salt by a two-electrode system. The treated metal sheet was taken out from the electrolytic solution, washed with distilled water and dried. An epoxy compound diluted to 10 wt% with acetone was applied to the portion of the metal sheet that had been subjected to electrochemical surface treatment at a rate of 0.2 g / cm ² and heat-treated at a predetermined temperature for a predetermined time. After the heat treatment, a polyester cloth as an adherend was adhered to the surface-treated portion using an epoxy adhesive mixed with a curing agent, and heat cured at a predetermined temperature for a predetermined time.

[Comparative Examples 1, 5, 7, 9, 11]
In Comparative Examples 1, 5, 7, 9, and 11, as shown in FIGS. 9 to 12, a polyester cloth is bonded using an epoxy adhesive in which a curing agent is directly mixed with the same metal sheet as in Examples 1 to 3. The resin was cured by heating at a predetermined temperature for a predetermined time.

[Comparative Examples 2, 3, 4, 6, 8, 10, 12]
In Comparative Examples 2, 3, 4, 6, 8, 10, and 12, as shown in FIG. 9 to FIG. 12, the metal sheet that was degreased and washed in the same manner as in the examples was subjected to electrochemical surface treatment, and washed and dried with distilled water. Thereafter, a polyester cloth was adhered to the surface-treated portion using an epoxy adhesive mixed with a direct curing agent, and heat cured at a predetermined temperature for a predetermined time.

  And the T-type peeling test was done about said Example and comparative example. As shown in FIG. 13, the T-type peel test is a test in which the peel strength at the time of peeling a polyester cloth as an adherend from a metal sheet is measured on a test piece prepared under the above conditions.

  The test results are shown in FIGS. From this test result, the metal without the triazine thiol film peels off at about 0.3 to 0.5 kN / m, whereas it is 2-3 times even if the epoxy adhesive is applied directly by forming the triazine thiol film. The peel strength is improved and the effectiveness of the triazine thiol film can be seen. However, according to the bonding method of the present invention, it can be seen that the strength is more than 10 times that of a metal without a triazine thiol film.

Moreover, in FIG. 14, the relationship of the peeling strength with respect to the peeling distance of said polyester cloth (cross | cross) is shown. The curve (A) in FIG. 14 shows the result of the peel test of the test piece prepared under the conditions of Example 1, the curve (B) shows the result of Comparative Example 2, and the curve (C) shows the result of Comparative Example 1. The result of the peeling test of the test piece created on condition is shown.
Example 1 in which an epoxy compound was applied onto a triazine thiol film and subjected to primary heat treatment was four times as large as Comparative Example 3 without a triazine thiol film, compared to Comparative Example 2 in which an epoxy adhesive was directly applied to the triazine thiol film. The peel strength is nearly 10 times. Moreover, in the test piece which apply | coated the epoxy adhesive directly to the triazine thiol film or the nickel sheet, after showing the maximum intensity | strength immediately after load loading, it peeled at a stretch. This is a peeling phenomenon that occurs when the epoxy adhesive has high rigidity and the bond between the nickel surface and the triazine thiol coating or the epoxy adhesive is weak. On the other hand, in Example 1 where the epoxy compound was applied and the primary heat treatment was performed, it was found that the material gradually broke down while maintaining high strength. This indicates that the bond is strong because the bond between the nickel and the triazine thiol film and the bond between the triazine thiol film and the epoxy compound and the epoxy adhesive are strong. In fact, it was confirmed that the fracture occurred in the adhesive layer.
In addition, the peel strength of the examples of FIGS. 5 to 8 shows the average strength, and the peel strengths of the comparative examples of FIGS. 9 to 12 show the maximum strength.

Next, examples according to the method for manufacturing the electroforming mold will be described together with the results of the peeling test.
[Example 13]
In Example 13, a bakelite cylinder having an outer diameter of 60 mm, a height of 15 mm, and a thickness of 1 mm was pasted on a bakelite plate (300 × 250 mm, thickness 10 mm), and a conductive layer was formed thereon by silver mirror reaction. Nickel plating was performed to form an electroformed nickel layer having a thickness of 3 mm. The electroformed nickel layer including the bakelite plate was washed with water, dried, and then subjected to electrochemical surface treatment in an aqueous triazine thiol solution at a potential of 3 V for 10 minutes. This was taken out, washed with water, dried, and then applied with Araldite LY5052 (manufactured by Ciba Geigy) diluted to about 5% with acetone at a rate of 0.2 g / cm ² and heat-treated in an oven at 140 ° C. for 2 hours. It cooled after heat processing, the epoxy adhesive (Araldite LY5052) which added the hardening | curing agent was apply | coated, and also the glass fiber was laminated | stacked with the said epoxy adhesive. After arranging cooling pipes in this, it was put in a zinc alloy frame of a predetermined size, poured concrete, and cured for 7 days. After curing, the electroformed nickel integrated with the concrete and zinc alloy frame was removed from the bakelite mother mold and sprue and runners were processed to make an injection mold. Using this electroforming mold, a thermoplastic elastomer was molded at a mold temperature of 40 ° C. and a resin temperature of 200 ° C. No peeling of electroformed nickel was observed after 30,000 shot forming.

[Example 14]
In Example 14, a polycarbonate lens was attached to a stainless steel plate, and platinum was coated by a sputtering method to impart conductivity to the lens surface. Then, electronickel plating was performed to form an electroformed nickel layer having a thickness of 0.5 mm. . The electroformed nickel layer containing the stainless steel plate was washed with water, dried and subjected to an electrochemical surface treatment in an aqueous triazine thiol solution at a potential of 2 V for 10 minutes. This was taken out, washed with water, dried, and then Epicoat 801 (made by Japan Epoxy Resin Co., Ltd.) diluted to about 10% with acetone was applied at a rate of 0.2 g / cm ² and heat-treated in an oven at 140 ° C. for 2 hours. went. After heat treatment, it was cooled and placed in an aluminum frame of a predetermined size, and Epicoat 630 (made by Japan Epoxy Resin Co., Ltd.) kneaded with nickel powder and a curing agent was poured into it, left at 60 ° C. for 12 hours, and then heated and cured to 200 ° C. After cooling, the electroformed nickel integrated with the epoxy resin kneaded with nickel powder was removed from the aluminum frame, and the polycarbonate lens was removed from the electroformed nickel. This was subjected to runners, gates, extrusion pin hole processing, etc., and then incorporated into a mold base as a nest, and a polycarbonate resin was molded at a resin temperature of 300 ° C. and a mold temperature of 100 ° C. Even after 1000 shot molding, peeling between the electroformed nickel and the epoxy resin backup material was not observed.

  In the above embodiments and examples, the triazine thiol compound is electrochemically coated on the surface of the metal. However, the present invention is not necessarily limited to this, and for example, by other means such as vapor deposition. You may make it coat | cover and may change suitably.

The method according to the present invention can be used to manufacture an electroforming mold having durability against heat shock in which an electroformed nickel shell and a backup material are firmly bonded. In addition, it is possible to firmly bond many metals and metals or metals and organic and inorganic materials such as nickel, nickel alloys, stainless steel, chromium, cobalt, etc., and sealability, adhesion, and high adhesive strength are required. It can be used for manufacturing electrical / electronic parts and automobile parts.

It is a figure which shows the adhesion principle which concerns on the principal part in the adhesion | attachment method of the metal and adherend of this invention, and the manufacturing method of an electroforming mold. It is process drawing which shows the adhesion method of the metal and adherend which concern on embodiment of this invention. It is process drawing which shows the manufacturing method of the electroforming metal mold | die which concerns on embodiment of this invention. It is process drawing which shows the manufacturing method of the electroforming metal mold | die which concerns on embodiment of this invention. It is a table | surface which shows Example 1 thru | or 3 process conditions and peeling strength which concern on the adhesion method of the metal and adherend of this invention. It is a table | surface which shows Example 4 thru | or 6 process conditions and peeling strength which concern on the adhesion method of the metal and adherend of this invention. It is a table | surface which shows Example 7 thru | or 9 process conditions and peeling strength which concern on the adhesion method of the metal and adherend of this invention. It is a table | surface which shows the Example 10 thru | or 12 process conditions and peeling strength which concern on the adhesion method of the metal and adherend of this invention. It is a table | surface which shows the comparative examples 1 thru | or 3 process conditions and peeling strength which concern on a peeling test. It is a table | surface which shows the comparative examples 4 thru | or 6 process conditions and peeling strength which concern on a peeling test. It is a table | surface which shows the comparative conditions 7 thru | or 9 process conditions and peel strength which concern on a peel test. It is a table | surface which shows the comparative examples 10-12 processing conditions and peeling strength which concern on a peeling test. It is a figure which shows the state of the test piece which concerns on a peeling test. It is a graph which shows the relationship between the moving distance of a crosshead, and peeling strength in connection with a peeling test.

Claims (8)

After coating the surface of the metal with a triazine thiol compound, an epoxy adhesive mixed with a curing agent is applied to the surface of the metal, and the metal to be adhered is adhered to the surface of the metal via the epoxy adhesive. In the bonding method with the dressing,
Before applying the epoxy adhesive, an epoxy compound containing at least two epoxy groups in one molecule is applied to the surface of the metal coated with the triazine thiol compound, and then the epoxy compound is heated. A method for adhering a metal and an adherend to each other.   The method for adhering a metal and an adherend according to claim 1, wherein the heat treatment is performed at 50 to 200 ° C. for 1 to 300 minutes.   The method for adhering a metal and an adherend according to claim 2, wherein the heat treatment is performed at 80 to 160 ° C. for 10 to 180 minutes.   4. The method for adhering a metal and an adherend according to claim 1, 2 or 3, wherein the triazine thiol compound is electrochemically coated on the surface of the metal. A metal is plated on the surface of the mother mold, an epoxy adhesive mixed with a curing agent is applied to the surface opposite to the metal mother mold, and the metal surface is covered with the epoxy adhesive. In the method for producing an electroforming mold, a back-up material as a dressing material is adhered, and then the mother mold is removed, and an electroforming mold is produced.
Before applying the epoxy adhesive, the surface of the metal on which the surface of the matrix is opposite to the metal matrix attached by plating is coated with a triazine thiol compound and the surface of the metal coated with the triazine thiol compound. And an epoxy compound containing at least two epoxy groups per molecule, and then heat-treating the epoxy compound.   6. The method for producing an electroforming mold according to claim 5, wherein the heat treatment is performed at 50 to 200 [deg.] C. for 1 to 300 minutes.   The method for producing an electroforming mold according to claim 6, wherein the heat treatment is performed at 80 to 160 ° C for 10 to 180 minutes. The method for producing an electroforming mold according to claim 5, 6 or 7, wherein the metal surface is electrochemically coated with the triazine thiol compound.

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