JP6918341B2 - Substrate composite and its manufacturing method - Google Patents

Description

The present invention relates to a substrate complex and a method for producing the same. More specifically, the present invention relates to a substrate complex in which two substrates are bonded by an anchor effect using a plurality of holes in the adhesive layer, and a method for producing the same. The substrate composite of the present invention is particularly useful for adhering two substrates for which there is no suitable adhesive for adhering at the same time.

In recent years, with the progress of resinification of metal parts for the purpose of weight reduction of vehicle bodies and the like, high-strength adhesion between a resin substrate and two substrates such as a metal substrate is required.
As the bonding method, a mechanical bonding method using rivets or bolts, a direct bonding method using surface adhesive force without using an adhesive, and an adhesive bonding method using an adhesive (Japanese Unexamined Patent Publication No. 2015-145461: Patent Document 1). )It has been known.
In the mechanical bonding method, stable bonding strength can be obtained regardless of the type of substrate. However, it is difficult to say that the adhesion is sufficiently high because the substrate needs to be drilled and stress is concentrated on the bonded portion. Further, it is difficult to apply to a substrate having a complicated shape.

With the direct bonding method, if the substrate is not treated at all, it is difficult to obtain sufficient surface adhesive force. Therefore, the adhesive surface of the substrate is roughened (for example, chemical conversion treatment, plasma treatment, laser irradiation, etc.) and wettability is improved (for example, primer coating). ) Is usually performed. However, all of the above processes require a separate large-scale processing device, so it is difficult to say that the workability is good. Further, as with the mechanical bonding method, it was difficult to apply to a substrate having a complicated shape.
Since the adhesive bonding method is basically surface bonding, it has the advantages that stress concentration on the bonded part is relaxed and it can be used on a substrate with a complicated shape as compared with the mechanical bonding method. be. In addition, the adhesive has the advantage that it does not require a large-scale device for coating on the substrate.

Japanese Unexamined Patent Publication No. 2015-145461

The adhesive bonding method is an effective bonding method when the adhesive has sufficient adhesiveness to both of the two substrates. However, it has been difficult to apply this bonding method when the adhesive does not have sufficient adhesiveness to either substrate. Therefore, it has been desired to ensure sufficient adhesiveness to both of the two substrates even when the adhesive does not have sufficient adhesiveness to both of the two substrates.

As a result of diligent studies to solve the above problems, the present inventor forms an adhesive layer using an adhesive having sufficient adhesiveness to one substrate, and adheres the other substrate to the adhesive layer. We have found that it is possible to provide a substrate composite including two substrates and an adhesive layer for adhering the two substrates by utilizing the anchor effect, and have arrived at the present invention.

Thus, according to the present invention, the first substrate, the second substrate, and the adhesive layer for adhering the first substrate and the second substrate are included.
The adhesive layer has a plurality of holes in the surface layer portion on the second substrate side.
The second substrate is provided with a plurality of protrusions on the surface on the first substrate side.
Provided is a substrate composite characterized in that the protrusions are located in the holes.

Further, according to the present invention, there is a method for producing the above-mentioned substrate complex.
When the adhesive layer is composed of thermosetting resin,
Adhesion provided with the plurality of holes by forming a mixture layer containing a thermosetting resin and a pore-forming material that gives the thermosetting resin on the first substrate and heat-curing the thermosetting resin. By forming a layer, removing the hole-forming material from the adhesive layer, and forming a plurality of the protrusions on the surface of the second substrate on the first substrate side so as to be located in the holes. Provided is a method for producing a substrate composite, which comprises a step of adhering the first substrate and the second substrate.

Further, according to the present invention, there is a method for producing the above-mentioned substrate complex.
When the adhesive layer is composed of a thermoplastic resin,
A step of forming a mixture layer containing the thermoplastic resin and a pore-forming material on the substrate and a step of forming an adhesive layer having the plurality of holes by removing the pore-forming material from the mixture layer. The step of adhering the first substrate and the second substrate by forming a plurality of the protrusions on the surface of the second substrate on the first substrate side so as to be located in the holes is included. A method for producing a characteristic substrate composite is provided.

According to the present invention, it is possible to provide a substrate complex in which two substrates are firmly adhered by an adhesive layer and a method for producing the same.

It is the schematic sectional drawing of the substrate complex of this invention. It is an SEM image of the monolith film of Example 1. It is a graph which shows the correlation of the porosity and the average pore diameter plot with respect to γ of the monolith film of Example 1. It is a graph which shows the correlation between the average pore diameter and the number of pores of the monolith film of Example 1. FIG. It is a TG-DTA curve of the monolith film of Example 1. FIG. It is a load-displacement curve of the substrate complex of Example 1. It is the schematic of the heat fusion state at the time of manufacturing the substrate complex for measuring the load-displacement curve of FIG. It is a photograph after breaking of the substrate complex of Example 1. It is a load-displacement curve of the substrate complex of Example 1. It is the schematic of the heat fusion state at the time of manufacturing the substrate complex for measuring the load-displacement curve of FIG. It is a photograph after breaking of the substrate complex of Example 1. 6 is an SEM image of a fracture surface of the substrate complex of Example 1. 6 is an SEM image of a fracture surface of the substrate complex of Example 1. It is a photograph after breaking of the substrate complex of Example 1. 6 is an SEM image of a fracture surface of the substrate complex of Example 1. It is a photograph after breaking of the substrate complex of Example 1. 6 is an SEM image of a fracture surface of the substrate complex of Example 1. 6 is an SEM image of a fracture surface of the substrate complex of Example 1. It is a graph which shows the bonding strength of the substrate complex of Example 1. It is a graph which shows the bonding strength of the substrate complex of Example 1. It is a graph which shows the bonding strength of the substrate complex of Example 1. It is a graph which shows the bonding strength of the substrate complex of Example 1. It is a graph which shows the bonding strength of the substrate complex of Example 1. 6 is an SEM image of a fracture surface of the substrate complex of Example 1. 6 is an SEM image of a fracture surface of the substrate complex of Example 1. 6 is an SEM image of a fracture surface of the substrate complex of Example 1. 6 is an SEM image of a fracture surface of the substrate complex of Example 1. It is an SEM image of the monolith film of Example 2. It is a load-displacement curve of the substrate complex of Example 2. It is a photograph after breaking of the substrate complex of Example 2. It is an SEM image of the fracture surface of the substrate complex of Example 2. It is a load-displacement curve of the substrate complex of Example 3. It is an SEM image of the Al substrate of Example 4. It is an SEM image of the monolith film of Example 5. It is an SEM image of the monolith film of Example 9. It is a stress-elongation graph of the substrate complex of Example 9 and Comparative Example 4. It is a photograph after the fracture of the substrate composite of Example 9 and Comparative Example 4. It is a stress-elongation graph of the substrate complex of Example 10 and Comparative Example 5. It is a photograph after breaking of the substrate complex of Example 10. It is a stress-elongation graph of the substrate complex of Example 11 and Comparative Example 6. It is a photograph after breaking of the substrate complex of Example 11. It is a stress-elongation graph of the substrate complex of Example 12. It is a photograph after breaking of the substrate complex of Example 12. It is a photograph of the monolith sheet of Example 13. It is a photograph of the monolith sheet of Example 13. It is a photograph of the monolith sheet of Example 13. It is a stress-elongation graph of the substrate complex of Example 13. It is a photograph after breaking of the substrate complex of Example 13. It is a stress-elongation graph of the substrate complex of Example 14.

(Substrate complex)
The substrate complex of the present invention includes a first substrate, a second substrate, and an adhesive layer for adhering the first substrate and the second substrate. Further, the adhesive layer has a plurality of holes in the surface layer portion on the second substrate side. Further, the second substrate is provided with a plurality of protrusions located in the holes on the surface on the first substrate side. Specifically, this substrate complex has the structure shown in FIG. In FIG. 1, 1 is a first substrate, 2 is a second substrate, 3 is an adhesive layer, 4 is a hole, and 5 is a protrusion.
In FIG. 1, the anchor effect is used for bonding the second substrate and the adhesive layer, but the anchor effect can also be used for bonding the first substrate and the adhesive layer.
Further, FIG. 1 illustrates a case where there are two substrates. However, the number of laminated substrates is not limited to two, and the number of adhesive layers for adhering the substrates to each other can be increased according to the number of laminated substrates. For example, the substrate complex is a laminate of a first substrate, a first adhesive layer, a second substrate, a second adhesive layer, a third substrate, ... N-1 adhesive layer, nth substrate. It may be (n is a natural number). In this case, the n-1 adhesive layers may be obtained by simultaneously adhering n substrates or sequentially adhering them in any order.

(1) First substrate The first substrate is not particularly limited as long as it is desired to be complexed with the second substrate. Examples of the constituent material of the first substrate include metals (for example, magnesium, aluminum, titanium, zirconium, chromium, iron, copper, nickel, zinc, silver, platinum, gold, etc.) and alloys of these metals (for example, stainless steel, etc.). Hasteroi, duralmin, brass, magnesium alloy, etc.), oxides of the above metals (eg, magnesium oxide, aluminum oxide, titanium oxide, zirconium oxide, etc.), thermoplastic resins (eg, polyethylene, polyethylene vinyl alcohol, polyolefins such as polypropylene, etc.) Resin, polyvinyl alcohol, polyvinyl chloride, polyvinylidene fluoride, poly (meth) acrylic acid ester, polyacrylonitrile, polycarbonate, polystyrene, AS resin, styrene resin such as ABS resin, polyamide resin such as nylon, polyethylene terephthalate, polybutylene Polyester resin such as terephthalate, polyimide resin, fluororesin, polyether ketone, polysulfone, polyoxymethylene, polyphenylene sulfide, etc., thermosetting resin (eg, epoxy resin, phenol resin, urea resin, melamine resin, etc.), glass, ceramics , Wood, paper, etc. The substrate made of resin may contain other components such as colorants, fillers and reinforcing fibers.

The first substrate may have any structure as long as it can be complexed with the second substrate. That is, the first substrate is not limited to a flat substrate, but has steps, includes protrusions and recesses, is curved, rod-shaped or columnar, spherical, fibrous or its woven fabric, and more. It may have a complicated shape, and the thickness of the first substrate is not particularly limited as long as it can be composited. Further, the portion of the first substrate that is desired to be complexed with the second substrate may be flat or may have an uneven shape. The uneven shape of the surface can be formed by, for example, a file.

(2) Second substrate The second substrate is not particularly limited as long as it is desired to be complexed with the first substrate. Examples of the constituent material of the second substrate include metals (for example, magnesium, aluminum, titanium, zirconium, chromium, iron, copper, nickel, zinc, silver, platinum, gold, etc.) and alloys of these metals (for example, stainless steel, etc.). Hasteroi, duralmin, brass, magnesium alloy, etc.), oxides of the above metals (eg, magnesium oxide, aluminum oxide, titanium oxide, zirconium oxide, etc.), thermoplastic resins (eg, polyethylene, polyethylene vinyl alcohol, polyolefins such as polypropylene, etc.) Resin, polyvinyl alcohol, polyvinyl chloride, polyvinylidene fluoride, poly (meth) acrylic acid ester, polyacrylonitrile, polycarbonate, polystyrene, AS resin, styrene resin such as ABS resin, polyamide resin such as nylon, polyethylene terephthalate, polybutylene Polyester resin such as terephthalate, polyimide resin, fluororesin, polyether ketone, polysulfone, polyoxymethylene, polyphenylene sulfide, etc., thermosetting resin (eg, epoxy resin, phenol resin, urea resin, melamine resin, etc.), glass, ceramics , Wood, paper, etc. The second substrate may contain other components such as colorants, fillers and reinforcing fibers.
When the second substrate is made of a material that is not deformed by heat such as metal or alloy, the surface on the second substrate side is made of a resin layer (thermoplastic resin or thermosetting resin) that is plastically deformed during heating and pressurization. It is preferable to have a layer to be formed). Specifically, the second substrate is composed of a substrate body made of a material that is not deformed by heat such as metal or alloy, and a resin layer having protrusions formed on the surface of the substrate body on the first substrate side. It may have been done.

The second substrate may have the same or different material as the second substrate laminated on a surface different from that of the first substrate. Different materials include metals (eg magnesium, aluminum, titanium, zirconium, chromium, iron, copper, nickel, zinc, silver, platinum, gold, etc.) and alloys of these metals (eg, stainless steel, hasterois, duralumin, brass, etc. Examples thereof include magnesium alloys), oxides of the metals (eg, magnesium oxide, aluminum oxide, titanium oxide, zirconium oxide, etc.), thermoplastic resins, thermocurable resins (eg, epoxy resins), and the like.

The second substrate may have any structure as long as it can be complexed with the first substrate. That is, the second substrate is not limited to a flat substrate, but has steps, includes protrusions and recesses, is curved, rod-shaped or columnar, spherical, fibrous or its woven fabric, and more. It may have a complicated shape, and the thickness of the second substrate is not particularly limited as long as it can be composited. Further, the portion of the second substrate that is desired to be complexed with the first substrate may be flat or may have an uneven shape. The uneven shape of the surface can be formed by, for example, a file.

(3) Adhesive layer The adhesive layer (hereinafter, also referred to as a monolith film) is provided with a plurality of holes on the surface layer portion capable of accommodating the protrusions extending from the second substrate. Due to the obtained anchor effect, it is firmly adhered to the second substrate.

As the constituent materials of the adhesive layer, thermoplastic resins (for example, polyolefin resins such as polyethylene, polyethylene vinyl alcohol, polypropylene, polyvinyl alcohol, polyvinyl chloride, vinylidene fluoride, poly (meth) acrylic acid ester, polyacrylonitrile, polycarbonate, etc. Polystyrene resin such as polyvinyl acetate, polystyrene, AS resin, ABS resin, polyamide resin such as nylon, polyester resin such as polyethylene terephthalate and polybutylene terephthalate, polyimide resin, fluororesin, polyether ketone, polysulfone, polyoxymethylene, Examples thereof include polyphenylene sulfide, cellulose resin, etc.), thermosetting resins (for example, epoxy resin, phenol resin, urea resin, melamine resin, etc.) and the like.

The present invention enables adhesion even in a combination in which an adhesive suitable for two substrates does not exist (for example, a combination of a metal and a polyolefin resin), which has been difficult to form a composite with an adhesive in the past. .. That is, in one aspect of the present invention, the adhesive layer enables strong adhesion to the first substrate by a chemical bond (for example, hydrogen bond, covalent bond, etc.), and has an anchor effect on the second substrate. It enables strong adhesion by physical bonding by. In addition to the combination of metal and polyolefin resin, the present invention also applies to the combination of metal and styrene resin, the combination of metal and fluororesin, the combination of glass and polyolefin resin, and the combination of ceramics and polyolefin resin. Can be preferably used. More specifically, in the present invention, when the adhesive strength between the adhesive layer and the first substrate is 10 MPa or more and the second substrate is directly adhered to the first substrate (materials constituting the first substrate and the second substrate). It is particularly effective when used in a combination in which the bonding strength (the bonding strength between the material constituting the first substrate and the material constituting the second substrate) is 1 MPa or less.
In the present invention, even when the material constituting the second substrate has an adhesive strength to the material constituting the adhesive layer (a flat material having no monolith structure and no holes) of 1 MPa or less. According to this, high adhesive strength can be obtained between the second substrate and the adhesive layer. This indicates that in the present invention, a wide range of materials can be used as the material constituting the adhesive layer.

The shape and number of the plurality of holes are not particularly limited as long as the anchor effect can be sufficiently exhibited. Here, it can be rephrased that sufficiently exhibiting the anchor effect indicates an adhesive strength greater than 1 MPa.

For example, the holes preferably have a diameter of 1 to 50 μm (the average value of the minimum diameter and the maximum diameter). The lower limit of the diameter may be 5 μm. Further, it is preferable that ^{10 to 100,000 holes / mm 2} are present on the surface layer portion of the adhesive layer on the second substrate side. Further, it is preferable that the holes satisfy the relationship of ^{100 to 500,000 μm · piece / mm 2} in the integrated value of the diameter and the number. Furthermore, the holes preferably have a depth of 10 μm or more in the thickness direction of the adhesive layer.

(4) Applications The substrate complex can be used in applications where it is desired to impart characteristics to the first substrate that are difficult to realize with the first substrate alone. Examples of this characteristic include light weight, heat resistance, low temperature characteristics, weather resistance, impact resistance, tensile strength, flexural strength, high toughness, high elasticity, chemical resistance, corrosion resistance, designability and the like. Be done. Specific uses include exteriors of vehicles (for example, automobiles, railroad vehicles, etc.), wind turbine wings, housings for electronic devices, building materials, and the like.

(5) Other Structures In the above aspect, the adhesive layer is bonded to the first substrate by chemical bonding, but in order to bond the adhesive layer to the second substrate, holes in the adhesive layer and protrusions on the second substrate are used. May be used for adhering the adhesive layer to the first substrate. That is, the first substrate has a plurality of protrusions on the surface on the second substrate side, the adhesive layer has a plurality of holes on the surface layer on the first substrate side, and the protrusions are located in the holes. Then, the adhesive layer and the first substrate may be adhered to each other. In this form, the adhesive layer and the first substrate can be adhered by the anchor effect even if the adhesive strength is not high when the adhesive layer and the first substrate are directly adhered to each other. This form is particularly useful when the adhesive layer is composed of a thermoplastic resin. For example, the first and second substrates once adhered can be separated without residual adhesive by simply heating them, which has the advantage of facilitating recycling of the first and second substrates. There is.
The adhesive layer used in the above structure need only have holes on the sides facing the first and second substrates. Therefore, the adhesive layer may be a single layer or a laminated body of a plurality of layers. For example, the two-layer laminate has a laminated structure of a first adhesive layer having at least holes on the side facing the first substrate and a second adhesive layer having at least holes on the side facing the second substrate. It can be taken. The first adhesive layer and the second adhesive layer may be fixed by an adhesive, or may be fixed by melting either or both of the two layers. By providing a plurality of holes in either one or both of the two layers for these fixings, it is possible to add an adhesive force due to the anchor effect between the protrusions and the holes generated from the adhesive or the melt.
(Manufacturing method of substrate complex)
The substrate complex can be produced by a method according to the resin type constituting the adhesive layer. Specifically, when the adhesive layer is composed of a thermosetting resin, the substrate composite can be produced by the following method A, and when the adhesive layer is composed of a thermoplastic resin, the substrate composite can be produced by the following method B, respectively.

(Method A)
A step of forming a mixture layer containing a thermosetting resin that gives a thermosetting resin and a pore-forming material (hereinafter, also referred to as porogen) on a substrate (mixture layer forming step).
A step of forming an adhesive layer having a plurality of holes by thermosetting the thermosetting resin (thermosetting step), a step of removing the pore-forming material from the adhesive layer (removal step), and a step of removing the pore-forming material from the adhesive layer.
A step of adhering the first substrate and the second substrate by forming a plurality of protrusions on the surface of the second substrate on the first substrate side so as to be located in the holes (projection forming step).
The substrate complex can be manufactured through the above.

(Method B)
A step of forming a mixture layer containing a thermoplastic resin and a pore-forming material on a substrate (mixture layer forming step),
By removing the pore-forming material from the mixture layer, a step of forming an adhesive layer having a plurality of holes (removal step) and a protrusion are located in the holes on the surface of the second substrate on the first substrate side. A step of adhering the first substrate and the second substrate by forming a plurality of the first substrate (projection forming step).
The substrate complex can be manufactured through the above.

(1) Method A
(A) Mixture layer forming step Examples of the thermosetting resin that gives the thermosetting resin used in the mixture layer forming step include a combination of an uncured polymer and a curing agent.

Specifically, when the heat-curable resin is an epoxy resin, the uncured polymer includes a bisphenol A type epoxy resin, a brominated bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol AD type epoxy resin, and a stillben type epoxy resin. , Biphenyl type epoxy resin, bisphenol A novolac type epoxy resin, cresol novolac type epoxy resin, diaminodiphenylmethane type epoxy resin, and polyphenyl base epoxy resin such as tetrakis (hydroxyphenyl) ethane base, fluorene-containing epoxy resin, triglycidyl isocyanurate. , Aromatic epoxy resin such as epoxy resin containing a complex aromatic ring (for example, triazine ring), aliphatic glycidyl ether type epoxy resin, aliphatic glycidyl ester type epoxy resin, alicyclic glycidyl ether type epoxy resin, alicyclic Examples thereof include non-aromatic epoxy resins such as group glycidyl ester type epoxy resins. These may be used alone or in combination of two or more.

On the other hand, as the curing agent, aromatic amines (for example, metaphenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, benzyldimethylamine, dimethylaminomethylbenzene, etc.) and aromatic acid anhydrides (for example, phthalic anhydride, trimellitic anhydride) Aromatic curing agents such as acids, pyromellitic anhydride, phenolic resins, phenol novolac resins, heteroaroamic ring-containing amines (eg, triazine ring-containing amines, etc.), aliphatic amines (eg, ethylenediamine, diethylenetriamine, triethylene). Tetramine, tetraethylenepentamine, iminobispropylamine, bis (hexamethylene) triamine, 1,3,6-trisaminomethylhexane, polymethylenediamine, trimethylhexamethylenediamine, polyetherdiamine, etc.), alicyclic amines (Isophoronediamine, Mentandiamine, N-aminoethylpiperazine, 3,9-bis (3-aminopropyl) 2,4,8,10-tetraoxaspiro (5,5) undecane adduct, bis (4-amino-3) Non-aromatic hardeners such as −methylcyclohexyl) methane, bis (4-aminocyclohexyl) methane, modified products thereof, etc., and aliphatic polyamideamines composed of polyamines and dimer acids can be mentioned. These may be used alone or in combination of two or more.

The combination of the epoxy resin and the curing agent includes a combination of an aromatic epoxy resin and an alicyclic amine curing agent, a combination of an alicyclic epoxy resin and an aromatic amine curing agent, and a combination of an aromatic epoxy resin and an aromatic amine curing agent. , A combination of an alicyclic epoxy resin and an alicyclic amine curing agent may be used.
The mixing ratio of the curing agent to the epoxy resin is preferably 0.2 to 2 with respect to 1 equivalent of the epoxy group. More preferably, the mixing ratio of the curing agent to the epoxy resin is such that the curing agent equivalent is 0.6 to 1.4 with respect to one epoxy group equivalent.

The pore-forming material is preferably a material capable of forming pores by separating from the thermosetting resin when the thermosetting resin is thermally cured. For example, when the thermosetting resin is an epoxy resin, the uncured polymer and / or the curing agent can be dissolved, and after the uncured polymer and the curing agent are polymerized, they can be separated by phase separation from the polymer. Materials can be used. Specifically, cellosolves such as methyl cellosolve ethyl cellosolve, esters such as ethylene glycol monomethyl ether acetate and propylene glycol monomethyl ether acetate, glycols such as polyethylene glycol and polypropylene glycol, polyoxyethylene monomethyl ether and polyoxyethylene. Examples include ethers such as dimethyl ether. These may be used alone or in combination of two or more. Among these specific pore-forming materials, it is preferable to use polyethylene glycol having a molecular weight of 600 or less.
The amount of the pore-forming material used is preferably 10 to 400 parts by weight with respect to 100 parts by weight of the uncured polymer.

The mixing method of the thermosetting resin that gives the thermosetting resin and the pore forming material is not particularly limited, and examples thereof include a mixing method using a known stirrer. The mixture may contain a viscosity modifier (eg, a lower alcohol) to adjust the viscosity to a suitable viscosity for forming the mixture layer on the substrate.
A mixture layer is obtained by dropping or applying the obtained mixture onto a substrate. The thickness of the mixture layer is not particularly limited.

(B) Thermosetting Step Next, by thermosetting the thermosetting resin, an adhesive layer having a plurality of holes is formed.
The conditions for thermosetting can be appropriately determined according to the type of thermosetting resin used. For example, when the uncured polymer is an epoxy resin, it is preferably held at 60 to 300 ° C. for 0.5 to 10 hours. By curing the thermosetting resin, the pore-forming material is separated from the thermosetting resin, so that a plurality of pores are formed in the adhesive layer.

(C) Removal Step Next, the hole forming material existing in the plurality of holes of the adhesive layer is removed. The removing method is not particularly limited and can be appropriately determined depending on the type of the pore-forming material. For example, when the pore-forming material is glycols, the pore-forming material is dissolved using water, DMF (N, N-dimethylformamide), DMSO (dimethyl sulfoxide), THF (tetrahydrofuran), a mixed solvent thereof, or the like. There is a way to do it.
After removing the pore-forming material, the adhesive layer may be subjected to a drying treatment.

(D) Protrusion formation step In the protrusion formation step, the first substrate and the second substrate are adhered to each other by forming a plurality of protrusions on the surface of the second substrate on the first substrate side so as to be located in the holes. .. Examples of the formation of the protrusions include the following methods.
(1) When the protrusion is made of a thermoplastic resin, the thermoplastic resin is heated by simultaneously placing the second substrate having the thermoplastic resin layer on the adhesive layer side on the adhesive layer or after placing the second substrate. Protrusions are formed by extending from the layer.
(2) When the protrusions are derived from an adhesive, the adhesive is solidified or cured after the second substrate is placed on the coating film obtained by applying the adhesive on the adhesive layer so as to extend to the holes. By letting it form a protrusion.
(3) When the protrusion is made of a thermoplastic resin, at least the second substrate having the thermoplastic resin layer on the adhesive layer side is softened by bringing the thermoplastic resin layer into contact with an organic solvent, and then on the adhesive layer. By placing it on the surface, a protrusion is formed by extending from the thermoplastic resin layer.

(D-1) Step (1)
In the heating step, a precursor layer of a resin layer is formed on the adhesive layer, and then the precursor layer is heated while being heated or pressurized to form a resin layer having protrusions extending in the pores. .. The protrusion extending in the hole can be fitted into the hole and have a shape suitable for the shape of the hole (a shape complementary to the hole).
The heating is performed under the condition that the adhesive layer does not melt and the precursor layer melts. By heating the thermoplastic resin layer under these conditions, the resin constituting the thermoplastic resin layer is melted and extends to the holes of the adhesive layer to form protrusions. The heating temperature is preferably 20 ° C. or higher than the glass transition temperature (Tg) of the resin constituting the thermoplastic resin layer. By lengthening the heating time, the heating temperature can be lowered, and the heating temperature in this case is preferably higher than the Tg of the resin constituting the thermoplastic resin layer. Further, by increasing the degree of pressurization, the heating time can be shortened, the heating temperature can be lowered, the heating time can be shortened, and the heating temperature can be lowered. For crystalline resins, the temperature is preferably above the melting point (Tm).

As a step of forming the resin layer having the protrusion extending in the hole, a step other than heating may be used. For example, using a resin having a low elastic modulus, a second substrate having protrusions extending in the holes is formed only by pressurization without heating.

(D-2) Step (2)
The method of forming the protrusion is an extremely simple method of adhering the adhesive layer and the second substrate using an adhesive. When the adhesive is applied onto the adhesive layer, it becomes a coating film that fills the holes existing in the adhesive layer. When the adhesive is solidified or cured, the adhesive in the holes becomes protrusions and the coating film becomes a part of the second substrate.
The adhesive that can be used here is not particularly limited, and known adhesives (for example, cellulose-based adhesives, vinyl acetate resin-based emulsion-type adhesives, adhesives of the type in which a monomer is applied and cured (polymerized), etc. Any type of adhesive that cures a liquid oligomer or a reactive liquid polymer) can be used.
The solidification and curing conditions can be appropriately set according to the type of adhesive used.

(D-3) Step (3)
The method of forming the protrusion is a method of softening the thermoplastic resin layer on the second substrate side with an organic solvent so that the thermoplastic resin layer extends from the thermoplastic resin layer. The organic solvent that can be used here is not particularly limited, and is appropriately selected from known organic solvents (for example, aromatic solvents such as toluene and aliphatic solvents such as acetone) depending on the type of the thermoplastic resin. You can choose.

(E) Others The size and number of pores in the adhesive layer can be adjusted by appropriately adjusting conditions such as the types and blending ratios of the uncured polymer, curing agent and pore-forming material used, and the temperature and time at the time of curing. can.

(2) Method B
(A) Mixture layer forming step In the mixture layer forming step, a mixture layer containing the thermoplastic resin and the pore-forming material is formed on the substrate. As the pore-forming material used here, it is preferable to use an organic solvent capable of dissolving the thermoplastic resin. Such an organic solvent can be appropriately selected from alcohol, toluene, xylene, ether, ester and the like depending on the type of the thermoplastic resin. As a method for forming the mixture layer on the substrate, the same method as in Method A can be used.

(B) Removal Step Next, by removing the pore-forming material from the mixture layer, an adhesive layer having a plurality of pores is formed. The pores can be formed by, for example, evaporating the pore-forming material contained in the mixture layer by heating.
(C) Protrusion formation step The protrusion formation step can be performed in the same manner as in the above method A.

Although the present invention will be described based on examples, the present invention is not limited to these examples.
Example 1
(Mixed layer forming process)
DGEBA (uncured polymer, epoxy resin: 2,2-bis (4-glycidyl oxaphenyl) propane), PEG200 (porogen: polyethylene glycol, manufactured by Tokyo Chemical Industry Co., Ltd.), BACM (amine curing agent: 4,4) in a reagent bottle A predetermined amount of'-methylenebis (cyclohexylamine)) was added to prepare a mixed solution. _{The epoxy resin and the amine curing agent were weighed so that the ratio γ (2 [NH 2} ] / [epoxy]) of the amine active hydrogen to the epoxy group was 0.8 to 1.5, and the total amount of these monomers was 30% by weight. Epoxy was added so that
The mixed solution was added dropwise to the SUS substrate to form a mixture layer containing a thermosetting resin and pologene.

(Thermosetting process)
The mixture layer was heated in an oven at 120 ° C. for 20 minutes and at 80 ° C. for 30 minutes to form an adhesive layer with a plurality of pores.
(Removal process)
Then, it was immersed in ion-exchanged water overnight to remove porogen, and dried at room temperature under vacuum for 2 hours to obtain a white monolith film.
As the SUS substrate (SUS430), one cut into 10 mm × 50 mm × 0.48 mm with an electron beam was used.

The prepared monolith membrane was observed under the following conditions.
(1) SEM observation of the surface morphology of the prepared monolith film was performed with non-deposited metal, an acceleration voltage of 0.8 to 1.0 kV, and a spot diameter of 10. A scanning electron microscope (VE-9800, manufactured by KEYENCE) was used for SEM observation.
(2) The prepared monolithic film having a thickness of 400 to 600 μm was peeled off from the SUS substrate, cooled with liquid nitrogen, and then crushed with a glass rod, and the porosity was measured by the BET adsorption method. A vacuum pretreatment device (BELPREP-vacII, manufactured by Microtrac Bell) and a gas adsorption amount measuring device (BELSORP-max, manufactured by Microtrac Bell) were used for the measurement by the BET adsorption method.

(3) The prepared monolithic film was peeled off from the SUS substrate, and TG-DTA measurement was performed under a nitrogen stream (flow rate 50 mL / min) at a heating rate of 10 ° C./min using a sample cut into about 1 mm square. The thermal decomposition start temperature (T _d5 ) was calculated based on the weight when no weight change due to evaporation of water was observed. The maximum decomposition temperature (T _max ) was determined as the maximum value of the TG differential curve. A differential thermogravimetric simultaneous measuring device (DTG-60, manufactured by Shimadzu Corporation) was used for the measurement.

(Heating process)
Next, the metal substrate on which the monolith film was formed and the resin substrate were placed on the lower plate of the heat press heated to a predetermined temperature in this order with a bonding area of 10 mm × 10 mm, and the upper plate at room temperature was used for a certain period of time to 0 MPa. It was lightly pressed with force and heat-welded under the conditions shown in Table 1 to obtain a substrate composite. As the resin substrate, the six types of resin substrates shown in Table 1 cut into a width of 10 mm and a length of 50 mm with a diamond cutter were used.

In Table 1, PET is polyethylene terephthalate (manufactured by Takiron), PC is polycarbonate (manufactured by AS ONE), POM is polyoxymethylene (manufactured by AS ONE), ABS is acrylic nitrile butadiene styrene resin (manufactured by AS ONE), and PP is polypropylene. (Manufactured by AS ONE), PE means polyethylene (manufactured by AS ONE).

Comparative Example 1
A substrate complex composed of a metal substrate and a resin substrate was produced in the same manner as in Example 1 except that a monolith film was not interposed.

(Test, observation and analysis)
The obtained substrate complex was subjected to the following tests, observations and analyzes.
(1) Tensile Shear Test The substrate complex (test piece) was subjected to a tensile shear test under the conditions of a distance between gripping tools of 50 mm, a test piece width of 10 mm, and a tensile speed of 1 mm / min. The test piece thickness was the value of each resin substrate in Table 2. The joint strength was calculated from the equation (1) (in the equation, L _max means the maximum load).
Bond strength (MPa) = L _max (N) / 100 (mm ² ) (1)
In addition, a tensile test was conducted with a distance between grippers of 30 mm, a test piece width of 10 mm, and a tensile speed of 0.3 mm / min, and the elastic modulus of the substrate complex was determined from the inclination in the range where the strain was 0.05 to 0.25%. rice field.

(2) Observation of fracture surface With respect to the test piece after the tensile shear test, the fracture surface on the metal substrate side is metal non-deposited, the acceleration voltage is 0.8 to 1.0 kV, the spot diameter is 10, and the fracture surface on the resin layer side is Au. Observation was performed using SEM under the conditions of thin film deposition (sputtering for 30 to 45 seconds), acceleration voltage of 2.0 to 3.0 kV, and spot diameter of 8 to 10.

(evaluation)
(1) Pore diameter, number of pores, porosity An SEM image of the surface of the monolith film obtained by curing at different ratios of amine curing agents (γ = 0.8, 1.0 and 1.2) is shown in FIG. 2 (Fig. 2). In a) to (c), the correlation of plots of each parameter (porosity and average pore size) with respect to γ is shown in FIGS. 3 (a) and 3 (b), and the correlation between the number of pores and the average pore size is shown in FIG. The average pore size and the number of pores per unit area on the surface of the monolith film were measured from SEM images. The porosity was calculated using equation (2) from the density ρ calculated by measuring the weight, film thickness, and area of the monolith film for each test piece and the density ρ _{0 of the smooth monolith film.}
Porosity (%) = (1-ρ / ρ ₀ ) x 100 (2)
As the ratio of the amine curing agent was increased, the porosity tended to decrease and the average pore size tended to increase. In addition, there was a correlation that the logarithmic value of the number of pores decreased linearly with the increase in the average pore size. From this result, it is considered that the higher the ratio of the amine curing agent, the higher the crosslink point density, and after phase separation, a structure closer to a smoother film is formed. From the above, it was found that it is possible to change the porosity, the pore size, and the number of pores by adjusting the ratio of the amine curing agent.

(2) BET Specific Surface Area BET adsorption measurement was performed on a monolith film cured at a ratio of two types of amine curing agents (γ = 1.0 and 0.5). The specific surface area of the monolith film cured at γ = 1.0 was 0.584 m ² / g (N ₂ ) and 0.662 m ² / g (Kr). The specific surface area of the monolith film cured at γ = 0.5 was 0.121 m ² / g (N ₂ ). From these specific surface area values, it is inferred that the larger the γ, the more the co-continuous structure can be formed.

(3) Heat resistance The TG-DTA curve obtained by thermogravimetric analysis of the monolith film when cured at γ = 0.8 is shown in FIG. In FIG. 5, the solid line means the relationship between the left vertical axis and the dotted line means the right vertical axis and the temperature. The weight loss accompanied by endothermic around 100 ° C. was considered to be evaporation of the adsorbed water, and stopped once at 196 ° C. After that, the weight decreased again after 200 ° C., which is judged to be thermal decomposition because it is accompanied by heat generation.

(4) Shear test (a) Obtained from a tensile shear test on a substrate composite obtained by heat-welding a SUS substrate and a PET substrate (resin substrate) on which a monolith film cured with γ = 0.99 to 1.01 was produced. The load-displacement curve obtained is shown in FIG. 6, and the joint strength calculated from the equation (1) is shown in Table 2. As shown in FIG. 7, heat welding was performed for 20 seconds by sandwiching only the joint portion between the SUS substrate and the PET substrate between the upper and lower stages. The heat welding temperature was 170 ° C.

When heat welding was performed for 20 seconds, the bonding strength could be measured without breaking the substrate on the way. The bonding strength of PET, which is a polar resin, was increased by forming a smooth epoxy-cured film on a SUS substrate, but the adhesive strength could be further increased by forming a monolithic film.
The test piece after breaking is shown in FIG. From FIG. 8, it can be seen that the substrate was not destroyed.

(B) A load-displacement curve obtained by a tensile shear test for a substrate composite obtained by heat-welding a SUS substrate on which a monolith film cured at γ = 0.98 and a PET and a PC substrate was formed is shown in FIG. 9 (a). ) And (b) show the bonding strength in Table 3. As shown in FIG. 10, heat welding was performed by sandwiching the SUS substrate and PET and the entire SUS substrate and PC substrate between the upper and lower stages, the PET substrate at 100 ° C. for 180 seconds, and the PC substrate at 200 ° C. for 180 seconds. The heat welding temperature was set to be 30 ° C. and 50 ° C. higher than Tg, respectively, as a temperature at which the substrate is not significantly deformed in the stage and sufficient bonding strength for measurement can be obtained.

Since the heat welding temperature was lowered to 100 ° C., the bonding strength with the PET substrate was generally lower than that in the case of heat welding at 170 ° C. (see Table 2).

(5) Difference in fracture surface depending on the amount of amine added (a) PET
Table 4 shows the bonding strength and the breaking morphology of the substrate composite with the SUS substrate on which the monolith film was prepared with γ = 1.19, together with the case of γ = 0.98. In Table 4, Mix means that there is a mixture of cases where fracture occurs at the SUS interface and the PET interface. Further, the test pieces after breaking at the ratio (γ) of each amine curing agent are shown in FIGS. 11 (a) and 11 (b), and the SEM images in which the fracture surface is enlarged 1000 times are shown in FIGS. 12 and 13. In FIGS. 12 and 13, (a) the surface of the monolith film and (b) mean the image of the PET surface.

When the ratio of the amine curing agent was large, the pore size on the surface of the monolith film increased, but the bonding strength decreased in PET. Regarding the fractured form, when γ = 0.98, which has higher strength, peeling at the interface of both the SUS substrate / monolith film and the PET substrate / monolith film was mixed. Further, from the SEM image of the fracture surface, it was found that PET more penetrated into the pores on the surface of the monolith film when γ = 0.98. The PET remaining in the pores on the surface of the monolith film has a slightly stretched shape, suggesting the expression of the anchor effect. From this, it is considered that the contribution to the improvement of the bonding strength of the co-continuous structure is large under the low heat welding condition of 100 ° C.

(B) PC
Table 5 shows the bonding strength and the breaking morphology of the substrate composite with the SUS substrate on which the monolith film was prepared at γ = 1.55, together with the case where γ = 0.98. In addition, SEM images of the test pieces after fracture at each amine addition amount are shown in FIGS. 14 (a) to 14 (c). 14 (a) is an image when the fracture form is SUS interface fracture, FIG. 14 (b) is an image when cohesive fracture is performed, and FIG. 14 (c) is an image when PC interface fracture is performed. Further, SEM images of the fracture surface when γ = 1.55 are shown in FIGS. 15 (a) and 15 (b). FIG. 15 (a) is an SEM image of the surface of the monolith film, and FIG. 15 (b) is an SEM image of the surface of the PC.

In the case of PC, as the ratio of the amine curing agent increased, the bonding strength increased. In addition, the fracture morphology is different for all substrate composites such as SUS substrate / monolith film interface peeling, monolith film cohesive fracture, and PC substrate / monolith film interface peeling, and SUS substrate / monolith film interface interaction, PC substrate / monolith It is presumed that the interaction between the membrane interfaces and the strength of the monolith layer were almost the same. The SEM image of the fracture surface is shown only when γ = 1.55, which is the PC substrate / monolith film interface peeling.

(C) POM, ABS, PP, PE
For each resin having a load-displacement curve obtained by a tensile shear test, a SUS substrate having a monolithic film cured at γ = 0.95 to 1.04 and a substrate composite obtained by heat welding various resin substrates were used. The joint strength is shown in Table 6.

Compared with the case of heat welding on the SUS substrate as it is, the bonding strength was increased by 1.5 to 3 times in POM, PP and PE, and increased by 30 times or more in ABS. From this, it can be seen that the co-continuous structure of the monolith film greatly contributes to the increase in bonding strength.
Regarding the substrate composite of the SUS substrate on which the monolith film was produced and each resin substrate, the test pieces after fracture were shown in the order of POM, ABS, PP, and PE in FIGS. 16 (a) to 16 (d), and the monolith film side was fractured. The cross-sectional SEM images are shown in FIGS. 17 (a) to 17 (d), and the fracture surface SEM images on the resin side are shown in FIGS. 18 (a) to 18 (d).

In POM, PP, and PE, most of them were interfacially peeled at the resin substrate / monolith film, and some fractured morphologies were observed in which the peeling at the SUS substrate / monolith film and the resin substrate / monolith film interface were mixed. In ABS, there were many cases of peeling only at the SUS substrate / monolith film interface. In addition, it was found from the SEM image that the resin remained in the pores on the surface of the monolith film. In POM, PP, and PE, the resin was stretched in a needle shape, and in ABS, it was observed that the resin did not stretch so much and broke. From this, it was confirmed that the resin melted during heat welding entered the monolith film in each case, and it is considered that the anchor effect was exhibited by the contribution of the co-continuous structure.

(6) Correlation between morphology and bonding strength (a) Monolith films prepared with the same surface morphology with film thickness γ = 0.95 to 1.04 and γ = 1.24 to 1.50 for each resin type. The bonding strength of the SUS substrate / monolith film / resin substrate composite with respect to the film thickness is shown in FIGS. 19 (a) to 19 (d). 19 (a) to 19 (d) are graphs using POM, ABS, PP and PE as the resin substrate. Further, in FIG. 19 (a), ◯ is a hole diameter of 7.6 ± 2.3 μm and the number of holes is 1858 ± 895 holes / mm ² , and ◇ is a hole diameter of 16.4 ± 1.4 μm and the number of holes is 376 ± 275 holes / mm ^2. Corresponds to the plot of. In FIG. 19 (b), ○ is a plot with a hole diameter of 12.8 ± 8.4 μm and a number of holes of 1456 ± 949 holes / mm ² , and ◇ is a plot of a hole diameter of 35.34 ± 11.9 μm and a number of holes of 128 ± 39 holes / mm ^2. Corresponds to. In FIG. 19 (c), ◯ corresponds to a plot with a hole diameter of 9.2 ± 1.5 μm and a number of holes of 1752 ± 295 holes / mm ^2. In FIG. 19 (d), ◯ corresponds to a plot having a hole diameter of 6.4 ± 0.6 μm and a number of holes of 2276 ± 426 holes / mm ^2.

In POM, the bonding strength tended to decrease as the film thickness increased. This is similar to the general tendency of bonding with adhesives, but the thicker the monolith film, the less heat is transferred to the POM during heat welding, and it is possible that it does not penetrate deeper than the surface layer of the monolith film. Conceivable. In ABS, when the pore diameter was relatively small, the bonding strength tended to decrease as the film thickness increased, but when the pore diameter was large, the bonding strength was low even if the film thickness was thin. No clear trend was seen for PP and PE.

(B) Average pore size and number of pores per unit area For a monolith film produced in the range of γ = 0.83 to 1.55 with the same film thickness, the average pore size on the surface of the monolith film and the number of pores per unit area. The bonding strengths of the SUS substrate / monolith film / resin substrate composite with respect to the above are shown in FIGS. 20 (a) to 20 (d) and FIGS. 21 (a) to 21 (d), respectively. 20 (a) to 20 (d) and 21 (a) to 21 (d) are graphs using POM, ABS, PP and PE as the resin substrate. Further, in FIGS. 20 (a) and 21 (a), ◯ corresponds to a plot having a film thickness of 152 ± 4 μm, and Δ corresponds to a plot having a film thickness of 228 ± 8 μm. In FIGS. 20 (b) and 21 (b), ◯ corresponds to a plot having a film thickness of 154 ± 15 μm, and Δ corresponds to a plot having a film thickness of 258 ± 13 μm. In FIGS. 20 (c) and 21 (c), ◯ corresponds to a plot having a film thickness of 150 ± 16 μm. In FIGS. 20 (d) and 21 (d), ◯ corresponds to a plot having a film thickness of 154 ± 9 μm.
From FIGS. 20 (a) to 21 (d), especially in ABS, the bonding strength tends to decrease as the pore diameter on the surface of the monolith film increases (or the number of pores decreases).

(C) Pore Cross-sectional Area For the substrate composite of the SUS substrate on which the monolith film was prepared and each resin, plots of the bonding strength with respect to the pore cross-sectional area of the surface of the monolith film are shown in FIGS. 22 (a) to 22 (d). The pore cross-sectional area was calculated from the formula (3) as a total value of the cross-sectional areas of the pores on the surface of the monolith film in the joint surface range.
Cross-sectional area (mm ² ) = πr ² × n × 100 (mm ² ) (3)
r: Average pore size, n: Number of holes per unit area FIGS. 22 (a) to 22 (d) are graphs using POM, ABS, PP and PE as the resin substrate. Further, in FIG. 22A, ◯ corresponds to a plot having a film thickness of 152 ± 4 μm, and Δ corresponds to a plot having a film thickness of 228 ± 8 μm. In FIG. 22B, ◯ corresponds to a plot having a film thickness of 154 ± 15 μm, and Δ corresponds to a plot having a film thickness of 258 ± 13 μm. In FIG. 22 (c), ◯ corresponds to a plot having a film thickness of 150 ± 16 μm. In FIG. 22 (d), ◯ corresponds to a plot having a film thickness of 154 ± 9 μm.

In ABS, the bonding strength tended to decrease as the pore cross-sectional area increased, and the decrease was more remarkable when the film thickness was thin. On the other hand, in POM and PE, contrary to ABS, the bonding strength tended to increase with the increase in pore cross-sectional area, and the increase was more remarkable when the film thickness was thin. It is presumed that the reason why the tendency is more remarkable when the film thickness is thin is that heat is easily transferred by the resin and the resin penetrates deep into the monolith film.

(D) Surface area of monolith film For the substrate composite of the SUS substrate on which the monolith film was produced and each resin substrate, plots of the bonding strength with respect to the surface area inside the monolith film are shown in FIGS. 23 (a) to 23 (d). The surface area of the monolith film is an approximate value assuming spherical voids having an average pore diameter and not connected to each other inside the monolith film in the joint surface range, and was calculated from the equation (4).
Surface area (mm ² ) = 4πr ² × (t / 2r) × n × 100 (mm ² ) (4)
r: average pore diameter, t: film thickness, n: number of holes per unit area FIGS. 23 (a) to 23 (d) are graphs using POM, ABS, PP and PE for the resin substrate. Further, in FIG. 23A, ◯ corresponds to a plot having a film thickness of 152 ± 4 μm, and Δ corresponds to a plot having a film thickness of 228 ± 8 μm. In FIG. 23 (b), ◯ corresponds to a plot having a film thickness of 154 ± 15 μm, and Δ corresponds to a plot having a film thickness of 258 ± 13 μm. In FIG. 23 (c), ◯ corresponds to a plot having a film thickness of 150 ± 16 μm. In FIG. 23 (d), ◯ corresponds to a plot having a film thickness of 154 ± 9 μm.
As a whole, the tendency was the same as in the case of the number of pores.

(E) Correlation between morphology and fracture surface SEM image of fracture surface of a SUS substrate / monolith film / resin substrate composite in which a monolith film was prepared under the conditions of γ = 0.83 and γ = 1.19 to 1.55. Is shown in FIGS. 24 (a) to 27 (d). In these figures, (a) to (d) are images when POM, ABS, PP and PE are used for the resin substrate. 24 and 25 are images of the fracture surface on the monolith film side and the fracture surface on the resin substrate side when γ = 0.83, and FIGS. 26 and 27 are images when γ = 1.19 to 1.55. It is an image of the fracture surface on the monolith film side and the fracture surface on the resin substrate side.

In POM, PP, and PE, when the pore diameter is small, the needle-shaped resin extends from one pore one by one, but when the pore diameter is large, a plurality of needle-shaped resins extend from one pore. It was seen that there was. In ABS, it was observed that the larger the pore diameter, the smaller the area occupied by the resin remaining with respect to the pores. Further, especially in ABS and PE, in the resin fracture surface when the pore diameter was large, a shape reflecting the fine structure in the pores was observed. It is probable that this particle-aggregated microstructure was formed by phase separation after the co-continuous structure was formed by phase separation, and then phase separation proceeded again from the polymer fraction of the remaining liquid phase.

Example 2
A monolith film and a substrate complex were obtained in the same manner as in Example 1 except that the temperature conditions shown in Table 7 were changed in the production of the monolith film. The SEM image of the obtained monolith film is shown in FIG.

(1) Shear test A load-displacement curve obtained from a tensile shear test is obtained for a substrate composite in which a PE substrate is heat-welded at 100 ° C. for 60 seconds on a SUS substrate prepared with a monolithic film having a co-continuous structure and a particle agglomeration structure. FIG. 29 shows the adhesive strength in Table 8. In FIG. 29, the solid line corresponds to the particle agglomeration type, and the dotted line corresponds to the monolith film having a co-continuous structure.

Compared with the case of the monolith film having a co-continuous structure, the test pieces of the particle-aggregated monolith film showed almost the same bonding strength. It is presumed that this result is due to the fact that the resin entered the gaps between the connected particles and exhibited the same anchor effect as in the case of the co-continuous structure.

(2) Observation of fracture surface The fractured form of the substrate composite of the SUS substrate / monolith film / PE on which the particle-aggregated monolith film was produced is shown in FIG. 30, and the fracture surface SEM image of the monolith film side is shown in FIG. 31 (a). The fracture surface SEM image on the substrate side is shown in FIG. 31 (b).
The fractured form was peeling at the PE substrate / monolith film interface. Since the needle-shaped resin extends from the gaps between the connected particles as in the case of the monolith film having a co-continuous structure, it is inferred that the anchor effect is also exhibited in the particle agglomeration structure.

Example 3
The SUS substrate was changed to a Cu substrate, the ratio γ (2 [NH ₂ ] / [epoxy]) of the amine active hydrogen to the epoxy group was 1.02, and the total amount of the epoxy resin and the amine curing agent was 29.8% by weight. A Cu substrate / monolith film composite was obtained in the same manner as in Example 1 except that the epoxy was added so as to be.
Six types of resin substrates (manufactured by POM, ABS, PP, PE, PET, and PC) are heat-sealed onto the Cu substrate / monolith film composite under the same conditions as in Example 1, and the Cu substrate / monolith film / A resin substrate composite was obtained. The obtained substrate complex was subjected to the same tensile shear test as in the examples. The load-displacement curves obtained from the tensile shear test of the substrate composite using POM, ABS, PP and PE as the resin substrate are shown in FIGS. 32 (a) to 32 (d), showing POM, ABS, PP, PE, PET and Table 9 shows the bonding strength of the substrate composite using PC.

Comparative Example 2
A substrate complex composed of a Cu substrate and a resin substrate was produced in the same manner as in Example 3 except that a monolith film was not interposed. The obtained substrate complex was subjected to the same tensile shear test as in the examples. The results are shown in Table 9.

When the resin substrate was heat-welded to the Cu substrate as it was, only low bonding strength was obtained. On the other hand, when a monolith film was produced, the bonding strength increased. High bonding strength was obtained by increasing the heat welding temperature or lengthening the heat welding time. Further, high bonding strength was obtained by increasing the heat welding temperature and lengthening the heat welding time. If heat welding is performed at a temperature higher than the heat welding temperature in the range shown above, or if heat welding is performed at a temperature longer than the heat welding time in the range shown above, the resin substrate is frequently deformed. , It became difficult to measure the joint strength accurately due to the variation in the joint strength.

Example 4
A substrate composite of Al substrate / monolith film / resin was obtained in the same manner as in Example 1 except that the SUS substrate was changed to an Al substrate. Further, an Al substrate / resin substrate composite was obtained in the same manner as the Al substrate / monolith film / resin substrate composite except that the monolith film was not used. The Al substrate used was cut into 10 mm × 50 mm × 0.52 mm with a P cutter. The Al substrate was used after being surface-treated in advance. The surface of the Al substrate was pretreated by immersing the Al substrate in a 10 wt% sodium hydroxide aqueous solution at room temperature for 2.5 to 10 minutes, and then a monolith film was prepared on the Al substrate. Four kinds of resin substrates (manufactured by POM, ABS, PP and PE) were heat-sealed onto the treated Al substrate to obtain an Al substrate / monolith film / resin substrate composite. The obtained substrate complex was subjected to the same tensile shear test as in Example 1. The results are shown in Table 10.

Comparative Example 3
An Al substrate / resin substrate composite composed of an Al substrate and a resin substrate was produced in the same manner as in Example 4 except that the surface of the Al substrate was not pretreated without interposing a monolith film. The obtained substrate complex was subjected to the same tensile shear test as in the examples. The results are shown in Table 10.

When the resin substrate was heat-welded to the Al substrate as it was, the bonding strength was so low that it could not be measured. On the other hand, when the monolith film was produced, the bonding strength of the Al substrate / monolith film / resin substrate composite increased. In the Al substrate / monolith film / resin substrate composite using ABS as the resin substrate, the bonding strength increased as the pretreatment time increased in the range of the pretreatment time of 2.5 minutes to 5 minutes. In the Al substrate / monolith film / resin substrate composite using PP or PE as the resin substrate, the bonding strength increased as the pretreatment time increased in the range of the pretreatment time of 2.5 minutes to 10 minutes.

The SEM image of the untreated Al substrate surface is shown in FIG. 33 (a), and the morphology of the Al substrate surface after immersing the Al substrate in a 10 wt% sodium hydroxide aqueous solution at room temperature for 5 minutes is shown in FIG. 33 (b). .. It can be seen that the oxide film on the surface of the Al substrate has been removed by the pretreatment using the sodium hydroxide aqueous solution. By removing the oxide film and reducing the surface smoothness in this way, the epoxy monolith film can be more fixed to the Al substrate.
Here, the pretreatment of the Al substrate surface can be performed by an alkaline treatment, but there is no particular limitation as long as it is generally known as a pretreatment method of the Al substrate surface, and the pretreatment can be performed by using an acid. It can be carried out. Pretreatment can also be performed by blasting.

Example 5
A substrate composite of Al substrate / monolith film / resin was obtained in the same manner as in Example 1 except that the SUS substrate was changed to an Al substrate and the surface of the Al substrate was pretreated by blasting. For the blasting treatment, a metal file or a sand sheet (Sand sheet extremely rough # 80, ST-01 manufactured by SHINEX, with polishing particles made of nylon non-woven fabric) was used to polish the surface of the metal substrate for 10 minutes. The obtained substrate complex was subjected to the same tensile shear test as in Example 1. The results are shown in Table 11.

As shown in Table 11, the bonding strength was improved by performing the blasting treatment using a metal file or a sand sheet. As can be seen from the results of POM and ABS, even in combination with a resin in which the bonding strength cannot be obtained by direct bonding without the intervention of the epoxy monolith film, the bonding strength is slightly developed by the intervention of the epoxy monolith film, and the metal By blasting with a file or a sand sheet, the bonding strength was further increased in any combination with any resin.

Example 6
A substrate composite of SUS substrate / monolith film / PET was obtained in the same manner as in Example 1 except that the surface of the SUS substrate was blasted with a metal file. A metal file was used for the blasting treatment, and the surface of the metal substrate was polished for 10 minutes. The obtained substrate complex was subjected to the same tensile shear test as in Example 1. The results are shown in Table 12.

As shown in Table 12, the bonding strength to the SUS substrate / monolith film / PET composite was improved by performing the blast treatment of the SUS substrate using a metal file. As described above, the SUS substrate / monolith film / PET composite shows a high value of 3.31 MPa to 6.09 MPa, and the monolith film and PET are firmly bonded by the manifestation of the anchor effect, so that the monolith film and PET are firmly bonded to each other at other bonding sites. The bond between a certain SUS substrate and the monolith film also needs to have sufficient strength. Since a normal bonding mechanism is used for bonding between the SUS substrate and the monolith film, the bonding strength can be improved by pretreating the surface of the SUS substrate.

Example 7
The ratio γ (2 [NH ₂ ] / [epoxy]) of amine active hydrogen to the epoxy group was set in the range of 1.03 to 1.11, and the total amount of monomers (total amount of epoxy resin and amine curing agent) and porogen A SUS substrate / monolith film composite was obtained in the same manner as in Example 1 except that the total amount of monomers (ω% by weight) with respect to the total amount was adjusted in the range of 30 to 31.3. An SEM image of the surface of the monolith film is shown in FIG.

Next, using the above-mentioned SUS substrate / monolith film composite and a resin substrate made of PET, a heat welding temperature in the range of 100 ° C. to 160 ° C. and a heat welding time in the range of 30 seconds to 270 seconds are used for the PET substrate. The adhesive strength was measured in the same manner as in Example 1 except that (the heating conditions shown in Table 13). The results are shown in Table 13.

For a substrate composite obtained by heat-welding a SUS substrate and a PET substrate on which a cured monolith film is produced, the bonding strength obtained by a tensile shear test is obtained by increasing the heat welding temperature or lengthening the heat welding time. , High bonding strength was obtained. When the heat welding temperature was 140 ° C., the bonding strength increased with the heat welding time, and the heat welding time reached the maximum value at 150 seconds.

Example 8
In the same manner as in Example 7, a SUS substrate / monolith film composite and a resin substrate made of PC are used, and the heat welding temperature in the range of 180 ° C. to 200 ° C. and the range of 180 seconds to 360 seconds are applied to the PC substrate. The adhesive strength was measured in the same manner as in Example 7 except that the heat welding time was set to. The range of the heat welding temperature and the heat welding time used here is the range of the temperature at which the PC substrate is not significantly deformed and sufficient bonding strength for measurement can be obtained. The results are shown in Table 14.

High bonding strength was obtained by increasing the heat welding temperature or lengthening the heat welding time. Further, high bonding strength was obtained by increasing the heat welding temperature and lengthening the heat welding time. When the heat welding temperature was 180 ° C., the bonding strength increased with the heat welding time, and the heat welding time reached the maximum value at 280 seconds. When the heat welding temperature was 200 ° C., the bonding strength increased with the heat welding time, and the heat welding time reached the maximum value at 220 seconds.

The methods shown in Examples 1 to 5 can be combined, and the heating temperature, heating time, and pretreatment of the metal substrate can be combined and used, and the metal substrate / monolith film / resin produced under these various conditions can be used. Table 15 shows a comparison of the maximum bonding strengths of the substrate composites. Metal substrate / monolith film / resin composite consisting of a combination of SUS substrate / monolith film composite, Cu substrate / monolith film composite, and Al substrate / monolith film composite with POM, ABS, PP, PE, PET and PC. The bond strength of the body is 1.22 MPa to 5.13 MPa for the SUS substrate / monolith film / resin composite, and 2.41 MPa to 6.88 MPa for the Cu substrate / monolith film / resin composite. , And a value of 0.71 MPa to 3.35 MPa for the Al substrate / monolith film / resin composite, and from Comparative Example 1 in the case where the monolith film is not used for any combination of composites. It showed a higher value than 0 MPa to 0.85 MPa shown in Comparative Example 4, and a high bonding strength was obtained by the anchor effect. Here, the values shown in Table 15 do not indicate the upper limit values for each combination of materials, but indicate that the joint strength was increased by the manifestation of the anchor effect under the joint conditions shown in the table. Is.

Example 9
_{Except that the ratio γ (2 [NH 2} ] / [epoxy]) of the amine active hydrogen to the epoxy group was set to 1.07, and porogen was added so that the total amount of the epoxy resin and the amine curing agent was 30.6% by weight. Obtained a SUS substrate / monolith film composite in the same manner as in Example 1. The SEM image of the obtained monolith film is shown in FIG.
A woodworking bond (manufactured by Konishi Co., Ltd., product number # 10122, components: vinyl acetate resin 41%, water 59%) was ^{applied on the monolith film at an amount of 0.1 g / cm 2} , and wood (manufactured by Konishi Co., Ltd., product number # 10122, 59% water) was applied to the obtained coating film. Lauan wood (thickness 3 mm) was ^{pressed against the SUS substrate with a force of 25 kg / m 2} and allowed to stand overnight to bond the SUS substrate and the wood. The obtained substrate complex was subjected to the same tensile shear test as in Example 1 except that the tensile speed was 0.1 mm / min. The results are shown in Table 16.

Comparative Example 4
The SUS substrate and wood were bonded with a woodworking bond in the same manner as in Example 9 except that the monolith film was not interposed. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 16.

It can be seen that the SUS substrate and the wood can be more strongly bonded to each other through the monolith film. FIG. 36 shows a graph in which stress (stress: MPa) is plotted on the vertical axis and elongation (strine:%) is plotted on the horizontal axis in order to obtain adhesive strength in the tensile shear test. The peak stress means the adhesive strength.
The SEM images of the fracture surface on the wood side and the monolith film side of the test piece after the substrate composite of Example 9 was subjected to a tensile shear test are shown in FIGS. 37 (a) and 37 (b). Further, FIG. 37 (c) shows an SEM image of a fracture surface on the wood side of the test piece after the substrate composite of Comparative Example 4 was subjected to a tensile shear test. In the case of passing through the monolith film, FIG. 37 (a) shows that the adhesive is broken, and FIG. 37 (b) shows that the adhesive has entered the pores on the surface of the monolith film. The expression of the anchor effect is suggested. When the monolith membrane is not interposed, FIG. 37 (c) suggests that the anchor effect is not exhibited at all.

Example 10
_{Except that the ratio γ (2 [NH 2} ] / [epoxy]) of the amine active hydrogen to the epoxy group was set to 1.23, and porogen was added so that the total amount of the epoxy resin and the amine curing agent was 30.2% by weight. Obtained a SUS substrate / monolith film composite in the same manner as in Example 1.
A plastic model adhesive (Cemedine Co., Ltd., plastic model adhesive, styrene resin: 14%, total of acetone, cyclohexane and butyl acetate: 86%) was applied on the monolith film at an amount of ^{0.05 g / cm 2.} A polystyrene plate (PS2031-1 manufactured by HIKARI, thickness 1 mm) is ^{pressed against the SUS substrate with a force of 25 kg / m 2} on the coated coating film, and allowed to stand overnight to form the SUS substrate and the polystyrene substrate. Was glued. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 17.

Comparative Example 5
The SUS substrate and the polystyrene plate were adhered with a plastic model adhesive in the same manner as in Example 10 except that the monolith film was not interposed. The obtained substrate complex was subjected to the same tensile shear test as in Example 10. The results are shown in Table 17.

It can be seen that the SUS substrate and the polystyrene substrate can be more strongly adhered to each other through the monolith film. FIG. 38 shows a graph in which stress (stress: MPa) is plotted on the vertical axis and elongation (strine:%) is plotted on the horizontal axis in order to obtain adhesive strength in the tensile shear test. The peak stress means the adhesive strength.
FIG. 39 shows an SEM image of a fracture surface on the monolithic film side of the test piece after the substrate complex of Example 10 was subjected to a tensile shear test. Through the monolith film, the adhesive has penetrated into the pores on the surface of the monolith film, suggesting the expression of the anchor effect.

Example 11
_{Except that the ratio γ (2 [NH 2} ] / [epoxy]) of the amine active hydrogen to the epoxy group was 1.24, and porogen was added so that the total amount of the epoxy resin and the amine curing agent was 30.2% by weight. Obtained a SUS substrate / monolith film composite in the same manner as in Example 1.
A few drops (about 0.05 mL) of toluene were dropped on the polystyrene substrate ^{per 1 cm 2} area using a pasteur pipette, left at room temperature for 10 minutes, and then the polystyrene substrate and the SUS on which the monolith film was prepared were prepared. The substrate was sandwiched between double clips (width 15 mm), left at room temperature overnight, and then vacuum dried in a vacuum oven heated to 70 ° C. for 1 hour to remove the remaining toluene, and the SUS substrate and the polystyrene substrate were adhered to each other. .. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 18.

Comparative Example 6
The SUS substrate and the polystyrene substrate were bonded with toluene in the same manner as in Example 11 except that the monolith film was not interposed. The obtained substrate complex was subjected to the same tensile shear test as in Example 11. The results are shown in Table 18.

It can be seen that the SUS substrate and the polystyrene substrate can be more strongly adhered to each other through the monolith film. FIG. 40 shows a graph in which stress (stress: MPa) is plotted on the vertical axis and elongation (strine:%) is plotted on the horizontal axis in order to obtain adhesive strength in the tensile shear test. The peak stress means the adhesive strength.
The SEM images of the fracture surface of the polystyrene substrate side and the monolith film side of the test piece after the substrate complex of Example 11 was subjected to a tensile shear test are shown in FIGS. 41 (a) and 41 (b). When the monolith film is used, FIG. 41 (a) shows that the polystyrene is broken, and FIG. 41 (b) shows that the polystyrene has entered the pores on the surface of the monolith film, and has an anchor effect. Is suggested.

Example 12
_{Except that the ratio γ (2 [NH 2} ] / [epoxy]) of the amine active hydrogen to the epoxy group was set to 1.23, and porogen was added so that the total amount of the epoxy resin and the amine curing agent was 29.8% by weight. Obtained a SUS substrate / monolith film composite in the same manner as in Example 1.
A few drops (about 0.05 mL) of acetone were dropped onto the polymethyl methacrylate (PMMA) substrate using a Pasteur pipette, and after leaving for 5 minutes, the PMMA substrate and the SUS substrate on which the monolith film was formed were formed. Was sandwiched between double clips (width 15 mm) and left at room temperature overnight to bond the SUS substrate and the PMMA substrate. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 19.

Comparative Example 7
The SUS substrate and the PMMA substrate were bonded with acetone in the same manner as in Example 12 except that the monolith film was not interposed. The obtained substrate complex was subjected to the same tensile shear test as in Example 12. The results are shown in Table 19.

It can be seen that the SUS substrate and the PMMA substrate can be more strongly adhered to each other through the monolith film. FIG. 42 shows a graph in which stress (stress: MPa) is plotted on the vertical axis and elongation (strine:%) is plotted on the horizontal axis in order to obtain adhesive strength in the tensile shear test. The peak stress means the adhesive strength.
The SEM images of the fracture surfaces of the PMMA substrate side and the monolith film side of the test piece after the substrate complex of Example 12 was subjected to a tensile shear test are shown in FIGS. 43 (a) and 43 (b). From FIG. 43 (a), it is shown that the PMMA is broken when the monolith film is used, and from FIG. 43 (b), the PMMA has entered the pores on the surface of the monolith film, and the anchor effect is obtained. Is suggested.

Example 13
(Making a monolith sheet)
The ratio γ (2 [NH ₂ ] / [epoxy]) of the amine active hydrogen to the epoxy group was set to 1.22, and porogen was added so that the total amount of the epoxy resin and the amine curing agent was 30.0% by weight. An Al substrate / monolith film composite was obtained in the same manner as in Example 1 except that it was prepared on the treated Al substrate. A photograph of the Al substrate / monolith film complex is shown in FIG. Since the adhesive force between the monolith film and the untreated Al substrate is small, the monolith film formed on the Al substrate can be easily peeled off, and the sheet-shaped monolith film as shown in FIG. 45 (hereinafter, the monolith film peeled off from the substrate is peeled off. A monolith sheet) is obtained. The film thickness of the monolith sheet produced by the above method was 0.328 ± 0.049 mm.

Of both sides of the monolith sheet, one surface has the same shape as the surface of the monolith film on the Al substrate prepared in Example 1 (this is called a monolith surface), and the other surface is smooth with no pores observed on the surface. It has a smooth surface (this is called a smooth surface). An SEM image showing the shape of the surface of the monolith sheet is shown in FIG. FIG. 46 (a) shows a porous structure (monolith surface) on the opposite side of the Al substrate when the monolith sheet is produced, and FIG. 46 (b) shows a smooth structure of the surface in contact with the Al substrate when the monolith sheet is produced. Smooth surface) is shown.
Here, as the substrate used for producing the monolith sheet, any material other than the Al substrate can be used as long as it is a material having low adhesiveness to the monolith film, and polyolefins such as Teflon (registered trademark) substrate, PE substrate and PP substrate can be used. You can use the board. The film thickness of the monolith sheet can be adjusted by adjusting the amount of epoxy resin, amine curing agent, and pologene applied per unit area.
In addition, the film thickness of the monolith sheet can be reduced by using a diluent when producing the monolith sheet. As the monolith sheet, a monolith sheet having a porous structure (monolith surface) and a smooth structure (smooth surface) may be used alone, or a plurality of them may be used at the same time. Further, when the smooth surfaces of two monolith sheets are bonded to each other, it can be used as a monolith sheet having a porous structure (monolith surface) on both sides. The two monolith sheets may be bonded in advance, at the same time as the substrate composite is produced, or after the substrate composite is produced. Further, by removing the smooth structure (smooth surface) of the monolith sheet until the porous structure is exposed, the monolith sheet may be used as a monolith sheet having a porous structure (monolith surface) on both sides.

(Preparation of substrate complex)
A plastic model adhesive (Cemedine Co., Ltd., plastic model adhesive, styrene resin: 14%, total of acetone, cyclohexane and butyl acetate: 86%) was applied to the monolith surface of the monolith sheet at an amount of ^{0.05 g / cm 2.} , A polystyrene substrate (PS2031-1 manufactured by HIKARI, thickness 1 mm) was ^{pressed on the coating film obtained on the monolith film with a force of 25 kg / m 2} , and the polystyrene substrate and the monolith sheet were adhered to each other.
Next, apply a two-component epoxy adhesive (Araldite manufactured by Nichiban Co., Ltd., product number AR-30, main agent epoxy resin 90%, other 10%, curing agent modified polyamine 90%, other 10%) to the monolith surface of another monolith sheet. The coating was applied in an amount of 0.05 g / cm ² , and the SUS substrate was pressed against the coating film obtained on the monolith film with ^{a force of 25 kg / m 2} , and the SUS substrate and the monolith sheet were adhered to each other.

Two-component epoxy adhesive (Araldite manufactured by Nichiban Co., Ltd., product number AR-30, main agent epoxy resin 90%) on the smooth surface of the monolith sheet adhered to the polystyrene substrate and the smooth surface of the monolith sheet adhered to the SUS substrate, respectively. , Other 10%, Hardener Modified Polyamine 90%, Other 10%) was ^{applied in an amount of 0.05 g / cm 2} , and the obtained coating surface was bonded on the monolith film with a double clip (width 15 mm). The mixture was sandwiched and left at room temperature overnight to obtain a polystyrene substrate / monolith sheet / SUS substrate composite. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 20.

FIG. 47 shows a graph in which stress (pressure: MPa) is plotted on the vertical axis and elongation (strine:%) is plotted on the horizontal axis in order to obtain adhesive strength in a tensile shear test. The peak stress means the adhesive strength. Adhesive strength of 0.88 ± 0.01 MPa was obtained for the polystyrene substrate / monolith sheet / SUS substrate complex. The SEM images of the fracture surface on the polystyrene substrate side and the monolith sheet side of the test piece after the substrate complex of Example 13 was subjected to a tensile shear test are shown in FIGS. 48 (a) and 48 (b). When the monolith film is used, FIG. 48 (a) shows that the polystyrene is broken, and FIG. 48 (b) shows that the polystyrene has entered the pores on the surface of the monolith sheet, which has an anchor effect. Is suggested.

Example 14
In the same manner as in Example 13, a woodworking bond (manufactured by Konishi Co., Ltd., product number # 10122, components: vinyl acetate resin 41%, water 59%) was applied to the monolith surface of the produced monolith sheet in an amount of ^{0.1 g / cm 2. By applying it and pressing wood (Lauan material, thickness 3 mm) against the SUS substrate with a force of 25 kg / m 2} on the coating film obtained on the monolith film, and letting it stand overnight, it becomes a SUS substrate. Glued with wood.
Next, apply a two-component epoxy adhesive (Araldite manufactured by Nichiban Co., Ltd., product number AR-30, main agent epoxy resin 90%, other 10%, curing agent modified polyamine 90%, other 10%) to the monolith surface of another monolith sheet. The coating was applied in an amount of 0.05 g / cm ² , and the SUS substrate was pressed against the coating film obtained on the monolith film with ^{a force of 25 kg / m 2} , and the SUS substrate and the monolith sheet were adhered to each other.

Two-component epoxy adhesive (Araldite manufactured by Nichiban Co., Ltd., product number AR-30, main agent epoxy resin 90%, respectively, on the smooth surface of the monolith sheet adhered to wood and the smooth surface of the monolith sheet adhered to the SUS substrate, respectively. Other 10%, curing agent modified polyamine 90%, other 10%) was ^{applied in an amount of 0.05 g / cm 2} , the obtained coated surfaces were bonded, sandwiched between double clips (width 15 mm), and at room temperature overnight. After being left to stand, it was heated at 70 ° C. for 1 hour under vacuum to obtain a wood / monolith sheet / SUS substrate composite. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 20.

FIG. 49 shows a graph in which stress (pressure: MPa) is plotted on the vertical axis and elongation (strine:%) is plotted on the horizontal axis in order to obtain adhesive strength in a tensile shear test. The peak stress means the adhesive strength. Adhesive strength of 2.50 ± 0.31 MPa was obtained for the wood / monolith sheet / SUS substrate complex.

Example 15
In the same manner as in Example 13, a woodworking bond (manufactured by Konishi Co., Ltd., product number # 10122, components: vinyl acetate resin 41%, water 59%) was applied to the monolith surface of the produced monolith sheet in an amount of ^{0.1 g / cm 2. By applying it and pressing wood (Lauan material, thickness 3 mm) against the SUS substrate with a force of 25 kg / m 2} on the coating film obtained on the monolith film, and letting it stand overnight, it becomes a SUS substrate. Glued with wood.
^{Next, 0.05 g / cm 2} of a plastic model adhesive (Cemedine Co., Ltd., plastic model adhesive, styrene resin: 14%, total of acetone, cyclohexane and butyl acetate: 86%) on the monolith surface of another monolith sheet. The polystyrene substrate (PS2031-1 manufactured by HIKARI, thickness 1 mm) is ^{pressed with a force of 25 kg / m 2} on the coating film obtained on the monolith film, and the polystyrene substrate and the monolith sheet are adhered to each other. did.

Two-component epoxy adhesive (Araldite manufactured by Nichiban Co., Ltd., product number AR-30, main agent epoxy resin 90%, respectively, on the smooth surface of the monolith sheet adhered to wood and the smooth surface of the monolith sheet adhered to the polystyrene substrate, respectively. (Other 10%, hardener modified polyamine 90%, other 10%) was ^{applied in an amount of 0.05 g / cm 2} , the obtained coating surfaces were bonded, sandwiched between double clips (width 15 mm), and at room temperature overnight. After being left to stand, it was heated at 70 ° C. for 1 hour under vacuum to obtain a composite of wood / monolith sheet / polystyrene substrate. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 20. Adhesive strength of 0.68 MPa was obtained for the wood / monolith sheet / polystyrene substrate complex.

Example 16
In the same manner as in Example 13 ^{, toluene was applied to the monolith surface of the produced monolith sheet at an amount of 0.1 g / cm 2} , and toluene was applied to the monolith surface coated with toluene and the joint surface at 0.1 g / cm ² . The toluene-coated surface of the PC substrate coated in an amount was ^{pressed with a force of 25 kg / m 2} , sandwiched between double clips (width 15 mm), left at room temperature overnight, and then heated at 70 ° C. for 1 hour under vacuum. A composite of PC substrate / monolith sheet was obtained. Next, the monolith surface of another monolith sheet and the PP substrate were heat-sealed at 170 ° C. for 60 seconds to obtain a PP substrate / monolith sheet composite.

Two-component epoxy adhesive (Araldite manufactured by Nichiban Co., Ltd., product number AR-30, main agent epoxy resin) on the smooth surface of the monolith sheet of the PC substrate / monolith sheet composite and the smooth surface of the PP substrate / monolith sheet composite, respectively. 90%, other 10%, curing agent modified polyamine 90%, other 10%) was ^{applied in an amount of 0.05 g / cm 2} , and the smooth surfaces of the monolith sheets ^{were pressed against each other with a force of 25 kg / m 2} , and the PC substrate was pressed. The / monolith sheet composite and the PP substrate / monolith sheet composite were adhered. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 20. An adhesive strength of 1.45 MPa was obtained with respect to the composite of the PC substrate / monolith sheet / monolith sheet / PP substrate.

Comparative Example 8
Two-component epoxy adhesive (Araldite manufactured by Nichiban Co., Ltd., product number AR-30, main agent epoxy resin 90%, other 10%, curing agent modified polyamine 90%) on wood (Lauan material, thickness 3 mm) and SUS substrate, respectively. , Other 10%) was ^{applied in an amount of 0.05 g / cm 2} , the obtained coated surfaces were bonded, sandwiched between double clips (width 15 mm), left at room temperature overnight, and then 1 at 70 ° C. under vacuum. After heating for hours, a wood / SUS substrate composite was obtained. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 20. An adhesive strength of 0.103 MPa was obtained for the wood / SUS substrate complex.

Comparative Example 9
Obtained by applying a woodworking bond (manufactured by Konishi Co., Ltd., product number # 10122, component: vinyl acetate resin 41%, water 59%) to wood (Lauan wood, thickness 3 mm) at an amount of ^{0.1 g / cm 2.} The coated surface was bonded to a polystyrene substrate, sandwiched between double clips (width 15 mm), left at room temperature overnight, and then heated at 70 ° C. for 1 hour under vacuum to obtain a wood / SUS substrate composite. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 20. An adhesive strength of 0.27 MPa was obtained with respect to the wood / polystyrene substrate composite.

Comparative Example 10
Toluene is applied to the PC substrate in an amount of 0.1 g / cm ² , pressed against the PP substrate with a force of 25 kg / m ² , sandwiched between double clips (width 15 mm), left at room temperature overnight, and then at 70 ° C. under vacuum. The mixture was heated in 1 hour to obtain a composite of a PC substrate / PP substrate. The obtained substrate complex was subjected to the same tensile shear test as in Example 9. The results are shown in Table 21. An adhesive strength of 0.028 MPa was obtained with respect to the PC substrate / PP substrate composite.

In Examples 13 and 14, the same adhesive strength as the results of Example 10 and Example 9 was obtained, respectively, and the substrate complex using the monolith sheet was a substrate composite in which a monolith film was directly produced in the form of a SUS plate. It can be seen that it has the same adhesive strength as the body. Further, in Examples 14 and 15, higher adhesive strength was obtained as compared with the results of Comparative Example 8 and Comparative Example 9, respectively. Further, in Example 16, higher adhesive strength was obtained as compared with the result of Comparative Example 10.

Example 17
_{Performed except that the ratio γ (2 [NH 2} ] / [epoxy]) of amine active hydrogen to the epoxy group was 1.25 and porogen was added so that the total amount of epoxy resin and amine curing agent was 30% by weight. A SUS substrate / monolith film composite was obtained in the same manner as in Example 1.
Adhesive tape (Nichiban Co., Ltd., No. 102N) is applied to the SUS substrate / monolith film composite so that the adhesive area is 50 mm x 150 mm, using a 2 kg hand roller, and two reciprocations at a speed of 20 mm / sec. And crimped to prepare a SUS substrate / monolith film / adhesive tape composite. The prepared SUS substrate / monolith film / adhesive tape composite was peeled off at a speed of 10 mm / min by 180 °, and the peeling strength was measured. The peeling strength was determined from the average load in the peeling region having a length of 100 mm in the portion corresponding to 25 mm or later from the peeling start point. The results are shown in Table 21.

Comparative Example 11
A SUS substrate / epoxy membrane complex was obtained in the same manner as in Example 17, except that no porogen was used. Here, the epoxy film formed on the SUS substrate is a densely packed bulk layer epoxy film having no pores, and the presence or absence of pores on the epoxy surface, that is, the presence or absence of an anchor effect determines the peel strength. It was used to clarify the effect. The results are shown in Table 21.

The peel strength of the SUS substrate / monolith film / adhesive tape composite obtained in Example 17 was 1.72 ± 0.04 N / cm, and the peel strength obtained in Comparative Example 11 was 1.29 ± 0.12 N / cm. Higher than cm, the anchoring effect of the monolith film increased the peel strength of the adhesive tape.

1 1st substrate, 2nd substrate, 3 adhesive layer, 4 holes, 5 protrusions

Claims (11)

A first substrate, a second substrate, and an adhesive layer for adhering the first substrate and the second substrate are included.
The adhesive layer is composed of a solidified thermoplastic resin or a thermosetting resin , and has a plurality of holes in the surface layer portion on the second substrate side.
The second substrate is provided with a plurality of protrusions on the surface on the first substrate side.
A substrate composite in which the protrusions are made of a solidified thermoplastic resin or adhesive or a thermosetting resin and are located in the holes. A claim in which the first substrate is selected from a substrate made of metal, alloy, thermoplastic resin, thermosetting resin, glass, ceramics, wood and paper, and the protrusion is made of a solidified thermoplastic resin or thermosetting resin. Item 2. The substrate composite according to Item 1. The substrate complex according to claim 1 or 2, wherein the first substrate is selected from a substrate made of a metal or an alloy. The substrate complex according to any one of claims 1 to 3, wherein the adhesive layer is a thermosetting resin layer. A first substrate, a second substrate, and an adhesive layer for adhering the first substrate and the second substrate are included.
The first substrate is selected from substrates made of metals and alloys.
The adhesive layer is, Ri epoxy resin layer der having a plurality of holes in the surface portion of the second substrate side,
The second substrate is provided with a plurality of protrusions on the surface on the first substrate side.
Based composite plate in which the projections, characterized in that located in the bore. The substrate complex according to any one of claims 1 to 5, wherein the second substrate and the adhesive layer are adhered to each other by utilizing the anchor effect generated by the protrusions and holes. The substrate complex according to any one of claims 1 to 6, wherein the second substrate is provided with a resin layer on the first substrate side, and the protrusion is made of the same resin as the resin layer. The hole has a diameter of 1 to 50 [mu] m, the surface side of the second substrate, 10 to 100,000 pieces / mm ² exist, the accumulated value of the number and diameter of 100～500000Myuemu · pieces / mm ² The substrate complex according to any one of claims 1 to 7, which satisfies the relationship. A first substrate, a second substrate, and an adhesive layer for adhering the first substrate and the second substrate are included.
The adhesive layer is made of a thermosetting resin and has a plurality of holes in the surface layer portion on the second substrate side.
The second substrate is provided with a plurality of protrusions on the surface on the first substrate side.
The protrusion is a method for manufacturing a substrate complex located in the hole.
By the thermosetting resin and forming on the first substrate a mixture layer comprising a pre-Symbol thermosetting resin and pore former to provide a thermosetting resin is thermally cured, provided with a plurality of holes A step of forming an adhesive layer, a step of removing the hole-forming material from the adhesive layer, and a plurality of protrusions are formed on the surface of the second substrate on the first substrate side so as to be located in the holes. A method for producing a substrate composite, which comprises a step of adhering the first substrate and the second substrate. A first substrate, a second substrate, and an adhesive layer for adhering the first substrate and the second substrate are included.
The adhesive layer is made of a thermoplastic resin and has a plurality of holes in the surface layer portion on the second substrate side.
The second substrate is provided with a plurality of protrusions on the surface on the first substrate side.
The protrusion is a method for manufacturing a substrate complex located in the hole.
By the mixture layer comprising a front Kinetsu thermoplastic resin and pore former removing the pore former from the mixture layer and the step of forming on said substrate, forming an adhesive layer having a plurality of holes And the step of adhering the first substrate and the second substrate by forming a plurality of the protrusions on the surface of the second substrate on the first substrate side so as to be located in the holes. A method for producing a substrate composite, which comprises. The protrusions are as follows (1) to (3):
(1) A second substrate made of a thermoplastic resin and having a thermoplastic resin layer on the adhesive layer side at least is placed on the adhesive layer at the same time or after being placed, and then heated to extend from the thermoplastic resin layer. Formed by being present,
(2) Formed by solidifying or curing the adhesive after placing the second substrate on the coating film derived from the adhesive and applying the adhesive on the adhesive layer so as to extend to the holes. Be done,
(3) A second substrate made of a thermoplastic resin and having a thermoplastic resin layer at least on the adhesive layer side is softened by bringing the thermoplastic resin layer into contact with an organic solvent, and then placed on the adhesive layer. The method for producing a substrate composite according to claim 9 or 10, which is formed in any step of being formed by extending from the thermoplastic resin layer.

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